Page 1
A QUANTUM THEORETICAL
STUDY OF THE 1,3-DIPOLAR
CYCLOADDITION REACTIONS
THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE
REQUIREMENT OF THE DEGREE OF
DOCTOR OF PHILOSOPHY (SCIENCE)
IN CHEMISTRY
OF
THE UNIVERSITY OF BURDWAN
TAPAS KUMAR DAS, M.Sc.
DEPARTMENT OF CHEMISTRY
THE UNIVERSITY OF BURDWAN
BURDWAN-713104
WEST BENGAL, INDIA
MAY-2012
TA
PA
S K
UM
AR
D
AS
2
01
2
Page 2
A QUANTUM THEORETICAL STUDY OF
THE 1,3-DIPOLAR
CYCLOADDITION REACTIONS
Submitted by
Tapas Kumar Das
DEPARTMENT OF CHEMISTRY
UNIVERSITY OF BURDWAN
A THESIS
SUBMITTED IN PARTIAL FULFILMENT OF
THE REQUIREMENT FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY
IN CHEMISTRY
TO
THE UNIVERSITY OF BURDWAN BURDWAN-713104
INDIA MAY-2012
Page 3
Dedicated to….
My parents….
.…for their untiring love and blessings
Page 4
The University of Burdwan
Dr. Manas Banerjee
Professor
Department of Chemistry Golapbag,
Burdwan 713104, India.
Tel: +91-342-2533913 (O)
+91-33-26845255 (R)
Fax: +91-342-2530452 (O)
E-mail: [email protected]
Dated, 04.05.2012
TO WHOM IT MAY CONCERN
This is to certify that the thesis entitled “A QUANTUM THEORETICAL STUDY
OF THE 1,3-DIPOLAR CYCLOADDITION REACTIONS” is the result of
work done by Mr. Tapas Kumar Das, M.Sc., who has been registered to The
University of Burdwan on 15.05.2006 for the award of Doctor of Philosophy
(Science) under my supervision. This work, neither in part nor whole, has been
submitted for fetching any degree by Mr. Das or others, to the best of my
knowledge.
This is also to certify that he has fulfilled all the requirements under the regulation
relating to the nature of work, qualifying course work, period of research satisfying
residential requirement and presentation of seminar talks etc. in the due time.
(Manas Banerjee)
[Supervisor]
Page 5
Acknowledgements
I take this golden opportunity to express my deepest sense of gratitude to my
Supervisor Prof. Manas Banerjee for his guidance, encouragement, support and help
rendered to me during my research tenure here without which my Thesis would have
not been completed.
I would like to thank the Head of the Department of Chemistry, University of
Burdwan, for providing the facilities for necessary items. I would also like to extend
my sincere thanks to the teachers of our Chemistry Department for their kind
assistance whenever I felt the need for anything necessary for the completion of my
Ph. D program.
I sincerely thank all my friends and colleagues of my school, Ramnagar Atul
Vidyalaya, Head Master: Mr. Prasanta Kumar Chakraborty, and Assistant Teachers:
Anirban Seth, Abhijit Ray, Susanta Maity, Amit Adhya, Ujjwal Bhar and specially
my research colleagues Mr. Kalyan Ghosh, Ms. Tandrima Chaudhuri, Mrs. Sneha
Salampuria for all their encouragement, help and support.
I would also like to thank all the research scholars and non-teaching staff of the
chemistry department for their help and support rendered to me in the course of my
research.
Without the encouragement, inspiration, blessings and support of my Parents Mr.
Nirapada Das and Smt. Susama Das, I would not have reached this stage. Here I
would like to mention specially my wife Smt. Sampa Das and sons Subhadeep Das
and Arghadeep Das without whose inspiration and moral support I would have never
reached this far.
Above all, I thank to the almighty God for His blessing and providing me so much.
Burdwan
May, 2012 Mr. Tapas Kumar Das
Page 6
Contents
Contents
Dedication
Letter of supervisor
Acknowledgements
PAGE
Chapter 1 1-18
General Introduction
1.1. Cycloaddition Reaction 2
1.2. Classification of Cycloaddition Reactions 8
1.3. Need for a Quantum-Theoretical Study 10
1.4. The Major Objectives of Study 11
1.5. Previous Works of Different Research Groups 11
1.6. General Scope of the Present Work 13
References 17-18
Chapter 2 19-48
General methodology and theoretical approach towards chemical reactions 2.1 . Theoretical Chemistry and Chemical Reactions 20
2.2 . Geometry Optimization 20
2.3 . Test for a True Minimum 21
2.4 . Transition State Optimization and its Location 22
2.5 . Test for True Transition State 23
2.6 . Quantum Chemical Tools for Electronic Energy Calculation 23
2.6.1. The Hartree-Fock Self-Consistent Field Method 23
2.6.2. Moller-Plesset Perturbation Theory 27
2.6.3. Density Functional Theory 29
2.7. Natural Bond Orbital (NBO) Analysis 33
2.7.1. Wiberg Bond Index 35
2.8. Chemical Reactivity Indexes 35
Page 7
Contents
2.8.a) Chemical Hardness 35
2.8.b) Electronic Chemical Potential 37
2.8.c) The Global Electrophilicity Index 37
2.8.d) The Fukui Function 38
2.8.e) The Local Electrophilicity Index 39
2.8.f) The Global Nucleophilicity Index 39
2.8.g) The Local Nucleophilicity Index 40
2.8.h) Global and Local Softness 40
2.8.i) Enthalpy or Heat of the Reaction 41
2.8.j) Enthalpy of Activation 41
2.8.k) Free Energy of the Reaction 42
2.8.l) Free Energy of Activation 42
2.8.m) Activation Energy 43
2.8.n) Rate Constant 43
2.8.o) Pauling’s Partial Bond Order (PBO) 46
2.8.p) Charge Transfer at Transition State (CT) 46
References 47-48
Chapter 3 49-70
Studies on cyclization of azomethine ylides with substituted alkenes
3.1. Introduction 50
3.2. Computational Method 52
3.3. Results and Discussion 53
3.3.1. Reaction of Acyclic Azomethine Ylides with Alkenes 57
3.3.2. Reactions of Cyclic Azomethine Ylides with Alkenes
Bearing Electron Withdrawing Substituents 60
3.4. Nature of the Transition State 65
3.5. Conclusion 67
References 68-70
Page 8
Contents
Chapter 4 71-86
Stereoselectivity in the 1,3-dipolar cycloaddition of 1-pyrroline-1-oxide to methyl cinnamate and benzylidene acetophenone
4.1. Introduction 72
4.2. Computational Method 74
4.3. Results and Discussion 75
4.3.1.Theoretical Explanation for the Cycloaddition of
1-pyrroline-1-oxide (N1) to Methyl Cinnamate (E1)
and Benzylidene Acetophenone (E2) 75
4.4. Exploring the Transition State 78
4.5. Selectivity and Reactivity of the Cycloadditions 80
4.6. Conclusion 83
References 84-86
Chapter 5 87-107
1,3-dipolar cycloaddition of 1-phenylethyl-trans-2-methyl nitrone to styrene and of 1-phenylethyl nitrone to allyl alcohol 5.1. Introduction 88
5.2. Computational method 89
5.3. Results and Discussion 89
5.3.1. Reaction of the Nitrones with Styrene 94
5.3.2. Reaction of Nitrones with Allyl Alcohol 99
5.4 Nature of Transition State in the Reactions 103
5.5 Conclusion 104
References 105-107
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Contents
Chapter 6 108-133
Theoretical studies on cyclization of azomethine imines with electron deficient dipolarophiles 6.1. Introduction 109
6.2. Computational Method 110
6.3. Results and Discussion 111
6.3.1. Reaction of Azomethine Imine with Unsymmetrically
Substituted Alkenes (E1 and E2) 119
6.3.2. Reaction of Azomethine Imine (AI) with the
Symmetrical Substituted Alkene ( E3) 123
6.4. Reactivity in Terms of Global and Local Electrophilicity
and Nucleophilicity of the Reactants 125
6.5. Nature of the transition State 128
6.6. Selectivity and Reactivity of the Cycloadditions 130
6.7. Conclusion 130
References 131-133
7. List of Publications 134-136
8.1. Annexure 1 A1-A46
8.2. Annexure 2 A47-A65
8.3. Annexure 3 A66-A105
8.4. Annexure 4 A106-A167
Page 10
Chapter: 1
General Introduction
Page 11
General Introduction
2
1.1. Cycloaddition Reaction
Organic cycloaddition is a very interesting and important chemical reaction due to
its role in organic synthesis as well as from academic considerations1. It gives cyclic
products without the loss of atoms i.e., without the formation of any side products
and requires nothing other than light or heat for initiation. These reactions are
stereospecific and regiospecific in nature and are obviously important for the
preparation of specific cyclic compounds. The cyclic compounds containing
heteroatoms are called heterocyclic compounds. Those are very important for
biological and industrial use.
Now, the question arises what precisely a cycloaddition reaction is. The addition
reaction of alkenes with polyenes or dipoles leading to the formation of cyclic
product/products is called cycloaddition reaction.
There are different types of cycloaddition reaction. Concerted pericyclic
cycloadditions involve reorganization of the -electron systems of the reactants to
form two new -bonds. Examples might include cyclodimerization of alkenes,
cycloaddition of allyl cation to an alkene, and the addition reaction between alkenes
and dienes (Diels-Alder reaction)2. The cycloadditions can be characterized by
specifying the number of π-electrons involved for each species, and for the above
three cases, this would be [2+2], [2+2] and [4+2] respectively. The pattern of
reactivity can be understood by application of the principle of conservation of orbital
symmetry. The most important of the concerted cycloaddition reactions is Diels-
Alder reaction between a diene and alkene derivative to form a cyclohexene. The
alkene reactant usually has a substituent and is called the dienophile. Concerted
reactions occur without an intermediate. The transition structure involves both bond
breaking and bond formation, although not necessarily to the same degree. There are
numerous examples of both unimolecular and bimolecular concerted reactions. A
particularly important group consists of the concerted pericyclic reactions, which is
characterized by a continuous reorganization of electrons through cyclic transition
structures (TS). Furthermore, the cyclic TS must correspond to an arrangement of
the participating orbitals that can maintain a bonding interaction between the
reacting atoms throughout the course of the reaction. The [4+2] cycloaddition
Page 12
General Introduction
3
reaction is the addition reaction, where 4 π-electrons of one-reactant and 2 π-
electrons of the other reactant are combined to form a cyclic product. This is actually
the case of Diels-Alder reaction (Fig. 1.1)2. But the mechanism of this reaction was
not so easy to understand, which is clear from the fact that the Nobel committee took
twenty-two years to understand the beauty of this reaction.
Fig. 1.1
The [2+2] cycloaddition reaction is the addition reaction, where 2 π-electrons of one
reactant and 2 π-electrons of the other reactant to form the cyclic product (Fig. 1.2).
Fig. 1.2
Another important type of [4+2] cycloaddition is 1,3-dipolar cycloaddition2. These
reactions involve heteroatomic systems that have four π-electrons and are
electronically analogous to the allyl or propargyl anions. Many combinations of
atoms are conceivable; among them are azides, nitrones, nitrile oxides and ozone. As
these systems have four π-electrons, they are analogous to dienes and their
cycloadditions with alkenes and alkynes are allowed [4+2] reactions. In a [4+2]
cycloaddition reaction one reactant has 4 π-electrons in the form of a dipole (1,3-
dipole) and the other reactant has 2 π-electrons and they combine to form a cyclic
product. A key to understand the mechanisms of the concerted pericyclic reactions
was recognized by Woodward and Hoffmann. That the pathways of such reactions
are determined by the symmetry properties of the orbitals and those are directly
+ (4+2)-cycloaddition reaction
+ (2+2)-cycloaddition reaction
Page 13
General Introduction
4
involved. Specifically, they stated the requirement for conservation of orbital
symmetry. The idea was that the symmetry of each participating orbital must be
conserved during the reaction process. In 1,3-dipolar cycloaddition reaction the
alkene is usually termed as dipolarophile. The dipoles include various heteroatoms.
(Fig. 1.3).
R N N N+
Azide
1 2 3
C N
R
R
O
R
+
Nitrone
1
23
C N+
C13 2
R
R
R
R
R
Ylide
C NR R+
N123
Imine
C NR O+
123
Nitrile oxide
O+
123
OO
Ozone
Some 1,3-dipoles
Fig. 1.3
O
N
C
-
+
+
O
N
Dipole Dipolarophile Adduct
1,3-dipolar cycloaddition reaction
1
2
3
Fig. 1.4
The 1,3-dipolar cycloaddition (1,3DC) reaction (Fig. 1.4) can be more precisely
defined as, the addition of 1,3-dipole to an alkene for the synthesis of five membered
heterocyclic rings. A dipole is a system of three crucial atoms over which 4 π-
electrons are distributed in two filled π-orbitals and there is one empty π-orbital with
Page 14
General Introduction
5
a central heteroatom, usually oxygen, nitrogen or sulphur. There are wide varieties
of dipoles that include a combination of carbon, oxygen and nitrogen atoms within
the structures1. They can be considered as electrically neutral molecules carrying a
positive and a negative charge centers in one of their major canonical structures.
However, they are not zwitterionic in nature. The 1,3-dipoles vary greatly in their
stability. Some can be isolated and stored, others are relatively less stable but are
usually prepared on the same day of their use and some like azomethine ylides,
azomethine imines etc. are so unstable that they are generated and reacted in situ.
Basically, the 1,3-dipoles can be divided into two major different types: the allyl
anion type and the propargyl/allenyl anion type.
Mostly, the outcome from 1,3-dipolar cycloaddition reactions are the heterocyclic
compounds. The chemistry of heterocyclic compounds is one of the most interesting
yet complex branches of organic chemistry, of equal interest for its theoretical
implications, diversity of its synthetic procedures, and for physiological and
industrial significance of the heterocycles. Many broader aspects of heterocyclic
chemistry are recognized as disciplines of general significance, which have impact
on almost all aspects of modern organic chemistry, medicinal chemistry, and
biochemistry. For this reason scientists initiated several years ago a parallel series
entitled General Heterocyclic Chemistry, which dealt with such topics like nuclear
magnetic resonance, mass spectra, and photochemistry of heterocyclic compounds.
The utility of heterocycles in organic synthesis, includes the synthesis of
heterocycles by means of 1,3-dipolar cycloaddition. This was intending to be of
interest to all organic, medicinal, and biochemically oriented chemists, as well as to
those whose particular concern was heterocyclic chemistry1. It is a major challenge
to this immense field of heterocyclic chemistry for the synthetic preparation of
compounds and theoretical study. One strategy is to study the new materials, as has
been done inter alia with isoxazolidine, pyrazolidine, pyrrolidines, pyridines,
purines, pyrimidines, quinazolines, isoxazoles, pyridazines and pyrazines.
Page 15
General Introduction
6
Since this fascinating and broadly useful subject has developed in the intermediate
period, the ability of the 1,3-dipolar cycloaddition (1,3DC) reaction to produce
heterocycles has been extended to two other areas of organic synthesis. Firstly, the
heteroatom-containing important cycloadducts may be transformed into a variety of
other functionalized organic molecules, whether cyclic or acyclic. Secondly, many
1,3DC have the ability to generate rings (and functionality derived ones from
transformations of such rings) containing several contiguous stereocenters in one
synthetic operation1. The configurations of these new stereocenters arise from the
geometry of the dipole and dipolarophile as well as the topography (endo- or exo-)
of the cycloaddition and also from the different faces of attack, i.e., the re or si face
for a prochiral molecule. An additional stereochemical feature arises when the
reactive p faces of either of the cycloaddends are diastereotopic. Relative
stereocontrol in 1,3DC can be dealt with some details, and asymmetric versions of
dipolar cycloaddition would emerge. Again the chemistry and synthetic applications
of 1,3DC in the broad context of organic chemistry can result in such products with
specific stereo-, regio- and enantio- selectivity3-5
. The 1,3DC reactions do not
require other reagents except for 1,3-dipoles and the dipolarophiles and also there is
no formation of byproducts. In this sense 1,3DC reactions are friendly to the
environment and they can be made useful for the development of green chemistry.
As the complexity of synthetic targets increase, so does the demand for solutions to
the synthetic problems. As such, development and refinement of established
methodologies continue. In particular, cycloaddition chemistry has continued to
maintain its place as one of the cornerstones of modern organic chemistry, for the
construction of mono- and polycyclic systems, a consequence of being able to
deliver high molecular complexity from relatively simple and accessible precursors.
The most important dipoles, which we have studied, are the azomethine ylides,
nitrones and azomethine imines.
For the construction of the five-membered nitrogen-containing heterocycles, among
the 1,3-dipoles, the ylides provide conceptually the most simple and efficient
Page 16
General Introduction
7
method. Generation of the ylides, usually in situ, followed by dipolarophile attack,
furnishes pyrrolidines and pyrrolines with operational simplicity. For the
synthetically orientated chemist it is necessary to have the requisite knowledge to
implement such methodology to meet the challenges posed by asymmetric and
natural product synthesis. But less theoretical study6-8
has been done in this regard.
Again, among the most thoroughly investigated 1,3-dipoles, the nitrones are
arguably most useful through their ability to generate nitrogen- and oxygen- based
functionality from the cycloadducts and these are potential to introduce multiple
chiral centers stereoselectively. The 1,3-dipolar cycloaddition reactions of nitrones
are important for the straight forward route to the synthesis of isoxazolidines. Again
the nitrones’ cycloadducts are very attractive intermediates for the synthesis of
various natural products and biologically active compounds9-13
. Their chemistry has
been widely varied and frequently reviewed. Extensive theoretical investigation on
the 1,3DC reactions using nitrones were done by many researchers compared to
those done with the other dipoles14
. The azomethine imines (AI), had been relatively
little studied and were less explored compared to the nitrones counterpart. The
1,3DC reactions of azomethine imines have found potential application in the
efficient regio- and stereo- controlled synthesis of pyrazolidine rings using the
appropriately substituted alkenes, thus having the possibility to generate three new
chiral centers simultaneously. Although cases of azomethine imines essentially
entering asymmetric cycloaddition reaction with alkenes are limited, we have
focused our attention to the chiral azomethine imines for the stereoselective
synthesis of C-nucleosides, which plays a very important role in the synthesis of
cyclic or bicyclic natural and bio-organic compounds with a very high or complete
selectivity. The synthetic utility of the 1,3DC reaction is evident from the number
and scope of targets that can be prepared by this chemistry15
. The mechanism of the
1,3DC is quite interesting and there was a debate over two decades3 between the two
pioneer researchers, R. Huisgen and R.A. Firestone, in attempt to recognize that a
duality of mechanism might exist on the whole. This discussion has been done
elaborately in chapter 3.
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General Introduction
8
Cycloaddition reactions figure prominently in both synthetic and mechanistic
processes. The monumental work of Rolf Huisgen and co-workers in the early 1960s
has led to building the general concept of 1,3-dipolar cycloadditions. Few reactions
rival this process in terms of the number of bonds that undergo transformation
during the reaction, generating products considerably more complex than the
reactants. Over the years, this reaction has developed into a generally useful method
for synthesis of five-membered heterocyclic rings, since many 1,3-dipolar species
are readily available which react with a wide variety of dipolarophiles. The utility of
this cycloaddition reaction in synthesis, deals primarily with information that has
appeared during the last few decades. Consequently, only a selected few numbers of
dipoles have been reviewed, with a major emphasis on their synthetic applications3.
We have investigated only the three types of dipoles-ylides, nitrones and imines
which are most important among all the 1,3-dipoles.
1.2. Classification of Cycloaddition Reactions
In connection with concertedness of the Diels-Alder (D-A) reaction, it is
argued that there might be an intermediate which is diradical in character. D-A
reactions are almost always stereospecific which implies that if an intermediate
exists it can not have a lifetime sufficient to permit rotation or inversion. The
majority of D-A reactions is concerted. It is recognized that in reactions between
unsymmetrical alkenes and dienes, bond formation might be more advanced at one
pair of terminal than at the other. This is described as an asynchronous process. Loss
of stereospecificity is expected only if there is an intermediate in which one bond is
formed and the other is not, permitting rotation or inversion at the unbound termini.
Cycloaddition reactions that occur through a pericyclic concerted mechanism can be
written as a continuous rearrangement of electrons. Orbital symmetry considerations
provide a fundamental insight into the electronic nature of cycloaddition reactions.
Woodward and Hoffmann formulated the orbital symmetry principles for
cycloadditions in terms of frontier orbitals. An energetically accessible TS requires
overlap of the frontier orbitals to permit smooth formation of the new -bond. If it is
assumed that the reactants approach one another face to face, as expected for
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General Introduction
9
reactions involving π-orbitals, the requirement for bonding overlap between the
Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular
Orbital (LUMO) are met for [2+4] but not for [2+2] or [4+4] cycloadditions. More
generally, (4n+2) π-electrons are favourable whereas systems with 4n π-electrons
are not. When systems interact with face to face topology, this addition is called
suprafacial denoted by subscript s and when they interact with opposite face
topology of the π system, the addition is called antarafacial denoted by subscript a.
Sustmann16-17
and Trill summarized these and related reactivity relationships in
terms of Frontier Molecular Orbital (FMO) theory and pointed out that 1,3-DC
reactions could be of three types, depending on relative placement of the frontier
orbitals: type-1, HOMOdipole–LUMOdipolarophile dominant; type-2, LUMOdipole–
HUMOdipolarophile dominant; type-3, both HOMO-LUMO interactions are significant.
Electron repelling group (ERG) in the dipole and electron withdrawing group
(EWG) in the dipolarophile should accelerate the first type. The second type should
be facilitated by an EWG in the dipole and an ERG in the dipolarophile. These
relationships suggest a parabolic substituent effect as type-3 reactions shift from
LUMOdipolarophile to mixed to HOMOdipolarophile controlled. Using a wider range of
reactants, Sustmann and Trill demonstrated a parabolic rate relationship and
developed a mathematical treatment in terms of FMO theory that provided a
semiquantitative explanation of relative reactivity.
Although the FMO approach provides a good foundation for understanding the
regioselectivity of 1,3DCs, there are many specific cases in which it fails to provide
a complete understanding. Steric factors are not considered by the FMO analysis and
in many instances steric factors control regiochemistry. 1,3DC can be broadly
classified as steric controlled or electronically controlled. There may also be specific
interactions in the TSs that are not considered by the FMO analysis.
Cycloaddition reactions are classified as nonpolar, polar and ionic depending on the
value of calculated charge transfer (CT) in the transition state. The reaction
becomes18
nonpolar if CT<0.15e, polar if 0.15e<CT<0.4e and ionic if CT>0.4e. The
detailed computational procedure and explanation have been given in the subsequent
section 2.8.p.
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General Introduction
10
1.3. Need for a Quantum-Theoretical Study
Computational approach provides a fundamental insight into the electronic nature of
the cycloaddition reactions and allows us to see that some of the TS structures are
electronically favourable, whereas others are not. As with the D-A reaction, the
concerted pericyclic mechanism can account for many aspects of stereochemistry
and regiochemistry of the 1,3DC reaction. Most 1,3DC reactions are highly
stereospecific with respect to the dipolarophile.
There have been many studies of individual systems by Molecular Orbital (MO) and
Density Functional Theory (DFT)19-22
methods and these provide further insight into
the factors that control regio- and stereo-selectivity. For example, there are two
possible regioisomers from the reaction of diazomethane and methyl vinyl ether, but
only the 3-methoxy isomer is formed. Calculations at several levels of theory
(Hartree-Fock (HF)/6-31G and Moller-Plesset second order (MP2)/6-31G*) found
lower activation energies for TS leading to the observed product. Among the various
methods, DFT becomes most popular, versatile, and applicable to all types of
reacting systems. This DFT method gives greater accuracy than the Hartree-Fock
method only at slight increase in cost but far less than that of MP223
for medium size
and large size molecular systems. The 1,3DC reactions are relatively less explored,
specially for the ylides and imines. Additionally, our interest is to explain the 1,3DC
reactions with the help of theoretical calculations. The computer revolution has
paved the way for accurate calculations made on the basis of Valence Bond (VB) or
Molecular Orbital (MO) theory on actual molecules, which gives very good
rationalization of the observed physical properties and chemical behaviour of the
systems. The results are an enormous output of the molecular orbital calculations on
an astonishing variety of chemical systems24-25
. This is more applicable to organic
chemistry, but now applicable to almost any field of chemistry. From the efforts of
theoretical and computational chemists, completely new field of research has
emerged, that of theoretical and physical organic chemistry26-28
. Again, the
parameters of reaction and electronic behavior of the reactants for the reaction can
be obtained easily and correctly from the DFT calculations. This makes our attention
to be attracted towards a theoretical study of the 1,3DC reactions.
Page 20
General Introduction
11
1.4. The Major Objectives of Study
1. Predicting theoretically the stereo-specific adducts in 1,3DC reactions, in
general.
2. Predicting the probable path of the reaction and nature of interactions in the
transition state.
3. Application of these reactions to asymmetric synthesis for the preparation of
important stereoisomers.
4. Exploring how the 1,3-DC reactions of nitrones, azomethine imines and ylides
produce predominantly 5-membered and differently substituted isoxazolidine,
pyrazolidine and pyrrolidines rings.
5. Predicting particularly the diastereofacial, regio- & enantio- selectivity of
1,3DC reactions of nitrones, imines and ylides in terms of local electrophilicity
and nucleophilicity since FMO predictions are not generally quite satisfactory.
6. Predicting the product ratios of different stereoisomers obtained in a particular
cycloaddition reaction.
1.5. Previous Works of Different Research Groups
There is a huge literature for the study of cycloaddition reactions and it is
practically impossible to state all such works here. Rather we mention here some
of the important works that we felt significant in the development of the subject
and related to our study. More references are given in the introduction section of
each chapter.
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General Introduction
12
K.V. Gothelf et al.2 done very good job on Asymmetric 1,3-Dipolar
Cycloaddition reaction experimentally and prepare a detailed review about this
matter.
S. Sakai et al.29
studied DFT-SHAB (Soft-Hard-Acid-Base) prediction of
regioselectivity, transition state, reaction mechanism of imine dipoles in 1,3-
Dipolar Cycloaddition.
Houk et al.30
studied the pericyclic reactions and also the 1,3-Dipolar
Cycloaddition reactions both by experimentally and computational theoretical
study. They used molecular orbital calculations in order to rationalize and
prediction of relative rates of regioselectivity of 1,3-dipoles and dipolarophiles.
Again by using Perturbation theory they studied the origin of reactivity,
regioselectivity and stereoselectivity in 1,3-Dipolar Cycloaddition reactions.
L.R. Domingo et al.31
studied the molecular reaction mechanism of the 1,3-
Dipolar Cycloaddition reaction by different computational methods. They are
especially interested on azomethine ylides. They have lots of theoretical paper
about these 1,3DC reactions.
Magnuson et al.32
studied the Molecular Orbital calculations to explain
theoretically the 1,3-Dipolar Cycloaddition reactions of nitrone with different
substituted ethylenes.
R.C.F. Jones et al.15
performed experimental study on 1,3-Dipolar Cycloaddition
reactions of Azomethine Imines with electron withdrawing substituted ethylenes
and prepared principally 4-substituted pyrazolidines. These reactions are very
much useful for the stereoselective synthesis of C-nucleosides.
M.T. Nguyen et al.33
used quantum mechanical methods, such as MP2 and DFT,
to study the mechanism of 1,3-Dipolar Cycloaddition reaction of simple Azides
and many nitrones with many simple dipolarophiles.
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General Introduction
13
C.D. Valentin et al.34
studied the Concerted vs Stepwise mechanism of 1,3-
Dipolar Cycloaddition reactions of Nitrones with some different alkenes with the
help of DFT study.
1.6. General Scope of the Present Work
We are very interested to investigate different aspects of 1,3-dipolar
cycloadditions for a better insight into its mechanism, specially for the dipoles
azomethine ylides, nitrones and azomethine imines. In order to explore the
nature of transition states and rationalizing the product ratios and the observed
selectivities in terms of Quantum chemical DFT based reactivity parameters.
Such essential parameters are philicity indices, activation parameters etc. We
have divided our investigations into four parts: first one is for the azomethine
ylides, second and third are for the nitrones and last one is for azomethine
imines. The section-wise summary of our work are given in the following.
DFT computational study has been done for the 1,3-dipolar cycloaddition
of a few acyclic and cyclic azomethine ylides (AY) with maleimide,
maleic anhydride, methylacrylate and also some simple substituted
alkenes6 bearing different electron withdrawing substituents. We have
explained the reactivity and the selectivity of these reactions using the
values of important thermodynamic quantities like free energy of reaction
(ΔrG), free energy of activation (ΔG ), and enthalpy of reaction (ΔrH)
obtained through Quantum-Theoretical computations. Those important
quantities include chemical hardness, electronic chemical potential,
global electrophilicity, which correlate well with experimental findings.
The DFT computations are performed35
using the B3LYP functional and
6-31G(d) as well as [6-311+G(d,p)] basis sets to rationalize the
reactivity, regioselectivity, enantioselectivity and diasteriofacial
selectivity in respect of those 1,3DC reactions-leading to enantiomeric/
diasteriomeric excess of the products. In particular, N-substituted and C-
Page 23
General Introduction
14
substituted AYs have been considered for reactions with the substituted
ethylenes: maleimide, maleic anhydride and methyl acrylate. From an
analysis of the results of calculation for the selected reactions, the regio-
and exo/endo-stereoselectivity have been explained. Reactions are
followed through transition state (TS) structure optimization, calculation
of Intrinsic Reaction Coordinate (IRC) and activation energies. Trends in
regioselectivity and enantioselectivity are followed with the help of
HOMO–LUMO energies, electrophilicity differences and an analysis of
Pauling’s bond order36
(PBO) in the TS.
Pyrolidine-N-oxide is a nitrone type 1,3-dipole. Experimentally it has
been found to add to dipolarophiles like methyl cinnamate and
benzylidene acetophenone to produce different stereo- isomeric products.
Possibility of formation of the various adducts is computationally
explored through optimization of the corresponding TS’s constituted
from the suitable approaching reactants. The effects of various factors
which control regioselectivity and endo/exo- selectivity are examined.
The reason for selecting a cyclic nitrone like 1-pyrroline-1-oxide (N1)
stems from its capability to delicately alter the diastereoselectivity of the
cyclic adducts through simple functional group alterations on the
dipolarophile moiety alone. That the cyclic nitrone N1 can exist only in
the E-isomer restricts the flexibility of addition to the nitrone end37
. The
results of theoretical calculation given in the present work will be useful
for the prediction of selectivities for similar cycloadditions. The present
work addresses the following questions: (1) what would be the structure
and energy of the transition states; (2) how could the experimentally
observed selectivities be rationalized on the basis of computational
results in terms of energy, enthalpy, and free energy of activation; (3)
whether the selectivities could be justified on the basis of global and
local electrophilicity, chemical potential and hardness parameters of the
reacting systems; (4) how could the structures of the isolated
cycloadducts be assigned with the help of spectroscopic means like the
Page 24
General Introduction
15
X-ray crystallography and the NMR analysis. Such theoretically
augmented experimental investigation about the variation in
stereoselectivity would provide an insight to understanding the process of
cycloaddition.
Cycloaddition reaction of allyl alcohol with the 1,3-dipole: 1-phenylethyl
nitrone is observed computationally to produce stereoisomeric products,
giving the re-face : si-face product ratio approaching unity which is also
observed experimentally38
. Similar results on products ratio are also
found for the cycloaddition between styrene and the dipole: 1-
phenylethyltrans-2-methyl nitrone, giving a product ratio agreeing with
the experimental ratio as observed by Belzecki et.al.39,40
Theoretical
calculations are performed at the modest B3LYP/6-31G(d) level of DFT.
The quantities that we employ to study these reactions include the rate
constant values and Wiberg bond index in the transition state.
Interpretation of the regioselectivity, enantioselectivity and prediction of
diastereofacial selecitivity for the 1,3DC reaction of these two known
nitrones, have led to a diastereomeric excess of the products. In this
regard, the N-substituted and C-substituted nitrones are considered for
reactions with the substituted dipolarophiles like styrene and allyl
alcohol. These reactions are studied by constructing the potential energy
surface of the addition process and rationalizing results in terms of the
global electrophilicity index of reactivity. For the reactions considered,
trends in reactivity, i.e., the regio- and exo/endo-selectivity and product
ratios have been explained in terms of frontier orbital interactions,
electrophilicity difference, the theoretical rate constant values and an
analysis in terms of Pauling’s bond order and Wiberg bond index41
in the
transition state. All these are found to be in good agreement with the
experimental findings.
Page 25
General Introduction
16
Cycloaddition of azomethine imines with three electron deficient
dipolarophiles: acrylonitrile, methylpropenoate, and dimethylmaleate
have been theoretically studied42
. This has produced predominantly 4-
substituted pyrazolidines, which are found to be very useful for the
stereoselective synthesis of C-nucleosides15
. The mechanisms of
regioselectivity, chemoselectivity and diastereofacial selectivity are
studied through an evaluation of activation energies and the parameters
of philicity indices on the assumption of a concerted path. The reactions
are followed by performing transition state optimization. The
regioselectivity and reactivity are amply predicted with the help of local
and global electrophilicity and nucleophilicity indices. The reactions are
found to be nonpolar or at the most weakly polar on the basis of Charge
Transfer (CT) calculated at the transition states. A rationalization is also
attempted in terms of chemical potential, hardness, global electrophilicity
differences, local electrophilicity, local nucleophilicity, Pauling’s bond
order and Wiberg bond indices in the transition state41
. Theoretical
evaluation of rate constants for elementary reaction steps employing the
transition state theory has been done for getting quantitative idea of the
kinetic rates associated with those steps. Calculation of rate constants are
performed with the Eyring’s TST rate equation43-44
and calculating total
partition functions of the concerned species at different temperatures. All
the computed results are derived from density functional calculations at
the B3LYP/6-31G(d) level of theory and with [6-311+G(d,p)] basis.
Considering the reality that the reactions are practically carried out in
solutions, some calculations are performed in solvents of different
polarity to examine the influence on the activation barrier and the
reaction rate.
Page 26
General Introduction
17
References
1. A. Padwa and W. H. Pearson, Synthetic Applications of 1,3-Dipolar
Cycloaddition Chemistry Toward Heterocycles and Natural Products. John
Wiley & Sons, Inc., New York, 2002.
2. T.W.G. Solomons, C. B. Fryhle, Organic Chemistry, Eighth Edition, John
Willey & Sons, Inc., 2004.
3. K.V. Gothelf and K.A. Jorgensen, Asymmetric 1, 3-Dipolar. Cycloaddition
Reactions. Chem. Rev., 98 (1998) 863.
4. R. Huisgen, in 1,3- Dipolar Cycloaddition Chemistry, ed. A. Padwa, Wiley,
New York. 1984; vol.1, Ch 1.
5. R. Huisgen, J. Org. Chem., 33 (1968) 2291.
6. L.M. Harwood, A. I. Lilly, Tetrahedron Lett. 34 (1993) 537.
7. A.S. Anslow, L.M. Harwood, I.A. Lilley, Tetrahedron: Asymmetry. 6 (1995)
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8. A.S. Anslow, G.G. Cox, L.M. Harwood, Khim. Geterotsikl. Soedin.
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9. C.M. Tice and B. Ganem, J. Org. Chem., 48 (1983) 5048.
10. A. Padwa, Y. Chen, W. Dent, and N. Hildegard, J. Org. Chem., 50 (1985)
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11. A. Padwa and J. R. Gasdaska, J. Am. Chem. Soc., 108 (1986) 1104.
12. A. Banerjee and D. Bandyapadhyay, J. Indian Chem. Soc., 81 (2004) 817.
13. P. Merino, J. Revuelta, T. Tejero, U. Chiacchio, A. Rescifina and G. Romeo,
Tetrahedron, 59 (2003) 3581.
14. L. R. Domingo, European J. Org. Chem. (2000) 2265.
15. R.C. F. Jones, S.J. Hollis, ARKIVOC, v (2007) 152.
16. R. Sustmann, Tetrahedron Lett. (1971) 2717.
17. R. Sustmann, Pure Appl.Chem. 40 (1974) 569.L. R. Domingo, European J.
Org. Chem. (2000) 2265.
18. L.R. Domingo and J.A. Sáez, Org. Biomol. Chem. 7 (2009) 3576.
19. R.G. Parr and Y. Wang, Density-Functional Theory of atoms and molecules
(Oxford Univ. Press: Oxford) 1989.
20. R.G. Parr, L.V.Szenpaly, S. Liu, J. Am. Chem. Soc. 121 (1999)1922.
21. P.K. Chattaraj, D.R. Roy, Chem. Rev. 107 (2007) 46-74.
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General Introduction
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22. R.G. Parr, R. G. Pearson, J. Am. Chem. Soc. 105 (1983) 7512.
23. C. Møller and M. S. Plesset, Phys. Rev., 46 (1934) 618.
24. P. Geerlings, F.De. Proft, W. Langenaeker,. Chem. Rev. 103 (2003) 1793.
25. M.J. Frisch et al., Gaussian 03, Revision D. 01, Gaussian Inc.,
Wallingford, CT, 2004.
26. P. Merino, J. Revuelta, T. Tejero, U. Chiacchio, A. Rescifina and G. Romeo,
Tetrahedron, 59 (2003) 3581.
27. C. Peng, P.Y. Ayala, H.B. Schlegel and M.J. Frisch, J. Comput. Chem., 17
(1996) 49.
28. H. Chermette, J. Comput. Chem. 20 (1999) 129.
29. S. Sakai, M.T. Nguyen, J. Phys. Chem. ,A 108 (2004) 9169.
30. K.N. Houk, J. Gonzalez and Y.Li, Acc. Chem. Res., 81 (1995) 28.
31. L.R. Domingo. J. Org. Chem., 64 (1999) 3922.
32. E.C. Magnuson and J. Pranata, J. Comput. Chem., 19 (1998) 1795.
33. M.T. Nguyen, A.K. Chandra, S. Sakai and K. Morokuma, J. Org. Chem., 65
(1999) 64.
34. C. DiValentin, M. Freccero, R. Gandolfi, A.Rastelli, J. Org. Chem., 65
(2000) 6112.
35. T.K. Das, M. Banerjee, J. Phys. Org. Chem. 23 (2009) 148.
36. L. Pauling, in The Nature of Chemical Bond, Cornell University, ITHACA,
NY, 3rd
.ed. 1960, p. 239
37. N. Acharjee, T.K. Das, M.Banerjee, A. Banerji, T. Prangé, J. Phys. Org.
Chem. 23 (2010) 1187.
38. T.K. Das, S. Salampuria, M. Banerjee, J. Mol. Struct.: THEOCHEM 959
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39. C. Belzecki, I. Panfil, J. Chem. Soc. Chem. Commun. (1977) 303.
40. C. Belzecki, I. Panfil, J. Org. Chem. 44 (1979) 1212.
41. K. B. Wiberg, Tetrahedron 24 (1968) 1083.
42. T.K. Das, S. Salampuria, M. Banerjee, Computational and Theoretical
Chemistry 979 (2012) 102–111.
43. K.J. Laidler,Chemical Kinetics, PEARSON Education Inc. 3rd
ed. 2009.
44. D.A. McQuarrie, J.D. Simon, Physical Chemistry, Viva Books Private
Limited, First South Asian Edition, 1998.
Page 28
Chapter: 2
General methodology and theoretical
approach towards chemical reactions
Page 29
General methodology and theoretical approach towards chemical reactions
20
2.1. Theoretical Chemistry and Chemical Reactions
Development of quantum mechanics in the 1920’s rapidly led to the formulation of
new quantum mechanical theory of molecular structure and bonding, as expressed in
the pioneering approaches of Pauling1 (the valence bond (VB) theory) and Mulliken
2
(the molecular orbital (MO) theory). Through such approaches, it became possible to
describe molecular structure in terms of position of the atoms in space and the
chemical bonds formed between them. It further became feasible to give
mathematical expression to chemical reactivity through the use of atomic charges
and the preferred sites for reactivity of the chemical molecule could be identified.
Recent revolution in computer technology could provide more accurate calculations
of properties for the actual molecules giving a very good rationalization of chemical
phenomena. In order to achieve a reliable accounting of the energies leading to a
chemical reaction, it is essential to obtain optimal geometry configurations of the
different species involved.
2.2. Geometry Optimization
Optimization of geometry of a molecule is usually attempted to locate minima on the
potential energy surface (PES), thereby predicting equilibrium structures of
molecular systems. Optimization to minima is also called energy minimizations.
This energy-minimized configuration in space is called the equilibrium geometry,
occurring at the bottom of a potential well. At both the minima and saddle points
over the reaction path, the first derivative of energy, known as the gradient is zero. A
point on the potential energy surface where the forces are zero is known as a
stationary point. All successful optimizations locate a stationary point, although not
always the one that was intended.
A geometry optimization begins at the molecular structure specified as its input, and
steps along the potential energy surface. It computes the energy and the gradient at
that point, and then determines how far and in which direction to make the next step.
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General methodology and theoretical approach towards chemical reactions
21
The gradient indicates the direction along the surface in which the energy decreases
most rapidly from the current point also known as the steepness of that slope. Most
optimization algorithms estimated or computed the value of the second derivative of
the energy with respect to the molecular coordinates, updating the matrix of force
constants which is known as Hessian. These force constants specify the curvature of
the surface at the point, which provided additional information useful for
determining the next steps. An optimization is complete when it has converged,
essentially when the forces are zero. The semi-emperical MO methods3 allow for a
more rapid search for energy minima using gradients which can be evaluated
analytically without much expense of computer time.
The steepest descent methods involves step-wise movement of the atoms of the
molecule towards the equilibrium point by calculating each step of movement as a
liner function of force or gradient acting on that atom. This causes the gradient norm
finally to cross a prescribed small threshold. This process may be carried out in
terms of cartesian coordinates or other systems like the internal coordinate system.
Optimizations of the individual reactants of a reaction are done isolatedly. But the
optimization of the reactants together is sometimes difficult. It requires some
important prior requirements such as force constants and some times the solvent as
default, otherwise the job gets terminated. Again the transition state optimization is
somewhat more difficult, and not as easy as that of a single molecule. This is
experienced from our observation through computation with the Density Functional
Theory (DFT)/ Lee, Yang and Parr (B3LYP) method4 and 6-31(d) basis.
2.3. Test for a True Minimum
Characterization of a given stationary point as a true minimum may be preformed by
setting up the Hessian matrix and diagonalising it. When internal coordinates are
used, for a system of X internal coordinates, the emergence of X positive
eigenvalues confirms the given point as an energy minimum or equilibrium
Page 31
General methodology and theoretical approach towards chemical reactions
22
geometry. When cartesian coordinates are used for a system of N atoms, an
equilibrium geometry, may be characterized by the emergence of 3N-3 positive non-
zero Hessian eigenvalues, and there will be only 3 eigenvalues becoming zero or
near zero corresponding to translation in three dimensions.
All these methods to locate energy minima would, in general, lead to that minimum
which is closest to the starting input geometry. Care should be taken that the input
geometry is not too far from the expected equilibrium geometry. A
multidimensional potential energy surface may have several local minima and which
one of these is actually sought is determined by educated guess. The local minimum
which is the lowest of all in energy is termed as the global minimum.
2.4. Transition State Optimization and its Location
The Transition State for a given reaction process is a saddle point on the potential
energy surface. The given process may be a bonafied chemical reaction with bond-
breaking and bond-making, or it may be a more physical process like simple rotation
around a bond or the stretching and compression of bonds. Whatever might be the
process, its rate is dependent on the activation energy barrier which lies on the path
along the reaction coordinate. This barrier corresponds to the point on the energy
hypersurface wherein the transition state is located. The location of this saddle point
is thus an important part of the study of chemical reactivity from the view point of
kinetic feasibility. The highest point of the on the reaction path way of the potential
energy surface or the activation energy diagram is the saddle point where the
transition state is supposed to exist. The most rigorous method to locate the saddle
point would be to plot the entire potential surface upon which all the reacting species
lie. It is a minimum in one direction and maximum in the others. This is a low point
along a ridge. As the potential energy surface becomes progressively
multidimensional, such a procedure becomes more and more time consuming and
tedious computationally. Although time consuming, it is essential to optimize the
Transition State (TS) to evaluate the kinetic part of the reactions and also to explore
Page 32
General methodology and theoretical approach towards chemical reactions
23
the product ratios and stereochemical feasibility of the reactions. Within the
Gaussians set of package the QST3 option5 (Quasi-Newton Synchronous Transit)
option for the optimization of TS does not require a pre-optimization of the reactants
brought together, but requires in the input an optimized product geometry as well as
a guess TS geometry. This option produces an optimized TS efficiently. In some
difficult cases an input of the geometry of an optimized orientation complex of the
reactants leads to successful attainment5 of the TS.
2.5. Test for True Transition State
Locating the true TS in a reaction is a very critical task. Within the Gaussian set of
packages we optimized the transition state with the option of (Opt+Frq) which on
successful completion produces one imaginary frequency in the result section, which
ensures obtaining the true transition state. Intrinsic Reaction Coordinate (IRC)6
corresponding to the optimized TS is the lowest possible minimum energy path,
which connects the reactants and products through the transition state. Obtaining
IRC confirms the location of a true Transition State on the saddle point of potential
energy surface. Every calculation of TS has been substantiated with calculation of
corresponding IRC throughout our entire work7.
2.6. Quantum Chemical Tools for Electronic Energy Calculation
2.6.1. The Hartree-Fock Self-Consistent Field Method
The formulation of actual molecular orbitals is a matter of design or
convenience, which makes a liner combination of the atomic orbitals (LCAO) of
constituents atoms to generate molecular orbitals (MO) for molecules. The atomic
Page 33
General methodology and theoretical approach towards chemical reactions
24
orbitals may be expressed in various ways i) hydrogenic orbitals, ii) Slater-type
orbitals, iii) Gaussian type orbitals. Again the net collection of all the atomic
functions used to express them is referred to as the basis set. According to Pauli’s
Exclusion Principle, the overall molecular wave-function is of antiasymmetric type,
which becomes possible when the total molecular wave-function is expressed as a
Slater determinant – a determinantal combination of the constituent electrons
molecular orbitals, or a liner combination of determinants.
Hartree-Fock (HF) Self Consistent Field (SCF) method8 gives
account of the explict electron repulsions in a molecular system by applying
columbic interactions and the Pauli’s Exclusion Principle with the help of Fock
operator. Employing the concept of an averaged-out field in which the electrons
move, the Slater determinantal wave-function has an iterative solution, when the
molecular orbitals take on a form which is consistent with the field they generate.
The repeated diagonalization of the ever-recreated energy matrix leads to the
solution in which the finally self-consistent field MO’s emerge as the eigenvectors
and their energies as the eigen values. In practice, the iterations are truncated when
the level of self-consistency of field falls below an acceptable threshold, expressed
in terms of successive difference of values of relevant component of mathematical
form adopted by the MO’s that is the total energy.
The Roothaan approach weds the LCAO approximation to the HF-SCF MO theory9.
In this case all the energy terms appear as various integrals involving the atomic
orbitals of the constituent atoms and centered over various atomic centers-one, two,
three, four or five at a time. The bottleneck lies here in the amount of computational
effort required to evaluate all these different types of integrals. When no
approximations are made and all the integrals are explicitly evaluated, the approach
is termed as ab initio, which of necessity is rigorous and time-consuming, depending
upon the basis set.
Hartree-Fock (HF) theory is fundamental to electronic structure theory10
.
It is the basis of molecular orbital (MO) calculation. This produces a situation that
each electron’s motion can be described by a single-particle function (orbital) which
Page 34
General methodology and theoretical approach towards chemical reactions
25
does not depend explicitly on the instantaneous motions of other electrons. In other
words, HF theory is effectively a one-electron theory that approximates a many
electron problem as a single electron one, where each electron is moving in an
effective potential field produced by the remaining electrons and nuclei in a system.
The ubiquity of orbital concepts in chemistry is a testimony to the predictive power
and intuitive appeal of Hartree-Fock MO theory. However, it is important to
remember that these orbitals are mathematical constructs which only approximate
reality. Only for the one-electron system, orbitals are exact eigen functions of the
full electronic Hamiltonion. As long as we are content to consider molecules near
their equilibrium geometry, HF-theory often provides a good starting point for more
elaborate theoretical methods which are better approximations to the electronic
Schrdöinger Equation. The HF wave function is the cornerstone of ab initio
electronic structure theory. In HF theory10
, the molecular wave function Ψ is
constructed with Slater determinants of molecular orbitals, namely;
)(),....,(),(
)2(),....,2(),2(
)1(),......,1(),1(
!
1
21
21
21
NNN
N
N
N
N
SDHF
……….. (2.1)
Where N is the total number of electron, an {χ} is the set of molecular spin-
orbitals i.e., a product of a spatial orbital and an electron spin eigen function. A
Slater determinant is used to make Ψ antisymmetrical with respect to the exchange
of co-ordinates of any two electrons, and thus, compliant to the Pauli Exclusion
Principle. The molecular orbital is normally expanded in terms of the atomic orbitals
.4,321 .......,, N
iC ……………. ( 2.2)
In which the limited set of m functions is called the “basis set”, and each
associated with a MO co-efficient iC . This construction is known as the liner
combination of atomic orbitals (LACO).
Page 35
General methodology and theoretical approach towards chemical reactions
26
Based on the variational principle, one can now minimize the expectation value of
total electronic energy with respect to the orbitals presenting a single Slater
determinant.
HFHF
HFHF HE
………………. (2.3)
And the Hartree-Fock energy is given as;
M
A
M
B
M
A AB AB
BAelec
AB
BAHFelecHFHF
R
ZZE
R
ZZHE
1
……. (2.4)
where; Z is the nuclear charge and ABR is the separation between two nuclei A and
B.
The HF wave function takes into account the interaction between two electrons only
in an average way. Actually, we have to consider the instantaneous interactions
between electrons. That means motion of electrons is correlated with each other
implying the importance of electron correlation. The lack of electron correlation
causes the main limitation of the HF theory. Therefore, several ab initio methods
have been developed in order to improve upon the HF wave function and to include
the effect of electron correlation.
These methods view HF theory as a stepping stone or the zeroth order wave function
on the way of exact solution of the Schrödinger Equation. HF theory provides a very
well-defined energy, one which converges in the limit of an infinite basis-set, and
the difference between that converged energy (EHF) and exact energy (Eexact) is the
electron correlation energy (Ecorr) given as;
Ecorr = EHF - Eexact ………….. (2.5)
Further approaches to the reality involves the creation of further models which treat
electron correlation, the instantaneous effect that every electron has on all the others
Page 36
General methodology and theoretical approach towards chemical reactions
27
that all move together and not to be confused with the time averaged electron
interaction of SCF theory. There is a limit to which the best Hartree-Fock interaction
can reach, and the difference in total energy of the system between the Hartree-Fock
limit and nature itself (exact) is termed as the correlation energy. Some of the
approaches to treat electron correlation include Moller-Plesset perturbation theory11
of varying orders, configuration interaction, the method of coupled clusters, etc.
2.6.2. Moller-Plesset Perturbation Theory
Prior to the widespread use of methods based on density functional theory, the
Moller-Plesset (MP) perturbation theory11
was one of the least expensive ways to
improve on Hartee-Fock and it was thus often the first correlation method to be
applied to new problems. It can successfully model a wide variety of systems, and
Moller-Plesset second order perturbation (MP2) geometries are usually quite
accurate. Thus, MP2 remains a very useful tool for computational chemists10
.
Using eigen functions and eigen values of the simplified operator, it is possible to
estimate the eigen functions and eigen values of the more complete operator.
Quantitatively, MP perturbation theory adds higher excitations to the HF manifold,
drawing upon the techniques from the area of mathematical physics known as many
body perturbation theory. The MP theory is a practical approach based upon
dividing the electronic Hamiltonian into two parts:
H = HHF + λV ………. (2.6)
Such that H0 or HHF is taken as the unperturbed Hamiltonian for an atom or molecule
as the sum of the one FOCK operators which are solveable exactly, i.e.,
)(iFHHF ……….. (2.7)
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General methodology and theoretical approach towards chemical reactions
28
where, the eigenfunctions of F are the occupied and virtual HF orbitals of the system
and the eigenvalues are the associated one electron energies.
iiiF ……….. (2.8)
The HF wavefunction is an eigenfunction of
HFH with an eigenvalue equal to the
sum of the one electron energies of the occupied spin orbitals.
The essential observation in MP perturbation theory is that all Slater determinants
formed by exciting electrons from the occupied to the virtual orbitals are also
eigenfunctions of
HFH with an eigenvalue equal to the sum of the one electron
energies of the occupied spin orbitals. So a determinant formed by exciting from the
ith
spin orbital of the Hartree-Fock ground state into the ath
virtual spin orbital.
λV is a perturbation applied to H0, a correlation which is assumed to be small in
comparison to it. In other words, it is the difference between the instantaneous and
average electron-electron interaction. This perturbation is sometimes called the
fluctuation potential as one imagines that it measures the deviation from the mean
electron-electron interaction.
N
i
N
ij
N
i
HF
ijHF iVrHHV1 1
1 )( ……….. (2.9)
The assumption that V is a small perturbation to H0 suggests that the perturbed wave
function and energy can be expressed as a power series in V. The usual way to do so
is in terms of parameter λ. The Moller-Plesset second order energy is obtained as;
2
1
)2(
0
srba srba
ji
rs
abijHF r
E
……… (2.10)
rs
ab is doubly excited determinant and ε’s are the corresponding energies of the
occupied and the virtual orbitals.
Page 38
General methodology and theoretical approach towards chemical reactions
29
There are problems for which MP2 theory fails as well, however. In general, the
more unusual the electronic structure a system has the higher level of theory that
will be needed to model it accurately.
Higher level (MP) orders are available for cases where the second order solution of
(MP2) is inadequate. In practice, however only Moller-Plesset fourth order (MP4)
sees wide use. Moller-Plesset third order (MP3) is usually not sufficient to handle
cases where MP2 does poorly, and it seldom offers improvement over MP2 which
are commensurate with its additional computational cost. In contrast, although
significantly more expensive than MP2, MP4 does successfully address many
problems which MP2 cannot handle.
2.6.3. Density Functional Theory
Density functional theory (DFT)10,12
is a quantum mechanical theory used in physics
and chemistry to investigate the electronic structure of many-body systems, in
particular atoms, molecules and the condensed phases. With this theory, the
properties of the many electron systems can be determined by using a functional,
i.e., a function of another function, which is spatially dependent on the electron
density.
DFT is among the most popular and versatile methods applicable to condensed
matter physics, computational physics and computational chemistry. During the last
few years, methods based on density theory have gained steadily in popularity. The
best DFT methods achieve significantly greater than the Hartree-Fock at only
modest increase in cost but far less than MP2 for medium size and large molecular
systems. This theory does so by including some of the effects of electron correlation
much less expensively than traditional correlation methods. DFT-based methods
were derived from quantum mechanics research since the 1920’s especially from
Thomas-Fermi-Dirac model, and from Slater’s fundamental work in quantum
Page 39
General methodology and theoretical approach towards chemical reactions
30
chemistry in 1950’s. The DFT approach is based upon a strategy of modeling
electron correlation via general functional of the electron density.
Such methods owe their origin to the Hohenberg-Kohn theorem13
, published in
1964, which demonstrated the existence of unique functional which determines the
ground state energy and density exactly. The theorem does not provide the exact
form of this functional. Following the work of Kohn and Sham14
, an approximate
energy functional was developed by the present DFT method15
which partitions the
electronic energy into several terms;
xcees EJVTE ……… (2.11)
Where sT is the kinetic energy term arising from the motion of the electrons,
J[ρ] includes the potential of the nuclear-electron attraction and the repulsion
between pairs of nuclei, Vee[ρ] is the electron-electron repulsion-term or columbic
self-interaction of the electron-density, and EXC[ρ] is the exchange-correlation term
which includes the remaning part of the electron-electron interactions. It contains the
difference between ground state kinetic energy T and kinetic energy for the N non
interacting electrons sT , a presumably fairly small and nonclasical part Vee[ρ].
JVTTE eesxc ][ ……… (2.12)
Ts[ρ] +Vee[ρ]+J[ρ] correspond to the classical energy of the charge distribution ρ.
The EXC[ρ] term is basically quantum mechanical in nature and the accounts for the
quantum mechanical effect* (non-classical).
* The exchange energy arising from the antisymmetry of the quantum mechanical
wavefunction.
* Dynamic correlation in motion of the individual electrons.
Therefore, the working expression for energy of density functional theory may be
written as;
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General methodology and theoretical approach towards chemical reactions
31
drrrVEdrdrrr
rrE xcxc
N
i
i )()(][''
)'()(
2
1
……… (2.13)
N
i
N
i
ieffii V 2
2
1 …….. (2.14)
N
i
effsi drrrVT )()(][ …….. (2.15)
where; ρ(r) electron density, Vxc and Veff exchange-correlation and effective
potentials.
Traditional Functionals:
A variety of functionals have been defined, generally distinguished by the way that
they treat the exchange and correlation functional;
Local and exchange functionals involve only the electron-spin densities. Slater
and X are well known local exchange functionals, and the local spin density
treatment of Vosko, Wilk and Nusair (VWN) is a widely used local correlation
functional.
The local exchange is virtually defined as follows:
rdE X
LDA
33/4
3/1
4
3
2
3
….... (2.16)
Where, ρ is a function of position vector r. This form was developed to
reproduce the exchange energy of a uniform gas. However, it has a weakness in
describing molecular systems.
Gradient-corrected functionals involve both the values of the electron spin
densities and their gradients. Such functionals are also sometimes referred to as
non-local. A popular gradient-corrected exchange functional is one proposed by
Becke in 1988; a widely used gradient corrected correlation functional is LYP
Page 41
General methodology and theoretical approach towards chemical reactions
32
functional of Lee, Yang and Parr15,16
. The combination of the two forms is the B-
LYP method. Perdew has also proposed some important gradient-corrected
correlation functional, known as Perdew 86 and Perdew-Wang 91.
The functional form of gradient-correlated exchange functional based on the
LDA exchange functional is given as;
rdEE X
LAD
X
Becke
3
1
23/4
88)sinh61(
….. (2.17)
where 3/4 .
γ is a parameter chosen to fit the known exchange energies of the inert gas
atoms, and Becke17
defines its values as 0.0042 Hatrees. As the above equation
makes it clear, Becke’s functional is defined as a correlation to the local LDA
exchange functional, and it succeeds in remedying many of the LDA
functional’s deficiencies.
Hybrid Functionals:
There are also several hybrid functionals which define the exchange functional as a
liner combination of Hartree, local and gradient-corrected correlation functionals.
The best known of these hybrid functionals is Becke’s three-parameter formulation.
Becke-style three parameter functional may be defined via the following
expression18
:
)( 338803
C
VWN
C
LYPC
X
VWN
X
BX
X
LDA
X
HF
X
LDA
XC
LYPB EECEECEECEE …… (2.18)
Here, the parameter C0 allows any admixture of Hartree-Fock and local exchange to
be used. In addition, Becke’s gradient correction to LDA exchange is also included,
scaled by the parameter CX. Similarly, the VWN3 local correlation functional is
used, and it may be optionally corrected by correlation functional proposed by Lee,
Yang and Parr (LYP) via the parameter CC. In the B3LYP functional, the parameter
Page 42
General methodology and theoretical approach towards chemical reactions
33
values are those specified by Becke, which he determined by fitting to the
atomization energies, ionization potentials, proton affinities and first-row atomic
energies in the G1 molecule set: C0 = 0.20, CX = 0.72 and CC =0.81. Becke style
hybrid functionals (such as B3LYP, B3PW91)19
have proven to be superior to the
traditional functionals defined so far for calculating ground state properties.
2.7. Natural Bond Orbital (NBO) Analysis
The localized bond orbital analysis such as natural bond orbital analysis20
can be
carried out to understand the orbital interaction involved with the hydrogen bond
formation and how it varies with the change in proton donor and acceptor atoms.
Natural bond orbital analysis is a technique for studying hybridization and covalency
effects in polyatomic wave functions.
Natural Orbital (NOs) can be described as unique optimal orbital chosen by the
wavefunction itself for its own description. Mathematically, the NOs i of a
wavefunction can be defined [2.19] as the eigenorbitals of the first reduced
density operator .
kkk p (k=1,2,…..) ………… (2.19)
In this equation, the eigenvalue kp represents the population (occupancy) of the
eigenfunction k for the molecular one electron density operator of . The
density operator is merely the 1-electron “projection” of the full N-electron
probability distribution (given by the square of the wave function 2
) for
answering questions about 1-electron subsystems of the total wave function .
Since is only quantity that defines the NOs, these orbitals are truly ’s “own”
(eigen) orbitals, intrinsic (“natural”) to description of the electron density and other
single-electron properties of . The natural bond orbitals (NBO) are determined
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General methodology and theoretical approach towards chemical reactions
34
through a sequence of orthogonal transformations from the input basis set i to
various localized basis sets [natural atomic orbitals (NAOs)].
Input basis → NAOs →NBOs
Natural Atomic Orbitals (NAOs) )( A
k are localized 1-center orbitals that can be
described as effective “natural orbitals of atom A” in the molecular environment.
Charges on individual atoms, hybridization, orbital occupancies and
hyperconjugative energies can be obtained from the natural bond orbital (NBO)
analysis scheme. The coupling between orbitals can be well approximated by simple
second-order perturbative expressions of type illustrated in Fig. 2.1.
*
E1
E2
Fig. 2.1 Perturbative donor-acceptor interaction, involving
a filled orbital and an unfilled orbital * .
The extent of coupling between a -orbital or a lone-pair orbital with * orbitals
can be assured from the hyperconjugative interaction energies estimated form the
second order perturbation theory:
E
Fn
F
nE
2
2
*
*
)2( *
………… (2.20)
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General methodology and theoretical approach towards chemical reactions
35
Where, represents a bond-orbital or a lone-pair orbital and * is the antibonding
orbital. F is the Fock operator and ’s represent orbital energies.
2.7.1. Wiberg Bond Index (from the NBO analysis)
Wiberg bond index
21 is one kind of bond order, which is applicable to
calculating bond order mainly from overlap of electron density and
especially significant for the study of transition states. Calculation of Wiberg
bond index can be done with the NBO analysis computationally by giving a
particular command in Gaussian program during NBO calculation.
2.8. Chemical Reactivity Indexes
Theoretical reactivity indexes22
and calculated thermodynamic parameters are very
much associated with a chemical reaction, more so for a cycloaddition reaction and
for that reason we have included some of them in the following. Among the various
entities are the electronic chemical potential (), chemical hardness (),
electrophilicity (), nucleophilicity (N), enthalpy (rH), and free energy (rG) of
reaction, enthalpy (H) and energy (E
) of activation
23.
a) Chemical Hardness
The chemical hardness24
specifies the resistance to flow of the electronic charge
during the reaction process and can be quantitatively represented as
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General methodology and theoretical approach towards chemical reactions
36
)()(
2
2
rrNN
E
………………...(2.21)
If HOMO and LUMO are the energies of highest occupied and lowest
unoccupied molecular orbitals, respectively then the above equation can be
rewritten as
= LUMO HOMO ………………...(2.22)
For a pair of reactants, a quantity *
is defined as the pair hardness of the
system R-Rˊ when R and Rˊ are widely separated and is has been defined
by *= R-Rˊ = (Imin –Amax )/2 where Imin is the smaller of the two ionization
potentials IR and IRˊ and Amax is the larger of the two electron affinities AR
and ARˊ. Following Koopman’s theorem this quantity *
has been taken in
our case to be the difference between LUMOalkene and HOMOdipole energy
values and can compare with the results alongside the heats of reaction rH.
It appears that pair hardness parameter for the two reacting species: dipole
and dipolarophile follows the sequence of stability (rH), satisfying
maximum hardness principle. As the hardness increases it is seen that the
reaction gets faster due to decrease in activation energy. This feature is a
reflection of the “Hardness maximization principle”. It should be highlighted
additionally that the HOMO – LUMO energy gap, even for different species,
is a measure of stability. Hard interactions are essentially electrostatic in
nature. Charges or associated quantities such as molecular electrostatic
potentials and local hardness are supposed to be better descriptors for hard
reactions25
. This observation is also confirmed through our calculation of rate
constant values and the corresponding activation energies that are presented
in the corresponding sections.
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General methodology and theoretical approach towards chemical reactions
37
b) Electronic Chemical Potential
The electronic chemical potential () can be expressed as
][
][)(lim
)(,0 r
Fr
E
N
A
N
E
r
…….. (2.23)
Simply the chemical potential can be written as
≈ (HOMO+LUMO)/2 ……… (2.24)
This can explain the direction of flow electrons from one reactant to the other
reactants, during the course of reaction. The flow of electrons occurs from the
reactant with higher value of to the reactant of lower electronic chemical
potential ()26
.
c) The Global Electrophilicity Index
The global electrophilicity index ()
measures the stabilization in energy when
the system acquires an additional electronic charge N from the environment.
has been expressed in terms of electronic chemical potential and chemical
hardness as = 22. The maximum amount of electronic charge Nmax that
can be accepted by an electrophile system is given by Nmax = -/. The global
electrophilicity index includes the propensity of the electrophile to acquire an
additional electronic charge as well as the resistance to exchange that electronic
charge with the environment, simultaneously. Thus, a good electrophile can be
characterized by a high value of and a low value of 25,26
.
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General methodology and theoretical approach towards chemical reactions
38
d) The Fukui Function
Fukui function is a measure of sensitivity of a system’s chemical potential to an
external perturbation at a particular point. This is a chemical reactivity index in
the sense of frontier electron theory and contains information about relative site
reactivity in a molecule. The calculation of Fukui functions of an atom in a
molecule proves to be a useful criterion to characterize the reactive sites within a
chemical species. To describe the site selectivity or reactivity of an atom in a
molecule, it is necessary to condense the values of Fukui function )(rf around
each atomic site into a single value that characterizes the atom in a molecule.
Nr rvN
rrf
)(
)()(
)(
……… (2.25)
This can be achieved through electronic population analysis. Thus, for an atom k
in a molecule, depending upon the type of electron transfer, we have the
condensed Fukui function of the atom k.
The value of )()1( NqNqf KKK for a nucleophilic
attack and )1()( NqNqf KKK for an electrophilic attack. Where,
)1( Nqk , )(Nqk , )1( Nqk are the Mulliken charge populations of the atom k
in the cation, neutral, and anion respectively of a molecule27
. These values are
calculated from the optimized geometry of neutral molecule, which calculations
are further submitted through single point energy calculations giving the
molecular charge –1 for anion and +1 for cation.
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General methodology and theoretical approach towards chemical reactions
39
e) The Local Electrophilicity Index
The local electrophilicity index k can be expressed as the product of global
electrophilicity and Fukui function )(rf around each atomic site i.e., k = k+
where k+ is the Fukui function. Hence condensed Fukui functions (for
electrophilic and nucleophilic) of the reactants were calculated on the basis of
the atomic sites in order to rationalize the observed regioselectivities in respect
of the investigated cycloadditions26
.
f) The Global Nucleophilicity Index
The global nucleophilicity (N) model has been recently introduced
28, based on
the relationship N = -IP, where IP is the gas phase (intrinsic) ionization potential
and can be straightforwardly extended to describe the local nucleophilicity.
Following those derivations concerning the local electrophilicity and philicities,
it is taken that the global nucleophilicity index (N) can be written as,
N = k
kN ……. (2.26)
The nucleophilicity index N for a given system was therefore defined as28
,
N(Nu) = EHOMO – EHOMO (TCE) ……… ( 2.27)
Where, EHOMO is the HOMO energy the nucleophile molecule in eV units for
the reactants we want to study and EHOMO (TCE) is the HOMO energy of the
reference tetracyanoethylene molecule in eV unit. The reference TCE is
taken due to the lowest HOMO energy allowing us to have a positive global
nucleophilicity scale. With the simplest approximation to neucleophilicity,
the IP values can be approximated in terms of the HOMO energy in a
molecule within a given molecular orbital (MO) scheme.
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General methodology and theoretical approach towards chemical reactions
40
g) The Local Nucleophilicity Index
The local nucleophilicity condensed to atom k through nucleophile is related
to the global nucleophilicity (N) and the Fukui function, fk+ by
kk NfN ……. ( 2.28)
This equation shows that the maximum nucleophilicity power in a molecule
will be developed at the site where the nucleophilic Fukui function fk+
displays its maximum value (i.e., the active site of the nucleophile). Note that
the projection to the local level is based on the normalization condition of the
Fukui function, namely 1)( drrf or in its condensed at k atom version
1
k
kf , it is wroth to mention that there might exit other systems where
philicity indexes would perform better, as far as numerical results are
concerned.
h) Global and Local Softness
The values of Global softness26
are needed to convert regional Fukui
functions into regional softness that were obtained from the frontier one
electron energies of HOMO and LUMO as;
S ≈ 1/(LUMO HOMO) ………..(2.29)
where, S is the global softness of a molecule. The local (regional)
softness of an atom in a molecule can be related to the Fukui functions as
given by Sk = Sfk+
. From the value of local softness it is easy to predict the
nature of atomic centers of the two reactants where they would attack or
would be attached to from chemical bonds.
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General methodology and theoretical approach towards chemical reactions
41
i) Enthalpy or Heat of the Reaction
The enthalpies of reaction (∆rH)29
are calculated from a deduction of sum of
the enthalpies of individual reactants from the sum of enthalpies of the
products. These thermal enthalpies can be obtained from the frequency
calculation of the optimized individual chemical species, and the data were
extracted from the thermochemistry section of the output (log) file. All the
optimization and frequency calculations were done by the DFT/B3LYP
method using 6-31G(d) basis.
This can be expressed as
∆rH = [H(products)] – [H(reactants)] …….. (2.30)
The enthalpy of reaction ∆rH is positive for the endothermic reactions and
negative for the exothermic reactions. It has been stated that pair hardness
parameter *for the two reacting species: dipole and dipolarophile follows
the trend of ∆rH. As the hardness increases it is seen that the reaction gets
faster due to decrease in activation energy. This feature is a reflection of the
“Hardness maximization principle”.
j) Enthalpy of Activation
The enthalpy of activation of the reactions (∆H)23,29
are calculated by the
deduction of sum of enthalpies of the optimized energy of the individual
reactants from the enthalpy of the transition state. The enthalpy can be
obtained from the similar calculation of the optimized individual chemical
species, and TS as stated above.
This can be expressed as;
∆H
= [H(Transition State)] – [H(reactants)] …………….(2.31)
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General methodology and theoretical approach towards chemical reactions
42
k) Free Energy of the Reaction
The free energy of the reactions (∆rG)
23,29 are calculated by the deduction of
sum of the free energies of the individual reactants from sum of the free
energies of the products. The free energies can be obtained from the
frequency calculation of the optimized individual chemical species, and the
data can be extracted from the similar process as stated in the above section.
This can be expressed as
∆rG = [G(products)] – [G(reactants)] …… (2.32)
l) Free Energy of Activation
The free energies of the reactions (∆G
)23,29
are calculated by the deduction
of sum of the free energies of the individual reactants from the free energy of
the transition state. These free energies can be obtained from the frequency
calculations of the optimized individual chemical species, and also for the
optimized TS. All the optimization and frequency calculations are done by
using the same basis as stated above.
This can be expressed as;
∆G
= [G(Transition State)] – [G(reactants)] …………….(2.33)
Using the value of free energy of the activation (∆G) in the Eyring equation,
the rate constants can be easily calculated. This also helps us to calculate
the probable products ratios from the ratio of rate constants.
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General methodology and theoretical approach towards chemical reactions
43
m) Activation Energy
The activation energies of the reactions (∆E)23,29
are calculated by the
deduction of sum of the free total electronic energies of the individual
reactants from that of the transition state.
This can be expressed as;
∆E
= [E(Transition State)] – [E(reactants)] …… (2.34)
n) Rate Constant
The Eyring equation29
of transition state theory has been applied for
determination of rate constants for elementary bimolecular reactions in the
gas phase. Following the theory of reactions rates, the rate constant for the
reaction between A and B is given by
RT
E
BA
Ba
eQQ
Q
h
Tkk
#
……………….(2.35)
in which Q represents the total partition function, for the concerned species.
A + B ⇌ AB# → Products
The bimolecular reaction is depicted in the activation energy diagram in
Fig. 2.2.
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General methodology and theoretical approach towards chemical reactions
44
Energy
Reaction co-ordinate
Reactants A+B
Products
Transition state AB#
Ea
Fig. 2.2
The total partition function Q is factorized into the various contributing
factors: rvt qqqQ .. incorporating translational, vibrational and rotational
motions. We have evaluated the component partition functions according to
their respective statistical mechanical expressions:
2/32/320
2/32/32/3232/3
10879264.1
)/(2/2
TM
TMNhkhTmkq BBt
………. (3.36)
all the terms having their usual meaning.
For the ith
mode of vibrational motion.
1)]/exp(1[ Tkhq Bii ……..(2.37)
ii
v qq … (2.38)
For a liner molecule, the rotational partition function
hcBTkhTkq BBr ))(/1(]/8)[/1()1( 2/12/122 …. (2.39)
Where, )8/( 2 chB
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General methodology and theoretical approach towards chemical reactions
45
In 3-dimensions,
CBA
B
CBABr
BBBTk
hTkq
2/3
2/322
)()/(
]/8)[/()3(
... (2.40)
CBA
rBBB
Tq
2/3027.13 …. (2.41)
where A, B, C denote the three principal components of rotation and B the
rotational constant and is a symmetry number.
The vibrational frequencies and rotational constants were taken from the
output of Gaussian calculation and were made input to a simple program and
the total partition function of each species was evaluated. Those together
with the Gaussian reported Ea value of activation energy were put into
equation (2.35) and the rate constant (k) was computed by using the simple
program from which we calculate the rate constants of the reaction at
different temperatures. For a given dipolar-dipolarophile pair of reactants,
calculations were performed for different faces (re/si-) of dipole attacked by
the different modes of approach (exo/endo-) of the dipolarophile describing
different channels of reaction.
A further plot of 1000/T vs -log(k) gave liner plot in each case, a
representative plot being shown in Fig. 2.3. Activation energy Ea was
recalculated from the slope of this plot.
2.4 2.6 2.8 3.0 3.2 3.4
23.0
23.5
24.0
24.5
25.0
25.5
26.0
-log(k
)
1000/T
Fig. 2.3
Page 55
General methodology and theoretical approach towards chemical reactions
46
o) Pauling’s Partial Bond Order
The index of Pauling’s partial bond order (PBO)1 gives the indication of
asynchronicity or synchronous, early or late nature of the TS. In the similar
investigation Magnuson et al30
. made use of the PBO in their study of
mechanism of the 1,3DC of nitrones.
The PBO is defined as1,
log10(PBO) = – (rTS-rSB)/0.71 … (2.42)
where rSB is the length of a single bond between two atoms, as present in the
product, and rTS is the length of the same bond in the TS, the atoms involved
being only of non-metallic representative 1st
row elements.
p) Charge Transfer at Transition State (CT)
Natural bond order analysis of Transition state indicates the charge transfer
(CT), which is actually the measure of transfer of electronic charge during
interaction of two reactants at the transition state. The polar model of
cycloaddition reactions are also characterized31
by dominant electrophile-
nucleophile interaction. The interaction of 1,3DC reaction can be classified
according to the CT31
calculated at transition states; the reaction is nonpolar
if CT is less than 0.15e, polar if 0.15e CT 0.4e and ionic if CT 0.4e.
Page 56
General methodology and theoretical approach towards chemical reactions
47
References
1. L. Pauling, in The Nature of Chemical Bond, Cornell University, ITHACA,
NY, 3rd
.ed. 1960, p. 239
2. R.S. Mulliken, Life of a Scientist, Springer, Verlag: New York, 1986, p. 90
3. U. Salzner, P.v.R. Schleyer, J. Am. Chem. Soc. 115 (1993) 10231.
4. M.J. Frisch et al., Gaussian 03, Revision D. 01, Gaussian Inc., Wallingford,
CT, 2004.
5. C. Peng, P.Y. Ayala, H.B. Schlegel and M.J. Frisch, J. Comput. Chem., 17
(1996) 49.
6. C. Gonzalez, H.B. Schlegel, J. Chem. Phys. 90 (1989) 2154.
7. C. Gonzalez, H.B. Schlegel, J. Phys. Chem. 94 (1990) 5523.
8. G.B. Bacskay, Chem. Phys. 61 (1981) 385.
9. R. Seeger, J. A. Pole, J. Chem. Phys. 2 (1976) 265.
10. A. Szabo and N. S. Ostlund, Modern Quantum Chemistry, McGRAW-HILL
PUBLISHING COMPANY, New York, 1982.
11. C. Møller and M. S. Plesset, Phys. Rev., 46 (1934) 618
12. F.M. Bickelhaupt and E.J Baerends, Review in Computational Chemistry,
Vol. 15, John Wiley & Sons, New York, 2000.
13. P. Hohenberg and W. Kohn, Physical Review, 136 (1964) B864.
14. W. Kohn and L. Sham, Phys. Rev., 140 (1965) A1133.
15. R.G. Parr, W. Yang, Density-Functional Theory of Atoms and Molecules,
Oxford University Press, New York, 1989.
16. J. P. Perdew and Y. Wang., Phys. Rev. B, 45 (1992) 13244.
17. A. D. Becke, Phys. Rev. A, 38 (1988) 3098.
18. A. D. Becke, J. Chem. Phys., 98 (1993) 1372.
19. A. D. Becke, J. Chem. Phys., 98 (1993) 5648.
20. A.E. Reed, L.A. Curtiss, F.Weinhold, Chem. Rev. 88 (1988) 899.
21. K. B. Wiberg, Tetrahedron 24 (1968) 1083.
22. P. Pérez, L.R. Domingo, A. Aziman, R. Contreras, Theoretical Aspects of
Chemical Reactivity, ed. A. Toro-Labbe, Elsevier Science, New York, 2007.
23. K.J. Laidler, Chemical Kinetics, PEARSON Education Inc. 3rd
ed. 2009.
24. P. K. Chattaraj, G. R. Roy, Chem. Rev. 107 (2007) PR46.
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General methodology and theoretical approach towards chemical reactions
48
25. P.K. Chattaraj, A. Cedillo, R.G. Parr and E.M. Arnett, J.Org.Chem., 60
(1995) 4707.
26. P.K. Chattaraj, U. Sarkar, D.R. Roy, Chem.Rev. 106 (2006) 2065.
27. K. Fukui, Theory of Orientation and stereoselection, Springer: Rerlin, 1973.
28. P. Pérez, L.R. Domingo, M.D. Norena, E. Chamorro, J. Mol. Struct.:
THEOCHEM 859 (2009) 86.
29. D.A. McQuarrie, J.D. Simon, Physical Chemistry, Viva Books Private
Limited, First South Asian Edition, 1998.
30. E.C. Magnuson and J. Pranata, J. Comput. Chem. 1998; 19, 1795.
31. L.R. Domingo and J.A. Sáez, Org. Biomol. Chem. 7 (2009) 3576.
Page 58
Chapter: 3
Studies on cyclization of azomethine
ylides with substituted alkenes
Page 59
Studies on cyclization of Azomethine ylides with substituted alkenes
50
3.1. Introduction Cycloaddition reactions are some of the most important processes from the view
point of both synthetic and mechanistic interest in organic chemistry1. Current
understanding of the 1,3-Dipolar cycloadditions (1,3DC) has grown from a fruitful
interplay between theory and experiment. The usefulness of these cycloaddition
reactions arises from their versatility and from their remarkable stereochemistry2,3
.
By varying the nature of the reagents many different types of carbocyclic or
heterocyclic 5-membered structures can be built up. Due to the importance of these
reactions, a strong effort has been directed towards the characterization of the
reagents in these cycloadditions as well as the elucidation of its reaction
mechanisms4. However, the nature of the 1,3DC reaction mechanism is still an open
problem in physical organic chemistry. The general concept of 1,3DC reactions was
introduced by Huisgen5 and co-workers in the early 1960s. Huisgen‟s work stated
the basis for the understanding of the mechanism of the concerted cycloaddition
reactions. The development of the 1,3DC reactions has, in recent years, entered a
new stage to control the stereochemistry in the addition step. It is now the major
challenge to us. The stereochemistry of these reactions may be controlled either by
choosing the appropriate substrates or by controlling the reaction using a metal
complex acting as catalyst. The concept of 1,3DC reaction was first suggested in
1983 by Smith. The chemistry of 1,3DC reaction is more than one century old.
Study of 1,3DC reactions is also historical5 and of immense interest
6 in both
academia and industry. The possible mechanism of these reactions which
encompasses those of pericyclic reactions in general, had created a lengthened
debate7 during the 1960‟s and 70‟s. The mechanism that received much attention
from Huisgen‟s group, and the picture which they drew in an convincing manner is
that of a single-step, four-centered, “no-mechanism” cycloaddition, in which the two
new bonds are both partially formed in the transition state, although not necessarily
to the same extent (Fig. 3.1.A). But it is nevertheless hoped to cover the vast
majority of these reactions, while it is finally recognized that a duality of mechanism
may exist in the field as a whole.
One the other hand, R. A. Firestone6 and his group proposed a two step reaction
mechanism instead of one step pathway with a discrete intermediate, a spin-paired
Page 60
Studies on cyclization of Azomethine ylides with substituted alkenes
51
diradical, with the first step being rate determining (Fig. 3.1.B). The stereochemical
facts imposed upon this mechanism by further restriction of the activation energies
for both advance and retrograde motion along the reaction coordinate from this
intermediate is very small, smaller in fact than that for rotation around a single bond.
Huisgen gave a experimental evidence of the 1,3DC reaction of benzonitrile oxide
with trans-dideuterated ethylene which gave only and exclusively the trans-
isoxazoline (Fig. 3.1.C). As the diradical intermediate would allow for a 180
rotation of the terminal bond and would thus be expected to yield a mixture of cis
and trans isomers6. On this basis of the stereospecificity of the 1,3DC reaction, the
dispute was ultimately settled in favour of concerted mechanism.
Fig. 3.1(A-C)
Reactants Transition State Products
C
.a
a abbb
c c
d d d ee e
+ -B
Firestone’s Diradical Mechanism
Reactant Transition State Product
a b+
c-
d e
ab
c
d e
ab
c
d e
A
Huisgen’s Concerted Mechanism
Ar C N O+
+ CC
D
D
N
O
C
C
C
D
D
Ar
Only product
C
Benzonitrile oxide Trans-dideuterated ethylene
Huisgen’s Experimental evidence
Page 61
Studies on cyclization of Azomethine ylides with substituted alkenes
52
The 1,3DC reaction of azomethine ylides with alkenes leads to the formation of the
pyrrolidines. A number of methods have been developed for the generation of
azomethine ylides, such as proton abstraction from imine derivatives of α-amino
acids, thermolysis or photolysis of aziridines, and dehydrohalogination of imonium
salts.
3.2. Computational Method
In recent years, theoretical methods based on the Density Functional Theory (DFT)8
have emerged as an alternative to traditional ab initio methods in the study of
structure and reactivity of chemical systems. Diles–Alder (DA) and 1,3DC reactions
have been the object of several DFT studies that include gradient corrections and
hybrid functional for exchange and correlation, such as B3LYP9,10
, together with the
standered 6-31G11
basis set which yields potential energy barrier in good agreement
with experiment. All our calculations are carried out on a Silicon Graphics
Workstation - Octane/2 employing the UNIX version of Gaussian0312
together with
Gaussview03. Energies of the isolated reactant moieties and the product (adduct) are
individually optimized to their respective equilibrium structures using the DFT/
B3LYP option. Considering the complexity of the reacting systems, we have
adopted the 6-31G(d) basis set throughout all our calculations since such
calculations are known to produce good ground state. We have routinely performed
accurate the single point energy calculations with the basis 6-311+G(d) at the
equilibrium structures previously optimized with 6-31G(d) basis. All the reacting
systems are studied by locating the correct TS through vibrational analysis
producing only one imaginary frequency followed by an Intrinsic Reaction
Coordinate (IRC) calculation, in each case. This would ensure that the potential
energy curve connecting the optimized reactants and the products passes through the
correct and lowest TS which are a first order saddle point. The TS structure
optimization is achieved through setting the option QST3 in the optimization step of
Gaussian program, which employs a synchronous transit quasi Newton (STQN)
procedure13
for locating the TS. Barrier height E≠ for the forward reaction is taken
as the difference of the sum of energies of isolated reactants and the energy of the
Page 62
Studies on cyclization of Azomethine ylides with substituted alkenes
53
optimized TS. In the same manner, the free energy of activation G≠ are calculated
from a similar difference of Gibb‟s free energies at 298K and have been included in
the same table in the text. The enthalpy rH and free energy rG of reaction are
calculated at 298K and provided in the table 3.4. While exploring the nature of TS,
we have calculated the index of Pauling‟s14
partial Bond Order (PBO) as explained
in chapter 2 by the equation 2.42. Magnuson et al.15
who also used the PBO values
in their similar study of nitrones.
3.3. Results and Discussion
The backbone structure of the 1,3-dipole, azomethine ylides is shown in Fig. 3.2.
C N+
C1 32
Fig. 3.2
The azomethine ylides are less stable and prepared in situ so it is very difficult to
study the property of the reactants and also the reaction experimentally, but the
theoretical computational study can be done easily. Again, the reactions of 1,3DC
reactions of ylides are relatively less explored than the nitrones moiety. In 1985
Padwa et al16
. published the first diastereofacial selective 1,3DC reaction of chiral
azomethine ylides with alkenes leading to optically active products. The chiral
template for the azomethine ylide has been further developed to form a chiral cyclic
product by Harwood et al17
. We have performed DFT calculations to rationalize the
reactivity, regioselectivity, enantioselectivity and diasteriofacial selectivity in the
context of 1,3DC reactions of a few acyclic and two cyclic azomethine ylides (AY)
leading to enantiomeric/ diasteriomeric excess of the products18
. In particular, N-
substituted and C-substituted AYs have been considered for reactions with the
substituted ethylenes, maleimide, maleic anhydride and methyl acrylate18
. Different
azomethine ylides (AY) reactants and dipolarophiles are abbreviated in Table 3.1.
Page 63
Studies on cyclization of Azomethine ylides with substituted alkenes
54
From an analysis of the results of calculation for the selected reactions, the regio-
and exo/endo- stereoselectivity have been explained. Reactions are followed through
transition state (TS) structure optimization, calculation of reactivity parameters and
activation barriers. Computed data have been provided in the annexure 1.
A rationalization of the trends in regioselectivity and enantioselectivity is attempted
with the help of HOMO-LUMO energies, electrophilicity differences ( ω) and the
related thermodynamic parameters of the reactants and for TS. Considering the need
for stereo-specific synthesis of the cycloadducts, theoretical characterization of the
probable products and a study of the preferred reaction path will be of much value.
In spite of the broadly accepted point of compromise on the question of concerted or
biradical mechanism, continued efforts18-24
in reconciliation between the theory and
experiment are still going on.
Table 3.1 The reactants and their abbreviations:
---------------------------------------------------------
Reactant Abbreviation
CH2NHCH2 = 1AY
CH2=CH2 = 1EN
CH2N(CH3)CH2 = 2AY
CH2CH(CH3) = 2EN
CH2N(C2H5)CH2 = 3AY
CH2CH(C2H5) = 3EN
CH2N[C(CH3)3]CH2 = 4AY
CH2CH[C(CH3)3] = 4EN
N
CH2
OO
+ H
= 5AY CH2CHCOOCH3 = 5EN
N
CH2
OO
+ H
H
Ph
= 6AY
maleimide = 6EN
maleicanhydride = 7EN
------------------------------------------------------------
We have taken interest in the present study because 1,3DC reactions of AYs are
relatively less explored compared to those of the nitrones. It has been found that the
1,3DC reaction of AYs is extensively used as an efficient regio- and stereo-
Page 64
Studies on cyclization of Azomethine ylides with substituted alkenes
55
controlled method for synthesis of pyrrolidine and pyrrole containing cyclic or
bicyclic natural and bio-organic compounds25
with a very high or complete
selectivity. The present study helps us to understand the phenomenon of regio- and
enantio- selectivity through ground state DFT26
calculations since such calculations
yield potential energy barriers in good agreement with experiment. It is known that
the control of stereochemistry in the addition step leads to enantioselectivity and
diastereoselectivity of the product. The stereospecificity dispute was finally settled
in favour of concerted, synchronous and early transition state (TS)27
.
The TS, according to Huisgen28
, is concerted for pericylic reactions. Dewar29
has
suggested to the TS be asynchronous and aromatic. Fukui30
has attributed the control
of 1,3DC to the Frontier Molecular Orbitals (FMOs) of substrates. We have
incorporated the FMO energies of the reacting species in Table 3.2. It should be
pointed out that in terms of second order perturbation theory the interaction energy
depends on the HOMO-LUMO energy gap between different species and this value
appears in the denominator of the perturbation energy expression.
Table 3.2 Energies of the frontier orbitals and related descriptors in eV.
---------------------------------------------------------------------------------------
Reactanting
systems HOMO LUMO
----------------------------------------------------------------------------------------
1AY -4.05 0.42 -1.82 4.47 0.371
1EN -7.26 0.51 - 3.38 7.77 0.735 0.364
2AY -3.94 0.35 -1.80 4.29 0.378
2EN -6.80 0.77 -3.02 7.47 0.602 0.224
3AY -3.89 0.39 -1.75 4.28 0.358
3EN -6.77 0.83 -2.97 7.60 0.580 0.222
4AY -3.82 0.37 -1.73 4.19 0.357
4EN -6.79 0.75 -3.02 7.54 0.605 0.248
5AY -5.25 -1.35 -3.30 3.90 1.396
5EN -7.40 -1.23 -4.32 6.17 1.512 0.116
6AY -5.09 -1.24 -3.17 3.85 1.305
6EN -7.46 -2.72 -5.09 4.74 2.733 1.428
6AY -5.09 -1.24 -3.17 3.85 1.305
7EN -8.15 -3.19 -5.67 4.96 3.241 1.936
-------------------------------------------------------------------------------------
Page 65
Studies on cyclization of Azomethine ylides with substituted alkenes
56
In our present work we have considered several C- and N- substituted AYs as the
dipole, which react with the symmetrically substituted ethylenes like maleimide and
maleic anhydride and also with the unsymmetrically substituted ethylene like
methylacrylate18
. Experimental results for the reaction of cyclic ylides 5AY and
6AY with maleimide and maleic anhydride are available31,32
. This data provides the
evidence that endo- isomer is produced in diastereoselective excess of the exo-
isomer. A systematic scheme for this cycloaddition reaction has been very concisely
worked out by Belzecki et al33
.
We have carried out theoretical calculations following their scheme and enumerated
results which are given in subsequent sections. Several workers18-24
have explored
the 1,3DC reactions by DFT employing the associated tools of hardness and
softness. Chattaraj et al.34,35
have extensively reviewed the subject over many
diverse facets of reactive and physicochemical processes with the help of
electrophilicity index defined earlier by Parr et al.26
It is attractive from the purview
of organic chemist to examine the proximity of TS to the reactant or product over
the reaction coordinate. In this regard the Hammond postulate36
says that TS for
exothermic reactions are reactant-like, and for endothermic it is product-like.
We can expect that FMO effects will be particularly strong in exothermic reactions.
Global electrophilicity ( ), chemical potential ( ) and hardness ( ) parameters for
the AY-alkene systems have been calculated (Table 3.2) to interpret their reactivity.
We have performed through the energy minimization procedure using DFT
8
calculations and optimized the geometries of reactants, products and the TS. We
have calculated the quantum chemical parameters like frontier orbital energies
(Table 3.2), bond order (Table 3.3) and the thermo-chemical parameters like the
energy of activation, free energy of activation, the enthalpy ( rH) and free energy
( rG) of reaction (Table 3.4).
Page 66
Studies on cyclization of Azomethine ylides with substituted alkenes
57
3.3.1. Reaction of Acyclic Azomethine Ylides with Alkenes
This section describes the reactions between (i) the simplest azomethine
ylide (1AY) and ethylene (1EN), (ii) the N-methyl substituted azomethine ylide
(2AY) and propene (2EN), (iii) the N-ethyl substituted azomethine ylide (3AY) and
1-butene (3EN) and (iv) the N-tert substituted azomethine ylide (4AY) and 3,3-
dimethyl-1-butene (4EN). In this section we have abbreviated the names of our
1,3DC reactants in Table 3.1. For all these reacting systems we have explored the
different approaches (exo- and endo-) of dipole towards the re- and si- faces of the
alkene (dipolarophile) as the four possible reactive channels. The systems are
labeled for the different channels of reaction according to scheme 3.1. Structural
symbols for the various products (psx, prx, psn, prn) together with their
corresponding TS (tsx, trx, tsn, trn) are shown in the scheme so as to identify the
various stereochemical species. We have followed the structural naming system:
[(product/ts)(re/si)(exo/endo)] for the product and/or transition state configurations.
For some approaching orientation of reactants, the structural naming system:
[(re/si)(exo/endo)] has been used18
. For the simplest azomethine ylide 1AY reacting
with ethylene 1EN, there will be expectedly no stereospecificity of the products due
to symmetry of the reacting species. According to scheme 3.1 and Fig. 3.3 the
dipolarophile (alkene) having only one prochiral center is placed in the middle of
figure to distinguish between the exo- and endo- approaches of dipole on the re- and
si- faces of the dipolarophile. Evidently, for the other achiral ylides 2AY-4AY and
achiral alkenes 2EN-4EN only two stereoisomeric reactive channels : the exo- and
endo-, out of all four probable channels, will be feasible because exo- attack on the
re- and si- faces lead to the same energy of TS and similar thing occurs for the endo-
channels of attack (Table 3.4). This particular feature of energetic identity is more
prominent with the results of DFT/B3LYP with 6-31G(d) basis. This feature is
obviously a consequence of symmetrical structures of the reactants which we have
practically observed through calculations over all the four channels. It may be noted
from Table 3.4 that for the system 2AY-2EN, the product energies are same in all
the channels, but activation energies differ in the exo- and endo- channels only,
irrespective of si-/re- faces.
Page 67
Studies on cyclization of Azomethine ylides with substituted alkenes
58
Scheme 3.1 Azomethine ylide(N-AY) and Alkene (N-EN)a:
Configuration of approaching Structure symbol Structure symbol Structure
symbol reactants of reactants of products of TS
si-face of ene + exo-ylide Nsx Npsx Ntsx
si-face of ene + endo-ylide Nsn Npsn Ntsn
re-face of ene + exo-ylide Nrx Nprx Ntrx
re-face of ene + endo-ylide Nrn Nprn Ntrn a
N=2,3,4 for different reacting AY-EN systems. Both exo- & endo- approaches on a particular
face give structurally the same product. The acyclic AYs do not present diastereoselectivity
because they have a symmetry plane.
H2C
N
CH2
+
-
R
RC
H
CH2
CH2
N
CH2
+
-
R
trx
tsx
N
R
R
H
N
R
RH
pr
ps
(R)
(S)
CH2
N
CH2
+
-
R
RC
H
CH2
CH2
N
CH2
+
-
R
trn
tsn
N
R
R
H
N
R
RH
pr
ps
(R)
(S)
[R= H, CH3-, C2H5-, (CH3)3C-]
Fig. 3.3 Transition states and products in the different facial approaches (re- and si-) on the
various substituted ethylenes by the acyclic AYs along exo and endo- paths.
Suitable schemes (scheme 3.1-3.4) are employed to define the various reaction
channels from reactants to specified products.
It may be noted from Table 3.3 that very low PBO values and larger interatomic
distances rC-C for the newly forming bonds in the TS indicate the existence of an
early transition state, as has been similarly found by Domingo37
in connection with
azomethine ylides. Following Fukui, an analysis of the HOMO-LUMO energy
values in Table 3.2 indicates that the reactions are favourably controlled through the
interaction of HOMO of the ylides 1AY, 2AY, 3AY, 4AY respectively with the
LUMO of dipolarophiles 1EN, 2EN, 3EN, 4EN. The control for such reactions is
indeed not solely with the FMOs, but certain other parameters like hardness and
electrophilicity38-40
having definite dependence on the HOMO and LUMO may have
more direct influence on the control. From the results of calculation we observe that
in absence of electron withdrawing groups on the alkene in all the three acyclic AY
Page 68
Studies on cyclization of Azomethine ylides with substituted alkenes
59
systems (2-4), the exo- path involves lesser energy and enthalpy of activation in
Table 3.4 than the endo- path on both re- and si- faces. The products (pr) and (ps)
differing in chirality are obtained in major yields through the exo- path (Fig. 3.3, left
portion).
Table 3.3 Structural parameters of transition states.
Ylide Ene str. symb rc-c in TS (A ) PBOs
1AY 1EN 1ts 2.53, 2.53 0.04, 0.04
2AY 2EN 2trx 2.50, 2.53 0.05, 0.04
2AY 2EN 2trn 2.49, 2.50 0.05, 0.04
2AY 2EN 2tsx 2.50, 2.54 0.05, 0.04
2AY 2EN 2tsn 2.49, 2.50 0.05, 0.04
3AY 3EN 3trx 2.49, 2.46 0.05, 0.05
3AY 3EN 3trn 2.48, 2.45 0.05, 0.05
3AY 3EN 3tsx 2.49, 2.46 0.05, 0.05
3AY 3EN 3tsn 2.48, 2.45 0.05, 0.05
4AY 4EN 4tsx 2.61, 2.43 0.03, 0.06
4AY 4EN 4tsn 2.59, 2.39 0.04, 0.06
4AY 4EN 4trx 2.61, 2.43 0.03, 0.06
4AY 4EN 4trn 2.59, 2.39 0.04, 0.06
5AY 5EN 5tsx 2.25, 2.73 0.11, 0.02
5AY 5EN 5tsn 2.24, 2.78 0.11, 0.02
5AY 5EN 5trx 2.28, 2.73 0.11, 0.02
5AY 5EN 5trn 2.26, 2.73 0.11, 0.02
5AY 5EN 5tsx-r 2.29, 2.49 0.09, 0.05
5AY 5EN 5tsn-r 2.29, 2.49 0.09, 0.05
5AY 5EN 5trx-r 2.29, 2.49 0.09, 0.05
5AY 5EN 5trn-r 2.29, 2.49 0.09, 0.05
6AY 6EN 6trx 2.58, 2.38 0.03, 0.07
6AY 6EN 6trn 2.60, 2.34 0.04, 0.08
6AY 7EN 7trx 2.37, 2.56 0.07, 0.04
6AY 7EN 7trn 2.54, 2.35 0.05, 0.08
-------------------------------------------------------
Here both the exo- and endo- attacks on the re- face of alkene generate only one and
the same stereoisomer (pr) with configuration R at the chiral centre. Similarly, on
the si- face both exo- and endo- attacks generate only one and the same stereoisomer
(ps) with configuration S at the chiral centre. Using ethylene (1EN) and the simplest
azomethine ylide (1AY) we have calculated the TS in which both the C-C distances
are 2.533 Å. We have also noticed that the energy of activation ( E≠), enthalpy of
activation ( H≠) and free energy of activation ( G
≠) increase systematically as in
Page 69
Studies on cyclization of Azomethine ylides with substituted alkenes
60
Table 3.4 with increasing size of alkyl substituents (Table 3.1), whether on the N-
alkyl site of the AY or on the alkene. While the exo- path is favoured over the endo-
path on both faces of the dilpolarophile, the difference in activation barriers between
the two paths also increases with size of the substituent, making the exo- way of
product formation more facile18
.
3.3.2. Reactions of Cyclic Azomethine Ylides with Alkenes Bearing
Electron Withdrawing Substituents
In this section we present the results of our calculation for the reaction of the
dipolarophiles methylacrylate, maleimide and maleic anhydride with the cyclic
azeomethine ylides18
5AY and 6AY as prepared by A.S. Anslow et al31,32
for which
experimental reports are available. The different approaches (exo- and endo-) of the
dipolarophile towards the re- and si- faces of the AY are labeled according to the
schemes 3.2-3.4 and depicted in Figs. 3.4-3.6.
O
O
N
Co
C O
re face exo attack
si face exo attack
tsx
trx
OMe
OMe
o
No
H
H
OMinorproduct
S
OMe
S
o
No
H
H
OMinorproduct
R
OMe
R5prx
5psx
H
(A)
OO
N
C
oMeO
CO
MeO
re face endo attack
si face endo attack
tsn
trn
o
No
H
H
OMajorproduct
OMe
S
R
o
No
H
H
OMajorproduct
R
OMe
S
5psn
5prn
H
Fig. 3.4. (A) Transition states and products in the different facial approaches (re- and si-) on
the cyclic AY (5AY) by the methyl acrylate (5EN), along exo- and endo- paths
producing the normal adducts.
Page 70
Studies on cyclization of Azomethine ylides with substituted alkenes
61
O
O
N
C
o
C O
re face exo attack
si face exo attack
OMe
OMe
o
N
o
H
H
OMajorproduct
R
OMe
S
o
N
o
H
H
OMinorproduct
R
OMe
S
tsx-r
trx-r
5psx-r
5prx-r
H
(B)
O
O
N
Co
MeO
CO
MeO
re face endo attack
si face endo attack
o
N
o
H
H
OMajorproduct
R
OMe
R
o
N
o
H
H
OMinorproduct
S
OMe
S
tsn-r
trn-r
5psn-r
5prn-r
H
Fig. 3.4. (B) Transition states and products in the different facial approaches (re- and si-) on the
cyclic AY (5AY) by the methyl acrylate (5EN), along exo- and endo- paths
producing the regio-isomeric adducts
.
O
O
N
O
O
Ph
N
H
o
N
N
o
o
H
H
HPh
O
exoattack
R
R
R
S
on re face
MinorProduct
O
O
N
O
O
Ph
N
H
o
N
N
o
o
H
H
HPh
O
endoattack
Majorproduct
R S
R R
on re face
Fig. 3.5 Transition states and products in the attacks on re- face of the cyclic AY (6AY) by
maleimide (6EN) along exo- and endo- paths.
O
O
N
O
O
Ph
H
o
No
o
H
H
HPh
O
exoattack
No producto
o
S R
R Ron re face
O
O
N
O
O
Ph
H
o
No
o
H
H
HPh
O
endoattack
Only product
o
o
R S
R Ron re face
Fig. 3.6 Transition states and products in the attacks on re- face of the cyclic AY (6AY) by
maleic anhydride (7EN) along exo- and endo- paths.
In each case the AY, having only one prochiral carbanionic center, is placed in the
middle of figure between the re- and si- face approaches of the dipolarophiles.
Structures of the various products (psx, prx, psn, prn) together with their
Page 71
Studies on cyclization of Azomethine ylides with substituted alkenes
62
corresponding TS (tsx, trx, tsn, trn) are shown in the figures to identify the various
stereochemical species. We have followed a similar naming system as that used in
the section 3.2.1. The question of regioselectivity in the matter of 1,3DC has been
adequately addressed41,42
by Aurell et al. in terms of TS calculations and
electrophilicity approach. In our present calculations two probable regio-isomers
(Figs. 3.4A, 3.4B) of product can arise when orientations of the substituent group
(-COOMe) of the attacking alkene 5EN are closer to or away from the carbanionic
centre of the ylide 5AY. For the regioisomers where the ester group is far away, we
have used the extra notation -r in the suffix of symbols. In this sense the cyclic ylide
5AY can have two additional regioisomeric channels due to asymmetry of this AY
adducts: 5psx, 5prx, 5psn, 5prn and the four –r (regio) isomers18
.
Scheme 3.2 Azomethine ylide(5AY) and Methylacrylate(5EN): Configuration of approaching Structure symbol, Structure symbol, Structure symbol,
reactants reactants products TS
si-face of ylide + exo-ene 5sx 5psx 5tsx
si-face of ylide + endo-ene 5sn 5psn 5tsn
re-face of ylide + exo-ene 5rx 5prx 5trx
re-face of ylide + endo-ene 5rn 5prn 5trn
si-face of ylide+ exo-ene (regio) 5sx-r 5psx-r 5tsx-r
si-face of ylide+ endo-ene (regio) 5sn-r 5psn-r 5tsn-r
re-face of ylide+ exo-ene (regio) 5rx-r 5prx-r 5trx-r
re-face of ylide+ endo-ene (regio) 5rn-r 5prn-r 5trn-r
Scheme 3.3 Azomethine ylide(6AY) and Maleimide(6EN)b:
Configuration of approaching Structure symbol, Structure symbol, Structure symbol,
reactants reactants products TS
re-face of ylide + exo-ene 6rx 6prx 6trx
re-face of ylide + endo-ene 6rn 6prn 6trn
bThere is no existence of the regioisomeric product. The si- face attack is not feasible,
computationally.
Scheme 3.4 Azomethine ylide(6AY) and Maleic anhydride(7EN)c:
Configuration of approaching Structure symbol, Structure symbol, Structure symbol,
reactants reactants products TS
re-face of ylide + exo-ene 7rx 7prx 7trx
re-face of ylide + endo-ene 7rn 7prn 7trn
cThere is no existence of the regioisomeric product. The si- face attack is not feasible,
computationally.
Page 72
Studies on cyclization of Azomethine ylides with substituted alkenes
63
Both methylacrylate (5EN) and the azomethine ylide 5AY described in Table 3.1
are achiral and possessing prochiral centers. They are considered for 1,3DC reaction
according to scheme 3.2. Here each of the possible products contains two chiral
centers, one coming from the dipole and one from the dipolarophile as presented in
Figs. 3.4A, 3.4B. So there should exist eight regio-stereo isomers all together among
the products since two chiral centers are being introduced. It is seen from the results
of calculation in Table 3.4 that the exo- path involves lesser activation energy on si-
face (5tsx<5tsn), while both endo- and exo- TS are energetically comparable on re-
face (5trx 5trn), both the products having lesser activation energy than those on the
si- face. Therefore, it appears that 5prn and 5prx should be the major
diasteriofacially selective products. For the regioisomeric approach it is found
computationally that endo- path on both the si- and re- faces have lesser energy,
enthalpy and free energy of activation in Table 3.4 than those in the exo- path. From
the values of activation energy, enthalpy and free energy of activation it could be
inferred that 5prn-r should be the major stereoselective product presented in Fig.
3.4B.
Mechanism of Diles-Alder as well as 1,3DC reactions has been very elaborately
studied by Domingo et al43-46
. They have also investigated the influence of Lewis
Acid46
on these reactions. We have taken up the cycloaddition reaction between
6AY and 6EN following the TS optimization procedure along the different channels
and have been able to calculate the thermodynamic parameters accurately. The
cycloaddition reaction between the ylide 6AY and maleimide 6EN can be described
with the help of Table 3.1 and scheme 3.3. There is one chiral centre already present
in 6AY and three new centers, one at the prochiral carboanionic atom of 6AY and
two at the ethylenic centers of 6EN, are being formed during cycloaddition. Among
the eight (23) stereoisomeric possibilities only two reaction modes viz. the exo- and
endo- channels on the re- face of the AY have been shown in Fig. 3.5. Two other
modes of approach corresponding to regio- attack on this face do not give rise to
new products due to the symmetric nature of 6EN. In consequence only enantio- and
diastereo- selectivity are presented but no regioselectivity is observed for the
symmetric alkenes 6EN and 7EN. A si- face attack on 6AY is not computationally
Page 73
Studies on cyclization of Azomethine ylides with substituted alkenes
64
feasible probably due to the presence of Ph- group on the attacking side of the dipole
6AY which would hinder sterically the approaching dipolarophile.
Table 3.4 Thermodynamic parameters for reactions in various orientations of attack.
-----------------------------------------------------------------------------------------------------------------
Ylide Ene str. symb. E (kcal/mol) H
G
rH
rG
*
[6-31G(d)] [6-311G+(d)] (kcal/mol) (kcal/mol) (kcal/mol) (kcal/mol) (eV) 1AY 1EN 1ts 1.19 2.91 2.27 14.50 -63.30 -49.97 4.56
2AY 2EN 2tsx 3.15 5.06 4.18 17.64 -62.51 -47.39
2AY 2EN 2tsn 3.90 6.05 4.97 18.47 -62.51 -47.39
2AY 2EN 2trx 3.15 5.06 4.17 17.64 -62.51 -47.39
2AY 2EN 2trn 3.90 6.05 4.97 18.47 -62.51 -47.39 4.71
3AY 3EN 3tsx 4.44 6.50 5.59 18.93 -56.53 -41.28
3AY 3EN 3tsn 5.48 7.69 6.68 20.57 -60.42 -44.80
3AY 3EN 3trx 4.44 6.51 5.58 17.55 -58.32 -43.25
3AY 3EN 3trn 5.48 7.72 6.68 20.57 -60.42 -44.80 4.72
4AY 4EN 4tsx 5.68 8.02 6.65 20.30 -60.55 -46.41
4AY 4EN 4tsn 7.96 10.93 9.06 22.77 -61.57 -45.17
4AY 4EN 4trx 5.68 8.11 6.65 20.25 -56.33 -41.52
4AY 4EN 4trn 7.96 10.93 9.06 22.78 -61.52 -45.11 4.57
5AY 5EN 5tsx 2.97 5.16 3.94 16.59 -43.76 -28.97
5AY 5EN 5tsn 3.36 5.68 4.39 17.29 -42.77 -28.30
5AY 5EN 5trx 2.62 4.67 3.53 16.08 -42.92 -28.97
5AY 5EN 5trn 2.17 4.70 3.11 16.19 -42.61 -27.98
5AY 5EN 5tsx-r 2.81 4.59 3.84 16.88 -44.03 -30.43
5AY 5EN 5tsn-r 1.56 3.67 2.61 16.00 -40.00 -26.49
5AY 5EN 5trx-r 1.69 3.26 2.66 15.59 -40.72 -29.52
5AY 5EN 5trn-r 0.95 3.08 2.17 15.41 -43.20 -29.23 4.02
6AY 6EN 6trx 0.31 2.59 1.15 13.70 -50.86 -36.53
6AY 6EN 6trn -0.05 2.32 0.94 14.08 -45.71 -30.94 2.37
6AY 7EN 7trx -1.24 0.43 1.45 12.28 -46.21 -33.97
6AY 7EN 7trn -3.26 -0.93 0.12 10.85 -41.81 -29.00 1.90
------------------------------------------------------------------------------------------------------------------
From scheme 3.3 and Table 3.4 it may be noted that on re- face the endo- approach,
having a negative activation energy (-0.05 kcal/mol), is favored over the exo-
approach as shown in Fig. 3.5. In order to avoid a negative activation energy value,
we have calculated the same system with 6-311G +(d) basis set and in consequence
obtained a positive value presented in Table 3.4 of the activation energy (2.32
kcal/mol). Similar findings were obtained in the works of Domingo et al37
. The large
basis single point calculations incorporating diffuse functions were performed over
the previously optimized TS-geometry. Thus positive values of activation energy are
Page 74
Studies on cyclization of Azomethine ylides with substituted alkenes
65
obtained in such critical cases of negative activation energy values. The product
6prn is expected in excess as the major kinetic product over 6prx, agreeing well with
experimental data47
. Similarly, it is found for the reaction between 6AY and 7EN
(Table 3.1, scheme 3.4) that both the exo- and endo- approaches produce negative
activation energies. But when the calculations are repeated with 6-311G+(d) basis,
the results have improved to a positive value in the case of exo- attack, however a
small negative activation energy still persists for the endo- attack (Table 3.4). Again
it is also observed that the enthalpy of activation H is very small for endo- as
compared with the exo- and the free energies of activation G≠ follow a similar
trend. This observation agrees very well with the experimental achievement31,32
of
endo- as the sole product. Similar to the reaction of 6AY-6EN system, the attack by
maleic anhydride (7EN) on the si- face of ylide 6AY is also not feasible (Fig. 3.6).
Due to the highly symmetric (C2V) structure of the dipolarophile 7EN, there is no
scope for any regioisomer.
We have calculated the Gibb‟s free energies, presented in Table 3.4 for the reactants
and TS in each case and also the corresponding free energies of activation G≠ at
298K. Moreover, the heats of reaction rH and free energies of reaction rG at 298K
have been calculated according to the equations 2.30 and 2.32 under section 2.8 in
chapter 2. We observe from Table 3.4 that with increasing electron withdrawing
nature of the dipolarophiles reacting with the same cyclic ylide 6AY, the energy of
activation decreases.
3.4. Nature of The Transition State
While these cycloaddition reactions pass through a transition state; the question
remains to be answered is whether the reactions considered follow a concerted or a
diradical path. Although the general consensus in this regard was in favour of
concerted mechanism, at a certain stage R.Huisgen48
reported the well-documented
example of a step-wise 1,3DC involving an intermediate. That encouraged
Firestone‟s contention49
that „no degree of stereospecificity could rule out diradical
mechanism‟ and claiming further support for his proposal49-51
that activation energy
Page 75
Studies on cyclization of Azomethine ylides with substituted alkenes
66
for single bond rotation was greater than that for either formation of the second bond
leading to the adduct or reversion to the reactants. In this context we have calculated
the PBOs for the forming C-C bonds in the TS (Table 3.3). It can be seen that in TS
the PBOs of the two forming C-C bonds are nearly equal for less substituted AYs
and alkenes but the difference increases with increasing substitution. The bond order
difference between the two newly forming bonds increases when the alkene is
substituted unsymmetrically with a more electron withdrawing group as may be
observed in the case of methylacrylate 5EN reacting with the ylide 5AY. In the case
of symmetrically substituted alkenes like maleimide 6EN and maleicanhydride 7EN
such difference in the PBOs at the two cyclizing ends is much less. It may be
assumed that unsymmetrical substitution by electron withdrawing group on alkene
leads to a more asynchronous but concerted (Fig. 3.6) and early TS. The bond
distances (Table 3.3) are found to be of the order of 2.3-2.7 Å in all cases. When
considering the reaction 5AY-5EN (scheme 3.2 and Table 3.4) it may be observed
that regioselectivity is along the more favourable regioisomeric path in which the
more nucleophilic centre of the 5AY, the carbanionic carbon atom, attacks to the
more electrophilic centre of the 5EN, that is the betaconjugated position of methyl
acrylate (Fig. 3.4). Thus the regiomer is favoured in this case. On the basis of
classification of 1,3DC in terms of FMOs30
, the interaction of different alkenes with
AYs appear to be (Table 3.2) controlled by HOMOdipole and LUMOalkene. Further
rationale behind the preferred stereo-/regio- selectivity in the light of FMO
interactions can be gained from an analysis on the basis of global electrophilicity
index ( )26
which has been found to be more reliable52
than the FMO theory.
Accordingly, the quantities: chemical potential ( ), hardness ( ) and electrophilicity
are defined in chapter 2 and their values are obtained by the equation 2.21 and 2.24
respectively.
These quantities have been calculated for all seven reacting systems
and the results are provided in Table 3.2. Quantitative characterization of reactivity
in connection with Diels-Alder and 1,3DC reactions in terms of global
electrophilicity power has been pioneered38,40,42
by Domingo et al. In their review
Chattaraj et al.34,35
have noted that “Larger electrophilicity differences correspond to
faster38
reactions”, we have found that the values of in Table 3.2 agree very well
Page 76
Studies on cyclization of Azomethine ylides with substituted alkenes
67
with the calculated E values in Table 3.4. Similar observations may also be found
in Table 3.2 from an analysis of the hardness values of the alkenes 6EN and 7EN
which react separately with the same dipole 6AY. As the hardness increases it is
seen that the reaction gets faster due to decrease in activation energy (Table 3.4).
This feature is a reflection of the “Hardness maximization principle”. It should be
highlighted additionally that the HOMO – LUMO gap, even for different species, is
a measure of stability through the maximum hardness principle53
. Following
Koopman‟s theorem54
this quantity *
(as explained in section 2.8.a) has been taken
in our case to be the difference between LUMOalkene and HOMOdipole and the values
are provided in Table 3.4 alongside the heats of reaction rH. It appears that pair
hardness parameter for the two reacting species: dipole and dipolarophile follow the
sequence of stability ( rH), satisfying maximum hardness principle55,56
. Hard
interactions are electrostatic in nature. Charges or associated quantities such as
molecular electrostatic potentials and local hardness are supposed to be better
descriptors for hard reactions. More detailed picture regarding site selectivity in the
cycloaddition processes can be achieved from a further analysis in terms of the local
electrophilicity descriptors.
3.5. Conclusion
The detail theoretical studies have performed on the 1,3DC reactions of four acyclic
azomethine ylides with four selected alkenes viz., the substituted ethylenes and also
for two cyclic AYs with methyl acrylate, maleimide and maleic anhydride. The
experimentally found products and their relative yields have been rationalized in
terms of our energy calculations. The present energy-based approach towards the
possible mechanism of the cycloaddition reactions has led to a prediction of the
major product and also to finding an early TS in all cases, some of which have been
found to be asynchronous. Further quantification about the products ratio might be
achieved through an evaluation of the local electrophilicity descriptors and also with
the calculation of rate constants
Page 77
Studies on cyclization of Azomethine ylides with substituted alkenes
68
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22. J. Liu, S. Niwayama, Y.You and K. N. Houk, J. Org. Chem., (1998) 1064.
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Page 80
Chapter: 4
Stereoselectivity in the 1,3-dipolar
cycloaddition of 1-pyrroline-1-oxide
to methyl cinnamate and
benzylidene acetophenone
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Stereoselectivity in the 1,3DC of 1-pyrroline-1-oxide to methyl cinnamate and benzylidene acetophenone
72
4.1. Introduction
The epistemological concerns of nitrone cycloadditions have been extensively
focused on experimental approaches historically1-2
. During the last four decades,
theoretical studies have also been devoted to anticipate the bonding nature,
mechanism and energy sequences of such reactions3-10
. Few communications have
also reported their energetics and kinetics on the basis of the transition state
calculations11-15
. Nowadays, the methods based on the Density Functional theory16
have emerged as alternative to traditional ab initio methods in terms of accuracy.
Recently17
, DFT/B3LYP/6-31G* study has been carried out for the reaction of
methacrolein with 1-pyrroline-1-oxide (N1) in which the coordination of a Lewis
acid (borane) and the effect of solvent polarity (dichloromethane) were also taken
into account. P. Merino et al18
recently rationalized the observed regioselectivities of
the 1,3-dipolar cycloaddition of C-(hetaryl) nitrones to methyl acrylate and vinyl
acetate from global electrophilicity indices. The lowered asynchronicity in case of
the cycloaddition of methyl acrylate compared to vinyl acetate was highlighted on
the basis of bond lengths in the geometries of transition states. Stecko et al19,20
recently reported DFT study of 1,3DC reaction of N1 to α, -unsaturated lactones
and vinyl ethers. We have recently reported21
the DFT study of the 1,3DC reaction
of azomethine ylides with maleimide, maleic anhydride, methylacrylate and some
simple substituted alkenes. However, theoretical implications still suffer to be a
cornerstone in comparison to the experimental findings due to the limitations of
powerful computing facilities to deal with complex reacting systems.
Experimental investigation22
on the cycloadditions of N1 with two substituted
alkenes viz. methyl cinnamate (E1) and benzylidine acetophenon (E2) were carried
out by our collaborating research group, furnishing first hand information regarding
the different isolated products, their structures, yields and observed stereo-isomers.
The related supporting data on synthesis, NMR spectra, X-ray data and structure
elucidation, have been provided in the annexure 2. The different stereoisomeric
products are presented in the following.
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Stereoselectivity in the 1,3DC of 1-pyrroline-1-oxide to methyl cinnamate and benzylidene acetophenone
73
N
O
+
-
+Toluene, N
2 ,
12
34
5
6
NO
HH
HCOR
Ph1
2
34
5
6
NO
H COR
H
H
Ph1
2
34
5
6
NO
HCOR
H
Ph
H+ +
12
3
5
6
NO
H H
COR
H
Ph
+
3a 3a 3a 3a
82 0C
2psx
(I)
1psx
2psn
1psn
(II)
2prn
1prn
(III)
2prx
(IV)
1prx
R = OCH3 (E1), Ph (E2)
(R = OCH3) (R = OCH3) (R = OCH3) (R = OCH3)
(R = Ph) (R = Ph) (R = Ph) (R = Ph)
1
23
O
R 1
2
4
N1
Fig. 4.1 The different stereoisomeric products of 13DC of N1 with E1 and E2
On ground of the above findings, we decided to attempt a theoretical study of 1,3-
dipolar cycloadditions of N1 to an α, -unsaturated ketone (E2) and to an α, -
unsaturated ester (E1) (Fig 4.1) in order to assess of various factors which control
the regioselectivity and endo/exo- selectivity in these reactions so as to rationalize
them with experimental findings. The reason to select a cyclic nitrone (N1) stems
from its capability to delicately alter the diastereoselectivity of the adducts by simple
functional group alterations on the dipolarophile moiety23-27
alone. Moreover, pseudo
aza-C-disaccharides can be obtained by simple reductive ring opening of
enantiopure tricyclic isoxazolidines28
derived from N1. That the cyclic nitrone N1
can exist only in the E-isomer restricts the flexibility of addition to the nitrone end.
The results of theoretical calculation given in the present work will be useful for the
prediction of selectivities for similar other cycloadditions. The theoretical
conclusions arrived in the present work22
will be informative for the prediction of
selectivities in the N1 cycloadditions.
The present report addresses the following questions regarding the investigated
cycloadditions: (1) What will be the structure and energy of the transition states; (2)
How the experimentally observed selectivities are to be rationalized on the basis of
computational results in terms of energy, enthalpy and free energy of activation; (3)
Whether the selectivities could be judged on the basis of Global electrophilicity ( ),
Page 83
Stereoselectivity in the 1,3DC of 1-pyrroline-1-oxide to methyl cinnamate and benzylidene acetophenone
74
chemical potential ( ) and hardness ( ) parameters for the reacting systems; (4)
How the assigned structures of the isolated cycloadducts could be established with
the help of theoretical calculations.
Such a theoretically augmented experimental investigation about the alteration in
stereoselectivity would be a great advantage in understanding the process of
cycloadditions.
4.2. Computational Method
The geometries of isolated reactants, orientation complexes, transition states, and
products were optimized using the hybrid density functional B3LYP method29
, i.e.,
Becke’s three parameter nonlocal-exchange functional30
with the nonlocal
correlation functional of Lee, Yang, and Parr31
, with the 6-31G* basis set32
. The
stationary points were characterized through vibrational frequencies analysis done at
the DFT/ B3LYP/6-31G* level. All the stationary points were definitely identified
for minima (number of imaginary frequencies = 0) or transition states (number of
imaginary frequencies = 1).
Intrinsic Reaction Coordinate (IRC)33-36
calculations starting at the saddle points
were performed to verify that the potential energy curve connecting the optimized
reactants and the products passes through the correct and the lowest TS which is a
first order saddle point as defined in the chapter 3.
In this study we have studied that the theoretically calculated NMR typically benefit
from an accurate geometry and a large basis set. Cheeseman37
and coworkers have
considered the B3LYP (6-31G(d)) optimized38
structures to be the minimum
recommended model chemistry for predicting NMR properties. Hence, GIAO/SCF
1H NMR calculations of the optimized nitrones were performed at B3LYP/ 6-311 +
G (2d,p) level of approximation.
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Stereoselectivity in the 1,3DC of 1-pyrroline-1-oxide to methyl cinnamate and benzylidene acetophenone
75
4.3. Results and Discussion
We have presented our experimental and computational results for the considered
reactions in two sections.
4.3.1. Theoretical Explanation for the Cycloaddition of 1-pyrroline-1-oxide (N1)
to Methyl Cinnamate (E1) and Benzylidene Acetophenone (E2).
The electronic chemical potential is the index pointing to the direction of the
electronic flux during the cycloaddition i.e. the charge transfer (CT) occurring
within the system in its ground state. However, the chemical hardness specifies the
resistance to this electronic change flow during the cycloaddition39
and can be
quantitatively expressed in terms of HOMO and LUMO energy values according to
equations as previously stated in section 2.8.a.
The global electrophilicity index39,40
measures the stabilization in energy when the
system acquires an additional electronic charge N from the environment. The
maximum amount of electronic charge Nmax that can be accepted by an electrophile
system is given by an expression which was explain in the chapter 2, section 2.8.c.
Table 4.1 Global and local properties of the isolated dipole (N1)
and dipolarophiles (E1, E2)
Global properties
____________________________________________________________
Optimized
Energy HOMO LUMO (eV) (eV) (eV) Nmax
(a.u) (eV) (eV)
Local properties
________________________
k f+ f k (eV)
(N1) -286.540959 -5.637 -0.169 -2.903 5.468 0.771 0.531 1 0.207 0.346 0.16
2 0.028 0.034 0.02
3 0.157 0.173 0.12
(E1) -537.529587 -6.390 -1.747 -4.068 4.643 1.782 0.876
4 0.044 0.079 0.08
5 0.066 0.030 0.12
(E2) -654.034373 -6.352 -1.962 -4.157 4.390 1.963 0.946 4 0.023 0.038 0.05
5 0.053 0.029 0.10
[k is the atom site in the molecule in Figs. 4.2 & 4.3 where the property is being evaluated.]
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Stereoselectivity in the 1,3DC of 1-pyrroline-1-oxide to methyl cinnamate and benzylidene acetophenone
76
The global electrophilicity index includes the propensity of the electrophile to
acquire an additional electronic charge as well as the resistance to exchange the
electronic charge with the environment simultaneously. Thus, a good electrophile
can be characterized by a high value of and a low value of . In Table 4.1 we have
presented the HOMO and LUMO energies of N1, E1 and E2 along with their
electronic chemical potential , chemical hardness and the global electrophilicity
. According to the absolute scale of electrophilicity41
based on the index, N1 can
be classified as a moderate electrophile whereas both the dipolarophiles belong to
the realm of strong electrophiles. The electronic chemical potential value of N1 (-
2.903 eV) was higher than those of E1 (-4.068eV) and E2 (-4.157eV) implying that
the CT would take place from the dipole to the dipolarophiles in these
cycloadditions resulting in normal electron demand (NED) reactions 42,43
.
In order to understand thermodynamically the difference in diastereoselectivity due
to functional group alteration in the dipolarophile, we have calculated the Gibb’s
free energies for the reactants and TS in each case and also the corresponding free
energies of activation G≠ at 298K. Moreover, the heats of reaction rH and free
energies of reaction rG at 298K have been calculated as stated in the chapter 2 in
section 2.8.i and 2,8.l. The pair hardness44
* for the reaction of N1 with E1 was
higher than that with E2 (Table 4.2). This also reflects the enhanced exothermicity in
the former reaction which was in agreement with the calculated values of rH in
Table 4.2. This result has substantiated the accuracy of our DFT computations.
Table 4.2 Free energy and enthalpy changes along the different paths of
reaction.
Reacting
system along
channel
Free energy
of activation
G
(kcal.mol-1
)
Enthalpy of
activation
∆H
(kcal.mol-1
)
Free energy
of reaction
rG
(kcal.mol-1
)
Enthalpy of
reaction
∆rH
(kcal.mol-1
)
(eV)
(eV)
*
(eV)
1rx to 1prx
1rn to 1prn
1sx to 1psx
1sn to 1psn
29.015
27.817
29.131
27.821
11.684
09.891
11.525
09.891
1.293
3.911
2.213
2.339
-17.054
-14.893
-15.810
-15.818
0.825
1.011
3.890
2rx to 2prx
2rn to 2prn
29.421
30.474
14.841
15.963
4.556
6.338
-11.207
-09.302
1.078 1.192 3.675
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Stereoselectivity in the 1,3DC of 1-pyrroline-1-oxide to methyl cinnamate and benzylidene acetophenone
77
As the hardness increases it is observed that the chemical reaction gets faster due to
decrease in activation energy in Tables 4.2 and 4.3. This feature is a reflection of the
“hardness maximization principle44
”. It should be highlighted additionally that the
HOMO – LUMO gap, even between different species, is a measure of stability that
has been explored through the maximum hardness principle44
. Hard interactions are
essentially electrostatic in nature. In this respect charges and the associated
quantities like molecular electrostatic potential, local hardness are supposed to be
better descriptors for hard reactions.
The calculation of fukui functions for the atoms in a molecule proves to be useful to
characterize the reactive sites. The local electrophilicity index45,46
k expressed as k
= fk+ where fk
+ is the fukui function for nucleophilic attack on the k-th site. Hence
the atom-centered condensed fukui functions44
(electrophilic and nucleophilic) of the
reactants were calculated on the basis of Mulliken charges at the atomic sites in
order to rationalize the observed regioselectivities in the cycloadditions considered.
It can be seen that E1 and E2 classified as strong electrophiles, have greater local
electrophilicity for C (k = 5, Fig. 4.2 and 4.3, Table 4.1) than for Cα (k = 4, Fig.
4.2, Table 4.1). Thus, C should be the preferred site for a nucleophilic attack by the
dipole. In case of the cyclic nitrone N1, oxygen had a larger fk− than that for carbon
(Fig. 4.2, Table 4.1), which suggested that both cycloadditions should preferentially
produce isoxazolidines where C gets linked to the oxygen atom of N1. This
conclusion arrived in terms of local electrophilicity index was in conformity with the
experimental observations of this reaction E1 and N1 and also for the reaction E2
with N1 in this section (Fig. 4.3).
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Stereoselectivity in the 1,3DC of 1-pyrroline-1-oxide to methyl cinnamate and benzylidene acetophenone
78
Table 4.3 Optimized energies of the orientation complexes and activation energies
of the transition states. No regioisomer was obtained computationally in
both the cycloadditions.
Configuration of
approaching reactants
Optimized
Energy of the
orientation
complex
(a.u)
Optimized
Product
energy
(a.u)
Transition state
Transition
states
Optimized
energy
(a.u)
Activation
Energy
(kcal.mol-1
)
N1 (re face) + E1 (exo-)
[1rx]
N1 (re face) + E1(endo-)
[1rn]
N1 (si face) + E1(exo-)
[1sx]
N1 (si face) + E1(endo-)
[1sn]
N1 (re face) + E2 (exo-)
[2rx]
N1 (re face) + E2 (endo)
[2rn]
-824.080106
-824.075109
-824.084113
-824.079892
-940.583942
-940.585683
-824.095922 [1prx]
-824.092480 [1prn]
-824.093922 [1psx]
-824.093884 [1psn]
-940.597683 [2prx]
-940.594728 [2prn]
1trx
1trn
1tsx
1tsn
2trx
2trn
-824.046961
-824.049917
-824.047345
-824.049917
-940.553142
-940.550928
14.775
12.893
14.775
12.893
13.805
15.060
4.4. Exploring the Transition State
We considered it convenient to attempt the transition state optimizations on the basis
of a concerted mechanistic approach carried out through DFT based calculations.
Our computations showed remarkable agreement with the experimental findings.
We were successful in locating the true transition states through vibrational
frequency analysis. Each such transition state corresponded to a single imaginary
frequency. From further IRC calculations33-36
, it was apparent that these transition
states connected the corresponding orientation complexes to the respective
cycloadducts. Consequently, we could relate the geometries of the orientation
complexes to those of the transition states and adducts for the systems being
considered. The two reacting systems N1-E1 and N1-E2 studied presently are
denoted by numbers (N) 1 and 2 respectively. For describing the different structures
of the approaching reactants (r), transition states (t) and the products (p), a
convenient naming system has been employed as in the previous chapter 3. The
generation of different product isomers with time and in that matter their product
ratios at different time intervals are presented in scheme 4.1, following the same
kind of notations and symbols as used in the previous chapter 3.
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Stereoselectivity in the 1,3DC of 1-pyrroline-1-oxide to methyl cinnamate and benzylidene acetophenone
79
Scheme: 4.1 IV/2psx : III/2psn=64:36 after 4hours
IV/2psx : III/2psn=64:36 after 14 hours III /1prn : IV/1prx = 89:11 after 4 hours III /1prn : IV/1prx = 87:13 after 8 hours III /1prn : IV/1prx = 65:35 after 14 hours
In this context, we also calculated the index of Pauling’s47
partial Bond Order (PBO)
as explained in the previous section 2.8.o. The C-C and C-O bond distances were
found to be 1.964 Å and 2.173 Å respectively (Table 4.4) for both faces of attack in
the endo-transition state for the reaction between N1 and E1. The comparable values
of PBOs ((PBO)C-O = 0.182 and (PBO)C-C = 0.143) were indicative of a
synchronous, concerted mechanism. Similar results were also observed for the
cycloaddition between N1 and E2 (Table 4.4).
Table 4.4 Bond distances and partial bond order values in transition states Transition
state rc-o (Å) (PBO)c-o rc-c (Å) (PBO)c-c
1trx
1trn
1tsx
1tsn
2trx
2trn
2.033
1.964
2.009
1.964
2.067
1.884
0.136
0.182
0.148
0.176
0.134
0.223
2.128
2.173
2.158
2.173
2.097
2.208
0.153
0.143
0.136
0.127
0.177
0.123
N
O
H
MeOOC
3 +N
I/1sn
4
5
4
5
1
I/1trn
I/1tsn
I/1prn
I/1psn
I/1rn
2
Ph
Ph
COOMe
Ph
N
O
H
MeOOC
Ph
COOMe
O
Fig. 4.2 Endo attack by E1 on re- and si- faces of N1.
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Stereoselectivity in the 1,3DC of 1-pyrroline-1-oxide to methyl cinnamate and benzylidene acetophenone
80
4.5. Selectivity and Reactivity of the Cycloadditions
Houk and Coworkers10,11
have gleaned a number of generalizations about the
molecular orbitals of 1,3-dipoles and dipolarophiles from their observation on results
of calculations and experimental facts. It is evident from our calculated HOMO and
LUMO energy differences that the present cycloadditions are favourably controlled
through HOMOdipole–LUMOdipolarophile frontier type interaction9,11,48,49
.
The cyclic nitrone N1 only can exist as the E isomer and was
considered as such in the calculation of transition states. Both the dipolarophiles E1
and E2 exist exclusively in trans- forms. The transition state optimization for the
corresponding regio- attacks were also computed. But, those results were not in
agreement with the experimental findings for both the reactions. Such computation
for regio- isomers had always terminated to unrealistic structures of the TS and to
wrong activation energies. In several calculations, DFT method predicted a different
regioisomer due to only small differences in calculated energy. Domingo et al50
also
reported about this deficiency of transition state calculations to predict the
experimental regioselectivities of 1,3DC reactions. On the other hand, the
regioselectivities were better predicted by the local electrophilicity index (Table 4.1)
and were found to be in good agreement with our experimental observation. So, we
were left with calculating four possible adducts (I-IV) involving both exo- and endo-
approaches to the re- and si- faces of N1 for each cycloaddition leading to the
generation of 3-substituted cycloadducts (Fig. 4.1). In Fig. 4.2, 1rn and 1sn were the
orientation complexes for the endo- approach of E1 to the re- and si- faces
respectively of N1 leading to the products 1prn and 1psn for the reaction between
N1 and E1. Similarly in Fig. 4.3, 2rx and 2sx were the orientation complexes for the
exo- approach of E2 to the re- and si- faces respectively of N1 leading to products
2prx and 2psx for the reaction between N1 and E2 in Fig. 4.3. The transition states
1trn and 1tsn in the former reaction are related to the products 1prn and 1psn
respectively of the isomer type-I. On the other hand, 2trx and 2tsx in the latter
reaction were the transition states for 2prx and 2psx respectively of the (Fig. 4.3)
isomer type- II. In the cycloaddition between N1 and E1, the calculated endo-
reaction path provided transition states (1trn and 1tsn) having fairly lower activation
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Stereoselectivity in the 1,3DC of 1-pyrroline-1-oxide to methyl cinnamate and benzylidene acetophenone
81
energy than those in the corresponding exo- path (1trx and 1tsx) on both faces. In
spite of redundancy due to molecular symmetry, the computations were carried out
for both the faces to justify the accuracy of the structures and it was found that the
computation results on both faces were identical (Table 4.3). The product 1psn or
1prn was obtained as the major cycloadduct (Table 4.5) through the endo- path.
Table 4.5
Stereoisomeric ratios were obtained experimentally for the cycloadditions of N1 to E1and
E2. The cycloadditions were carried out at 82˚C in toluene under nitrogen atmosphere.
On the ground of structural symmetry, it is expected that the results of calculation
would be equivalent between the structures I and IV and also between II and III
(Figs. 4.2 and 4.3). While discussing exo/endo- selectivity, we focus our attention to
the structures III and IV only, which provide understanding of the products ratios
presented in Table 4.5. It may be seen from Fig. 4.2 and 4.3 that carbomethoxy
group at C4 in E1 in the former system is replaced by ketophenyl group in E2 in the
latter (Fig. 4.3). In the former reaction (N1-E1), the higher product ratio 1prn : 1prx
is understandable from the higher activation energy of 1trx, which predicts an endo-
selectivity. For the second reaction (N1-E2) the ratio 2prx: 2prn 64:36, indicates
that exo- electivity is favored, and the situation is rationalizable from higher
activation energy of 2trn. When we consider the entire system as a substitution of
functional group and compare the two reactions in the same channel (i.e., exo- or
endo- on the same face)29
, it is revealed that the exo- channel is stabilized by a small
difference of 0.97 kcal mol-1
between 1trx and 2trx. In a similar manner the endo-
channel is destabilized by a fair amount of 2.167 kcal mol-1
of energy between 1trx
and 2trx. This computational feature could establish a notion that this functional
group alteration has brought about a weak stabilization of exo- channel and a
Nitrone Dipolarophile Reaction
time (hrs)
Ratio of the cycloadducts
Overall yield
of
cycloadducts
N1 E1 4 89(III/1prn):11(IV/1prx) 20%
N1 E1 8 87(III/1prn):13(IV/1prx) 19%
N1 E1 14 65(III/1prn):35(IV/1prx) 19%
N1 E2 4 64(IV/2prx):36(III/2prn) 30%
N1 E2 14 64(IV/2prx):36(III/2prn) 54%
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Stereoselectivity in the 1,3DC of 1-pyrroline-1-oxide to methyl cinnamate and benzylidene acetophenone
82
simultaneous but large destabilization of the endo- channel. Mechanistically, while
selecting the favored reaction channel, the system possibly encounters stronger steric
interaction through the phenyl C-H bonds along the endo- channel which is thereby
destabilized. It has been reported so from experimental findings that the reaction
between N1 and 1-cinnamoyl piperidine were in accordance with the preference for
the endo- mode of attack. Thus, it could be anticipated that for reactions with N1,
the amide carbonyl or ester carbonyl substituent moiety on the dipolarophile
diverted effectively the diastereofacial mode of attack in comparison to the keto-
carbonyl moiety.
3 +N
I/2sx
4
5
4
5
1O
I/2trx
I/2tsx
I/2prx
I/2psx
I/2rx
2
Ph
Ph
Ph
Ph
PhOC
PhOCN
O
H
PhOC
N
O
H
PhOC
Fig. 4.3 Exo attack by E2 on re-and si- faces of N1.
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Stereoselectivity in the 1,3DC of 1-pyrroline-1-oxide to methyl cinnamate and benzylidene acetophenone
83
4.6. Conclusion
Cycloadditions of 1-pyrroline-1-oxide to methyl cinnamate and benzylidene
acetophenone have been reported and the results were rationalized through both
experimental reports and theoretical findings. The theoretical analyses of energy,
enthalpy and free energy of activation, as well as global and local electrophilicities in
the ground state of the reactants have been presented to substantiate the
experimentally observed selectivities in these cycloadditions. The reactions were
100% regioselective leading to the exclusive generation of 3-carbomethoxy and 3-
oxophenyl substituted isoxazolidines which were monitored both experimentally as
also through DFT calculations of the appropriate transition states. However, the
reaction involving E1 was endo-selective, whereas that of E2 was found to be exo-
selective due to functional group modification from carbomethoxy to keto-carbonyl
in the dipolarophile moiety.
The reactivity analysis performed using global and local electrophilicity indexes were
found to be in line with the experimental results. Hence, the global electrophilicity
index could be employed to understand the significance of polar character as well as
the direction of CT along the cycloaddition process. The dominant electrophilic and
nucleophilic centers in the reactants could be identified effectively through an
analysis of local electrophilicity in connection with predicting regioselectivity in
these reactions.
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84
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Stereoselectivity in the 1,3DC of 1-pyrroline-1-oxide to methyl cinnamate and benzylidene acetophenone
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19. S. Stecko, K. Paniczek, C. Michel, A. Milet, S. Perez, M. Chmielewski,
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Stereoselectivity in the 1,3DC of 1-pyrroline-1-oxide to methyl cinnamate and benzylidene acetophenone
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Page 96
Chapter: 5
1,3-dipolar cycloaddition of
1-phenylethyl-trans-2-methyl
nitrone to styrene and of 1-
phenylethyl nitrone to allyl alcohol
Page 97
1,3DC of 1-phenylethyl-trans-2-methyl nitrone to styrene and of 1-phenylethyl nitrone to allyl alcohol
88
5.1. Introduction
The chemistry of 1,3-dipoles has created great interest and application over more
than a century1. A historical study
2 of their cycloaddition reactions has been of
immense importance3 in both academia and industry. The 1,3-dipolar cycloaddition
(1,3DC) reaction of nitrones with alkenes leading to isoxazolidines is a fundamental
reaction in organic chemistry. Considering the need for stereo-specific synthesis of
the 5-membered heterocyclic cycloadducts, theoretical prediction of the probable
adducts and their ratios along with their preferred path of formation would be of
much importance for us. In fact, understanding of this reaction with the help of
different electronic and chemical property is also a challenge for physical chemists.
Quantum chemical study can be very useful to interpret the regioselectivity and
enantioselectivity and also to predict diastereofacial selecitivity for 1,3DC reaction
of some nitrones leading to a diastereomeric excess (de) of the products. In this
regard, N-substituted and C-substituted nitrones were considered for reactions with
the substituted dipolarophiles like styrene and allyl alcohol4. These reactions are
studied by calculating the potential energy surface of the addition process and also in
terms of the of global electrophilicity reactivity index. The trends in reactivity i.e.,
the regio- and exo/endo- selectivity and the product ratios for these reactions have
also been rationalized with the help of frontier orbitals interaction energies,
electrophilicity differences ( ω), the rate constant values, and an analysis of
Pauling‟s bond order (PBO)5 and Wiberg bond index
6 in the transition state. All
these are found to be in good agreement with the experimental findings. As such
reactions of the nitrones leading to 5-membered isoxazolidine rings are of particular
interest in bio-organic chemistry. Considering the need for stereo-specific synthesis
of the cycloadducts, theoretical exploration of the probable products together with
their preferred reaction path would be of much importance to us. All the necessary
computed data of this study have been provided in the annexure 3.
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1,3DC of 1-phenylethyl-trans-2-methyl nitrone to styrene and of 1-phenylethyl nitrone to allyl alcohol
89
5.2. Computational Method
We have chosen the density functional theory(DFT) method using similar basis set
as in previous chapter for studying the stereochemistry of these reacting systems,
since it gives good enough and correct results. The reacting systems are studied by
optimization of TS followed by the well established technique of characterization of
the TS through QST3 option within the optimization step of Gaussian program. For
locating the TS, synchronous transit-guided quasi Newton (STQN) procedure7 is
employed. Confirmation of the right transition structure in each case is ensured
through Intrinsic Reaction Coordinate (IRC) calculations on the TS which are
carried out over a 31-point grid of reaction coordinate with 15 points in each of
forward and reverse directions on the path. In a similar way, the enthalpy of
activation ( H≠), free energy of activation ( G
≠), the heats of reaction ( rH) and
free energies of reaction ( rG) at 298K are calculated as explained before in chapter
2 under section 2.8. The rate constants for different channels of the reaction path
have been evaluated by using standard TST rate equation (eq. 5.1).
RT
G
B ehc
Tkk
…… (5.1)
where kB is Boltzmann constant, h is the Planck constant, c is the standard-state
concentration (often taken to be 1.00 mol dm-3
) and R is gas constant.
5.3. Results and Discussion
The results obtained from our theoretical calculation are divided into two sections
and presented hereunder.
Page 99
1,3DC of 1-phenylethyl-trans-2-methyl nitrone to styrene and of 1-phenylethyl nitrone to allyl alcohol
90
The backbone structure of 1,3-dipole, nitrones is shown in Fig. 5.1.
Fig. 5.1
The mechanism of cycloaddition reactions and of those encompassing the pericyclic
reactions in general, had created a lengthened debate during the 1960‟s and 1970‟s3.
Many experimental reports and theoretical calculations continued to populate the
literature over different areas of the 1,3DC chemistry. Keeping in mind the generally
accepted views regarding these reactions8-10
, continued efforts in reconciliation
between the theory and experiment are still going on11–16
. Our interest in the present
theoretical investigation stems from an attempt to provide an in-depth account of
1,3DC reactions of the nitrones17
. We have taken up the present systems from
literature with an aim to visualize the processes of regio- and enantio-selectivity
through DFT calculations. It is known that the control of stereochemistry in the
addition step leads to enantioselectivity and diastereoselectivity of the products11
.
The stereospecificity dispute had ultimately settled down in favour of the
synchronous and concerted mechanism rather than the step-wise, diradical
mechanism3,18
. According to Huisgen18
, the transition state (TS) for pericylic
reactions was concerted, whereas Dewar suggested19
it to be an asynchronous and
aromatic transition state. Fukui attributed the control of 1,3DC to frontier molecular
orbitals (FMO) of the substrates20
. Again according to Sustmann21,22
the
classification of our reactions following Scheme 5.1 would be of type-I if they
incorporate highest occupied molecular orbital (HOMO) of the dipole to react with
lowest unoccupied molecular orbital (LUMO) of „ene‟ and those following Scheme
5.2 would of type-II if those were effected through LUMO of dipole interacting with
HOMO of „ene‟. The HOMO, LUMO energy values for all the reactants are
presented in Table 5.1.
C N O+ -
1 32
Page 100
1,3DC of 1-phenylethyl-trans-2-methyl nitrone to styrene and of 1-phenylethyl nitrone to allyl alcohol
91
Table 5.1 Total energy, HOMO, LUMO, chemical potential, hardness, electrophilicity of the
isolated dipoles (N1 & N2), the dipolarophiles (E1 & E2) and their differences
_______________________________________________________________________ Global properties
_______________________________________________________________________
Optimized
Energy HOMO LUMO Nmax
*
(a.u.) (eV) (eV) (eV) (eV) (eV)
N1 -518.801981 -5.543 -0.513 -3.03 5.03 0.91 0.60
E1 -309.648272 -6.032 -0.831 -3.43 5.20 0.17 1.13 0.22 0.66 4.712
N2 -479.480661 -5.996 -0.569 -3.28 5.43 1.00 0.60
E2 -193.108432 -6.673 0.835 -2.92 7.51 2.08 0.57 0.43 0.39 6.105
...............................................................................................................................................
0Energy
-6.674eV
0.835eV
-5.996eV
-0.569eV
-6.032eV
-0.831eV
-5.543eV
-0.513eV
N2
Diff of
&LUMO
HOMO
energy
N1
4.712 eV
5.519 eV
6.105 eV
6.831 eV
HOMOHOMO HOMO
HOMO
LUMO LUMO LUMO
LUMO
E1 E2
Fig. 5.2
We have displayed this observation in Fig. 5.2. It is well known that cycloaddition
of unsaturation („ene‟) to a nitrone like benzonitrile oxide gives predominantly the
5-substituted isoxazolidine8, a feature which is not readily explained by the polar
arguments, but can be readily interpreted with mechanism involving biradical
intermediates. The relative stability of the different regiomers of the biradical
intermediate has been pointed out in Fig. 5.3.
Page 101
1,3DC of 1-phenylethyl-trans-2-methyl nitrone to styrene and of 1-phenylethyl nitrone to allyl alcohol
92
Ph N + CH2 =CH-Ph
N
Ph
OPh
NPhO
Ph
+
N
Ph
Ph
NPh
Ph
C O
C
O
O
C
more stable
less stable
major product
minor product
123 4 51
2
3
4 5
12
3
4 5
12
3
4 5
12
3
45
Fig. 5.3
In a theoretical mechanistic study23
of the 1,3DC of fulminic acid and diazomethane,
the analysis was done in terms of ab initio molecular orbital (MO) theory instead of
DFT and they demonstrated the formation of a biradical state through cleavage of
the -bond of the dipolarophile. In the present work we have considered reactions
between several substituted nitrileoxides taken as the dipolar nitrones and the
unsymmetrically substituted „enes‟ like styrene and allyl alcohol4. Experimental
reports24,25
about the reaction between N(1- phenylethyl)-trans-C-methyl nitrone
(N1) and styrene (E1) shown in Fig. 5.4, indicate production of the exo-isomer in
diastereoselective excess of the endo-isomer.
Fig. 5.4
N+
H
C
OMe
Me
Ph (s)
H
C
Dipole (N1)
c c
H
Ph
H
H
Dipolarophile (E1)
(R)
MePh
C
H
C
H
HO N
+
Dipole (N2)
CH2OH
CC
HH
H
Dipolarophile (E2)
Page 102
1,3DC of 1-phenylethyl-trans-2-methyl nitrone to styrene and of 1-phenylethyl nitrone to allyl alcohol
93
Belzecki and Panfil25
very concisely presented a scheme for this
cycloaddition reaction as stated in previous chapter 3. We have developed
calculations on the basis of their scheme and the results of our calculations are given
in the subsequent sections. Very recently spiroisoxazolidines were synthesized as
antimycobacterial agents26
from 1,3DC of C-aryl-N-phenyl nitrones and substituted
pyridinones and were identified as potential anti-tuberculosis drug. As key steps for
total synthesis of virus inhibitors, 1,3DC involving azides, nitrones and azomethine
ylides are most appropriate27
with high biological response. Several workers28–32
have explored the 1,3DC reactions using DFT calculations along with the associated
reactivity tools of hardness and softness. More recently, several workers have
explored33–35
the energetics of stereo- and regio-selectivity of 1,3DC reactions of
nitrones using the DFT/B3LYP/6-31G(d) method. We have similarly adopted
DFT/B3LYP/6-31G(d) method for calculating the energies of reactants, products
and the TS. The rate constant of the addition process has been calculated by using
the standard transition state theory (TST) and applied the same to rationalize the
product ratios. The control for such reactions is indeed not solely by the FMOs, but
certain other parameters like hardness and electrophilicity36–39
having definite
dependence on the HOMO and LUMO have more direct influence on the reactions.
Chattaraj et al.40,41
have extensively reviewed the diverse facets of reactive and
physicochemical processes with the help of electrophilicity index defined earlier by
Parr et al.42
Geerlings et al.43
have reviewed the conceptual aspects of DFT and have
shown how the various physicochemical parameters are derived from theory and
applied successfully to chemical systems. Chemical reactivity has been correlated44
in terms of local softness, hardness, Fukui functions and certain other response
functions. Among these new concepts are the perturbative perspectives45
on
chemical reactivity. The thermodynamic analog such as electronic chemical
potential, although not an observable physical quantity, has its success linked with
the electron density which is instrumental in bearing most information about the
ground state. It is attractive from the purview of organic chemist to examine the
proximity of TS to the reactants or the products over the reaction coordinate. In this
respect the Hammond postulate46
says that TS for exothermic reactions is more
reactant-like, and for endothermic it is more product-like. We can expect that FMO
effects will be particularly strong in exothermic reactions. The global electrophilicity
Page 103
1,3DC of 1-phenylethyl-trans-2-methyl nitrone to styrene and of 1-phenylethyl nitrone to allyl alcohol
94
( ), chemical potential (μ) and hardness (η) parameters help one to explore the
nature of the reactions and reactivity. Theoretical calculated activation parameters
for 1,3DC reactions, their regioselectivity and exo/endo-, i.e., enantioselectivity
show good agreement with the experimental findings. In our pervious chapter, we
have reported the DFT study of 1,3DC reaction of azomethine ylides with
maleimide, maleic anahydride, methylacrylate and some simplesubstituted alkenes47
.
We have also explored both experimentally and theoretically48
the 1,3DC reaction of
1-pyrroline-1-oxide with methyl cinnamate and benzylidene acetophenone leading
to different exo/endo-adducts due to modification of functional group in the
dipolarophile moiety explained in chapter 4. In this work we have rationalized the
experimentally observed products ratio. A coordination by Mg2+
ion in the complex
formation process between benzonitrile oxides and acrylopyrazolidinone had
established49
that the complexation did not produce any change in mechanism which
was asynchronous, concerted and non-polar in character, thereby presenting a 5-
regioselectivity of the product.
5.3.1. Reaction of the Nitrones with Styrene
In this section we present our results for reaction between the N-phenylethyl
substituted nitrone (N1) and dipolarophile: styrene (E1) (Fig. 5.4) for which
experimental reports24,25
were available. Belzecki et.al. had studied the reaction
between 1-phenylethyl-2-methyl nitrone (N1) with styrene (E1) (Fig. 5.5)
experimentally. We have investigated theoretically the different reactive channels
(exo- and endo-) of styrene addition towards the re- and si- faces of nitrone which
are labeled in Fig. 5.4. and the reactions are exemplified pictorially in Fig. 5.5.
Structure symbols for the various products (psx, prx, psn, prn) together with their
corresponding TS (tsx, trx, tsn, trn) are shown in the scheme 5.1, so as to identify
the various stereochemical species. For the approaching orientation of reactants, the
structural naming system are same as our previous discussions.
Page 104
1,3DC of 1-phenylethyl-trans-2-methyl nitrone to styrene and of 1-phenylethyl nitrone to allyl alcohol
95
Scheme 5.1 Reaction of 1-phenylethyl-trans-2-methyl nitrone(N1)
with styrene (E1)a
Configuration of approaching Structure symbol, Structure symbol, Structure symbol,
reactants reactants products TS
si-face of nitrone + exo-ene 1sx 1psx 1tsx
si-face of nitrone + endo-ene 1sn 1psn 1tsn
re-face of nitrone + exo-ene 1rx 1prx 1trx
re-face of nitrone + endo-ene 1rn 1prn 1trn
aThere are no regio- products
Fig. 5.5 The transition states and products in different (re- and si-) facial attacks to the
substituted nitrone N1 (at the middle) by styrene E1 in exo- and endo- approaches
As each product contains two chiral centers in the isoxazolidene moiety, one coming
from the dipole and one from the dipolarophile, there should exist four stereo-
isomers among the products. It is found that the exo- path involves lesser activation
energy (Table 5.2) than the endo- path in both re- and si- faces with the normal
isomer (sustituent entering 5-position of the ring). The products prx and psx are thus
expected to generate in excess as the major kinetic products over prn and psn
agreeing well with experimental data. The electron withdrawing nature of phenyl
group in the substituent of the dipolarophile might be the reason for favouring the
exo- attack. Again any attempt for generating the corresponding regiomers with N1
and E1 had failed because all the starting reverse orientations of the reactants had
led to unrealistic and totally different structures having no relevance with the
C
N+
H
CN
O
Me
H
Ph
H
Ph
C
RPh
OMe
C
(R)
H
N
O
(R)
Me
Ph
H
R
C
rx
sx
(prx)
(psx)
trx
tsx
re & si face of N1 + exo attack of styrene
R
Me
Ph
(s)
H
CR =
C
N+
(R)
H
CN
O
MeH
Ph
H
Ph
C
Ph
OMe
sn
rn
CH
CN
O
Me
Ph
H
R
trn
tsn
(s)
(R)
(S)
(prn)
(psn)
R
R
re & si face of N1 + endo attack of styrene
1
1
2
2
3
3
4
4
5
5
(S)
(S)
23
4
5
4
5
12
3
4
5
45
1
1
1
2
2
3
3
4
4
5
5
Page 105
1,3DC of 1-phenylethyl-trans-2-methyl nitrone to styrene and of 1-phenylethyl nitrone to allyl alcohol
96
optimized product. This consequence has been supported by the experimental
existence of only two stereoisomers, in which the predominance of exo- product is
consistent with lower activation energy of the exo- isomer as shown in Table 5.2.
Adding further precision to our treatment, we have calculated the zero point
corrected (ZPE) Gibb‟s free energy, enthalpy of the reactants and TS in each case
and have calculated the free energies of activation G≠, enthalpy of activation H
≠
and heat of the reaction rH at 298K (Table 5.3). Similar conclusions11-18,24,25,48
arrived by earlier investigators both theoretically and experimentally have indicated
that the substituents should enter preferentially at the 5-position of the
isoxazolidines.
Table 5.2 Energy data for the reaction: 1-phenylethyl-trans-2-methyl nitrone (N1)
with styrene (E1) normal product isomera
__________________________________________________________
Orientation Products Transition States
complex optimized -------------------------------------------------
optimized Energy Eact Eact
(Energy in a.u.) (Energy in a.u.) (in a.u.) (kcal/mol) (kcal/mol) [6-31G(d)] [6-311+G(d,p)]
1sx -828.454835 1psx -828.478962 -828.420823 18.47 22.39
1sn -828.455172 1psn -828.482870 -828.418012 20.23 24.88
1rx -828.456308 1prx -828.485254 -828.425407 15.59 19.09
1rn -828.457253 1prn -828.475033 -828.423839 16.58 21.04
__________________________________________________________________________ aThere was no regio-product, computationally
Table 5.3 Free energy of activation, enthalpy of activation, rate const. and enthalpy
of reaction: 1-phenylethyl-trans-2-methyl nitrone (N1) with styrene (E1)
__________________________________________________________ Reaction Free energy Enthalpy of Numerical values Enthalpy of
Considered of activation activation of the rate constant reaction
G ∆H
k1 ∆rH
(in kcal/mol) (in kcal/mol) (in kcal/mol)
____________________________________________________________________ 1sx to 1psx 33.37 19.30 1.7 10
-12 -15.14
1sn to 1psn 36.14 21.01 1.6 10-14
-23.79
1rx to 1prx 30.51 16.21 2.2 10-10
-19.10
1rn to 1prn 31.51 17.22 4.1 10-11
-12.63
Average, k1 = 6.6 10-11
Page 106
1,3DC of 1-phenylethyl-trans-2-methyl nitrone to styrene and of 1-phenylethyl nitrone to allyl alcohol
97
Now from the Table 5.4, we have found that in TS the newly forming C-C bond
distances are smaller (2.0Å) than the C-O bond distances (2.2Å). Moreover, the
PBO values and from the value of Wiberg bond index in the various TS are around
0.05 for C-O bonds and around 0.16 for C-C bonds which indicates that the TS are
asynchronous.
Table 5.4 Bond orders and bond distances in transition states of the reaction:
1-phenylethyl-trans-2-methyl nitrone (N1) with styrene (E1).
__________________________________________________________
Name of Pauling‟s bond order analysis Wiberg bond index
the TS
------------ ------------------------------------- -------------------------------
rC-O rC-C (PBO)C-O (PBO)C-C (NBO)C-O (NBO)C-C
__________________________________________________________
1tsx 2.37 2.05 0.046 0.192 0.2604 0.4578
1tsn 2.38 2.03 0.047 0.100 0.2542 0.4807
1trx 2.36 2.10 0.051 0.172 0.2513 0.4229
1trn 2.32 2.11 0.056 0.158 0.2594 0.4222
The values of rate constants obtained from eq. 5.1 have been provided in Table 5.3.
From these values of rate constants, we can calculate the products ratio, which can
be conveniently expressed according to the following expressions:
kexo/total = kexo/si+ kexo/re = 2.2 10-10
and kendo/total = kendo/si+ kendo/re = 4.1 10-11
Therefore, the ratio of overall exo to endo product formation is
kexo/total / kendo/total = 2.2 10 -10
/ 4.1 10 -11
= 5.48.
This result in excellent agreement with the experimental result (exo- and endo-
isomers in ratios between 68:32 to 87:13) as reported by Belzecki Panfil23
.
Page 107
1,3DC of 1-phenylethyl-trans-2-methyl nitrone to styrene and of 1-phenylethyl nitrone to allyl alcohol
98
Quantitative characterization of reactivity in DA and 1,3DC reactions in terms of
global electrophilicity power was pioneered33,38,39
by Domingo et al. In their
review30,41
Chattaraj et al. have reported that “Larger electrophilicity differences
correspond to faster34
reactions”. In our present study we observed similar trends:
the for reaction scheme 5.1 is 0.22 (eV) and for the reaction scheme 5.2 it is 0.43
(eV) (Table 5.1) while their average rate constants values were 6.6 10-11
and
4.8 10-7
respectively (Tables 5.3 and 5.5). Therefore, our investigation
accommodates the theory and experiment very well.
In Table 5.1 we have presented the HOMO and LUMO energies of N1, E1 and N2,
E2 along with their electronic chemical potential ( ), chemical hardness ( ) and the
global electrophilicity ( ). According to the absolute scale of electrophilicity38
based
on the global electrophilicity index, E1 can be classified as a strong electrophile
whereas the dipole N1 belongs to the realm of moderate electrophile for the reaction
scheme 5.1. But for the reaction scheme 5.2, N2 can be classified as a strong
electrophile where as the dipolarophile E2 belongs to the realm of moderate
electrophile. The electronic chemical potential ( ) value of N1 (-3.03 eV) is higher
than that of E1 (-3.43eV) implying that the CT will take place from the dipole to the
dipolarophile in this cycloaddition resulting in a normal electron demand (NED)
reaction34
. Whereas the electronic chemical potential ( ) value of E2 (-2.92 eV) is
higher than that of N2 (-3.28eV) (Table 5.1), this will imply that the CT will take
place from the dipolarophile to the dipole in this cycloaddition resulting in also a
normal electron demand (NED) reaction32
. The greater electrophilicity difference of
0.43eV between the pair of reactants N2 and E2 than that (0.22eV) of the reaction
between N1 and E1 provides the higher driving strength (k2) for the former reaction
(Tables 5.3, 5.5). It was experimentally observed that the cycloaddition reaction
between N1 and E1 produced poor yields due to slower reaction rate. Thus, it might
be concluded that the reactivity predicted in terms of global electrophilicity index
showed good agreement with the experimental findings.
The pair hardness50
* for the pair of reactants N1 and E1 in scheme 5.1 is lesser
than that for N2 and E2 given in scheme 5.2 (Table 5.1), reflecting the enhanced
exothermicity for the latter cycloaddition which is also in agreement with the
Page 108
1,3DC of 1-phenylethyl-trans-2-methyl nitrone to styrene and of 1-phenylethyl nitrone to allyl alcohol
99
calculated values of rH presented in Tables 5.3 and 5.5. This fact further
substantiates the reliability of our DFT based results.
As the hardness for N2 and E2 reaction increases, it can be observed the reaction
gets faster due to decrease in activation energy as compared to that of the N1-E1
reaction. This feature is a reflection of the “Hardness maximization principle.” It
should be highlighted additionally that the HOMO – LUMO gap, even for different
species, is a measure of stability through the maximum hardness principle51
. Hard
interactions are essentially electrostatic in nature. Charges or more appropriately
associated quantities such as molecular electrostatic potentials and local hardness are
supposed to be better descriptors for hard-hard reactions. From this out look one can
gain a qualitative perspective for the enhanced reactivity of the N2-E2 system.
5.3.2. Reaction of Nitrones with Allyl Alcohol
Tice and Ganem52
carried out the reaction of 1-phenylethyl nitrone (N2) with allyl
alcohol (E2) (Fig. 5.6), the dipolarophile containing relatively less (than phenyl)
electron withdrawing group –CH2OH, and being investigated computationally in our
present study4.
Structural naming systems similar to those in scheme 5.1 are used for reaction
between N2 and E2, given in the scheme 5.2.
Scheme 5.2 Reaction of 1-phenylethyl nitrone(N2) with allyl alcohol (E2)b
Configuration of Structure symbol Structure symbol Structure symbol
approaching reactants reactants products TS
si- face of ene + exo-nitrone 2sx 2ps 2tsx
si- face of ene + endo-nitrone 2sn 2ps 2tsn
re- face of ene + exo-nitrone 2rx 2pr 2trx
re- face of ene + endo-nitrone 2rn 2pr 2trn
bSince the nitrone C-atom is not prochiral, both exo- and endo- attacks of nitrone on si-face of allyl
alcohol give the same product. Similar case occurs for the re-face. Again there are no regio products.
Page 109
1,3DC of 1-phenylethyl-trans-2-methyl nitrone to styrene and of 1-phenylethyl nitrone to allyl alcohol
100
CH2OH
C
H
H
H
H
H
O
CN
+H
O
H
N+
CN
O
H
(R)
CH2OH
CN
OH
(S)
CH2OH
rn trn
sn tsn
(ps)
(pr)
re & si face of aa + endo attack of N2
CH2OH
C
H
H
H
H
(R)
H
O
CN
+H
O
H
N+
CN
O
H
MePh
(R)
CH2OH
CN
OH
(S)
CH2OH
C
rx trx
sx tsx
(ps)
(pr)
HR ' =
re & si face of aa + exo attack of N2
R'
R'
R'
R'
1
1
2
2
3
3
4
5
R'
R
R'
R'
12
3
45
4 5
1
23
1 2 3
12
3
4
5
1
1
2
2
3
3
4
4
5
5
Fig. 5.6 The transition states and products in different (re- and si-) facial attacks to allyl alcohol
(E2) (at the middle) by the substituted nitrone N2 in exo- and endo- approaches
In connection with regioselectivity of 1,3DC reactions, Magnuson et al.53
made the general remark that for electron donating groups in dipolarophile, the
favoured orientation would be that of the normal isomer with the substiuent at 5-
position of the ring, whereas for electron withdrawing groups it would be the
regioisomer with substituent at the 4-position. It has been reported52
experimentally
that the electron withdrawing phenyl group of styrene goes to the 5-position of ring
leading to the normal isomers and we have also found the same thing to occur from
our TS optimization (Fig. 5.6) calculations. With regard to Magnuson‟s observation,
the phenyl group is considered as having -donating effect as well as –R effect of
attracting electron density, the former dominating in overall, the phenyl could be
considered as normal orienting in this reaction. For allyl alcohol, the primary
alcoholic group –CH2OH being less withdrawing than phenyl has been found from
our calculations to be normal orienting and depicted in Fig. 5.6 which is in
compliance with experimental findings24
. It may be seen from our calculations that
for si-face of allyl alcohol (E2), the endo- attack by nitrone N2 is energetically
favourable whereas for the re-face the exo- attack is favoured (Table 5.6).
Page 110
1,3DC of 1-phenylethyl-trans-2-methyl nitrone to styrene and of 1-phenylethyl nitrone to allyl alcohol
101
Table 5.5 Free energy of activation, enthalpy of activation, rate const. and enthalpy
of reaction: 1-phenylethyl nitrone (N2) with allyl alcohol (E2)
_________________________________________________________
Reaction Free energy Enthalpy of Numerical values Enthalpy of
Studied of activation activation of the rate constant reaction
G ∆H
k2 ∆rH
(in kcal/mol) (in kcal/mol) (in kcal/mol)
____________________________________________________________________ 2sx to 2ps 26.39 12.75 2.4 10
-7 -26.51
2sn to 2ps 26.29 12.48 2.8 10-7
-26.74
2rx to 2pr 25.36 12.22 1.4 10-6
-27.99
2rn to 2pr 31.06 16.38 8.8 10-11
-27.99
Average, k2 = 4.8 10-7
____________________________________________________________________
Table 5.6 Energy data for the reaction: 1-phenylethyl nitrone (N2) with allyl
alcohol (E2) normal product isomerb
____________________________________________________________________
Orientation Products Transition States
complex optimized ------------------------------------------------
optimized Energy Eact Eact
(Energy in a.u.) (Energy in a.u.) (in a.u.) (kcal/mol) (kcal/mol) [6-31G(d)] [6-311+G(d,p)]__
2sx -672.594015 2ps -672.636686 -672.570344 11.77 17.15
2sn -672.598137 2ps -672.636684 -672.570974 11.37 16.67
2rx -672.596509 2pr -672.639134 -672.571198 11.23 15.72
2rn -672.596769 2pr -672.639134 -672.564967 15.14 21.15
__________________________________________________________________________ b There was no regio- product, computationally.
In Fig. 5.6 the different attacks by nitrone N2 to the two faces of allyl alcohol
molecule E2 possessing one prochiral centre have been shown. It follows from
molecular symmetry as evident from Fig. 5.6 that exo- and endo- attacks on each of
the re- and si- faces of the alcohol lead to the same product in each face.
Experimentally, the two diastereomers pr and ps were obtained in 1:1 ratio. From the
values of Eact in Table 5.6, we can observe that in the si- face the endo attack is
favoured, while in the re- face the exo attack is favoured. Other things remaining
identical we may assume that their frequency factors are almost equal and the ratio
Page 111
1,3DC of 1-phenylethyl-trans-2-methyl nitrone to styrene and of 1-phenylethyl nitrone to allyl alcohol
102
of their products should be very close to1:1, as may seen from their comparable
values of G (Table 5.5). The product ratio obtained experimentally can be
explained theoretically through our computational results as are given below4:
kps = kps(si/exo)+ kps(si/endo) = 5.2 10 -7
10 – 6
and
kpr = kpr(re/exo) + kpr(re/endo) = 1.3 10-6
10 – 6
Therefore, the ratio of formation of total exo- product and total endo- product is,
kps / kpr = 1.
This value is good agreement with the experimental result as was reported by Tice
and Ganem52
.
According to the quantitative characterization of reactivity in connection
with DA and 1,3DC reactions in terms of global electrophilicity “the larger
electrophilicity differences correspond to faster42
reactions”. In our present study we
observed similar trends: the for reaction scheme 5.2 is 0.43 (eV) and for reaction
scheme 5.1 it is 0.22 (eV) (Table 5.1) and their average rate constants values are
respectively 6.6 10-11
and 4.8 10-7
. Therefore, our investigation results correlate
with the theory and experiment very well.
Now from the Table 5.7, we found that in TS the newly forming C–C bond distances
are smaller (2.0 Å) than the C–O distances ( 2.2 Å). Moreover the PBO values in the
TS in different reactive channels are around 0.08 for C–O bonds and around 0.16 for
C–C bonds which indicates that the TS is asynchronous. From a similar analysis of
NBO based Wiberg bond indexes6 given in Table 5.7, it is also indicated that the TS
is asynchronous.
Page 112
1,3DC of 1-phenylethyl-trans-2-methyl nitrone to styrene and of 1-phenylethyl nitrone to allyl alcohol
103
Table 5.7 Bond orders and bond distances in transition states of the reaction:
1-phenylethyl nitrone (N2) with allyl alcohol (E2)
__________________________________________________________________
Pauling‟s bond order analysis Wiberg bond index
Name of ------------------------------------------- ------------------------------------
the TS rC-O rC-C (PBO)C-O (PBO)C-C (NBO)C-O (NBO)C-C
____________________________________________________________________
2tsx 2.26 2.09 0.071 0.168 0.2929 0.4275
2tsn 2.20 2.15 0.089 0.137 0.3093 0.4005
2trx 2.23 2.13 0.075 0.146 0.2955 0.4023
2trn 2.17 2.08 0.093 0.172 0.3365 0.4493
------------------------------------------------------------------------------------------------------
5.4. Nature of Transition State in the Reactions
While such cycloaddition reactions pass through a transition sate there remains to
answer the question as to whether the reactions considered follow a concerted or a
diradical path. Although the general verdict in this regard was in favour of
concerted mechanism, at a certain stage R.Huisgen18,54
reported the well-
documented example of a step-wise 1,3DC involving an intermediate which
encouraged Firestones‟s contention55
that „no degree of stereospecificity could rule
out diradical mechanism‟ gaining support from his proposal. That the activation
energy for single bond rotation was greater than that for either formation of the
second bond leading to the adduct or reversion to the reactants. In this context we
have calculated (Tables 5.4, 4.7) the PBOs for C-C and C-O bonds in the TS. It can
be seen from Table 5.4 that for TS with nitrone N1 and styrene (E1), the C-C bond is
formed early with a shorter rC-C distance than the rC-O distance, the bond order values
agreeing correspondingly with bond distances. The reaction in this case can be
considered to be asynchronous and concerted.
In the case of nitrone N2 reacting with allyl alcohol, the pattern of activation
energies and the trend of relative PBO values (Fig. 5.6, Table 5.7) are similar to
those of nitrone N1 and E1 (Fig. 5.5, Table 5.4). Even if the possibility of a diradical
mechanism is cancelled, it may be concluded that the process is highly asynchronous
Page 113
1,3DC of 1-phenylethyl-trans-2-methyl nitrone to styrene and of 1-phenylethyl nitrone to allyl alcohol
104
which was at some stage predicted by Dewar18
. In our present work we reported
only about our observations. On the basis of classification of 1,3DC in terms of
FMOs, the interaction of styrene (E1) with the nitrones N1 and N2 with allyl alcohol
(E2) appears to be (Fig. 5.6) controlled by both HOMOdipole - LUMOalkene and
LUMOdipole – HOMOalkene and are of type-I for scheme 5.1 where as type-II for
reaction scheme 5.2.
5.5. Conclusion
The 1,3-dipolar cycloaddition reactions of two well-known nitrones with two
selected alkenes have been studied in detail using the B3LYP/6-31G(d) method. The
experimentally observed products, their interactions, TS and the relative proportion
of yields of different have been rationalized using calculated potential energy
barriers for the reactions, rate constants and reactivity parameters. This type of
investigation can be easily extended to larger natural systems of stereochemical
significance in asymmetric synthesis. Further quantification about the products ratio
might be achieved through an evaluation of the local electrophilicity descriptors. But
calculation of local electrophicility using the Mulliken population sometime fails to
predict the preferred regioselective attacks. Other type of population analysis
scheme, such as electrostatic potential driven charge, may be explored in this matter.
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1,3DC of 1-phenylethyl-trans-2-methyl nitrone to styrene and of 1-phenylethyl nitrone to allyl alcohol
105
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1,3DC of 1-phenylethyl-trans-2-methyl nitrone to styrene and of 1-phenylethyl nitrone to allyl alcohol
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1,3DC of 1-phenylethyl-trans-2-methyl nitrone to styrene and of 1-phenylethyl nitrone to allyl alcohol
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Page 117
Chapter: 6
Theoretical studies on cyclization of
azomethine imines with electron
deficient dipolarophiles
Page 118
Theoretical studies on cyclization of azomethine imines with electron deficient dipolarophiles
109
6.1. Introduction
We are interested for stereospecific synthesis of 5-membered different substituted
pyrazolidine rings, which could be useful for the stereoselective synthesis of C-
nucleosides. The azomethine imines cyclizing with alkenes forms pyrazolidines,
which have synthetic application for bioactive products. For this purpose the 1,3-
dipolar cycloaddition (1,3DC) reaction of imines and electron deficient
dipolarophiles, have been investigated theoretically with the help of Quantum
chemical computation. The azomethine imines are very much unstable and so it is
prepared in situ during the study of the reactions. But this reactant entity is very
much interesting for the preparation of important products. As less stability or
shorter life span puts no additional difficulty, at least in principle, for computational
study, we plan to compute different important data required to study these types of
chemical reactions. Further, our interest grows from the fact that the intermolecular
cycloadditions through 1,3DC reaction by the use of different substituted
azomethine imines and different substituted alkenes have been relatively less
explored. Again we have examined the scope and limitations of this azomethine
imines and alkenes reaction through 1,3DC reaction, investigating the effects of
varying the nature of different components. The 1,3DC reactions of azomethine
imines with alkenes lead to formation of pyrazolidines, which is important for the
synthesis of our biologically active important products. Moreover the use of imines
in asymmetric 1,3DC reactions alkenes is very important, and attention has been
focused on the use of chiral azomethine imines for the stereoselective synthesis of
C-nucleosides1. The dihydropyrazole derivative has been transformed into chiral
azomethine imines, such as by the reaction with carbohydrate derivative aldehydes.
The 1,3DC reactions of azomethine imines with some electron deficient
dipolarophiles viz. acrylonitrile, methylpropenoate, and dimethylmaleate leading
predominantly to 4-substituted pyrazolidines have been computationally studied2
which can be useful for the stereoselective synthesis of C-nucleosides. All the
necessary computed data of this study have been provided in the annexure 4.
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Theoretical studies on cyclization of azomethine imines with electron deficient dipolarophiles
110
6.2. Computational Method
Using the Gaussian03 program3 together with Gaussview03 we have performed
DFT computation for this reacting system. Again, by considering the complexity of
the reacting systems, we have adopted the same basis set as in chapter 5. All the
reacting systems are studied by locating the correct TS through vibrational analysis
producing only one imaginary frequency followed by an IRC4 calculation in each
case, one such plot being presented in Fig. 6.1. This would ensure that the obtained
TS is a first order saddle point on the PES5. The DFT based indices chemical
potential (μ), chemical hardness (η), global electrophilicity (ω), global
nucleophilicity (N) etc. are computed from the calculated HOMO, LUMO energies
obtained within a Kohn Sham6 orbital model in density functional theory. Apart
from TST calculation of the activation barrier, it would be much desirable to
evaluate theoretically the values of rate constant for elementary bimolecular
reactions in the gas phase. These together with the Gaussian calculated value of
activation energy (Ea), the theoretical magnitude of rate constant (k) were calculated
at different temperatures. A further plot of -log(k) vs 1000/T gave a good liner plot
in each case, a representative plot being shown in Fig. 2 in chapter 2. Again from the
slope of the plot the value of Ea for the reactions were recomputed as explained in
chapter 2 section 2.8.n. We also calculated Wiberg7 bond index and Charge Transfer
(CT)8 at transition states in order to predict the polarity of the 1,3DC reaction.
Fig. 6.1
Page 120
Theoretical studies on cyclization of azomethine imines with electron deficient dipolarophiles
111
6.3. Results and Discussion
The results of our calculations are presented in the three following sections:
The backbone structure of 1,3-dipole, azomethine imines are shown in Fig. 6.2.
C N+
N1 32
Fig. 6.2
The reaction mechanisms of the regioselectivity, chemoselectivity and
diastereofacial selectivity are studied through the evaluation of activation parameters
and philicity indices on the assumption of a concerted mechanism. The local and
global electrophilicity and nucleophilicity indices have been used regularly for
predicting regioselectivity and reactivity. The reactions are considered to be
nonpolar or at the most weakly polar on the basis of charge transfer calculated in the
transition states. In the present cases, no facial selectivity could be observed due to
energetic identity of the different enantiomeric transition states. A rationalization of
the trends in regio- and chemo-selectivity were also attempted in terms of μ, η, ω, N
global electrophilicity differences ( ω), local electrophilicity (ωk), local
nucleophilicity (Nk), Pauling’s bond order (PBO)9 and Wiberg bond indices
7 in the
transition state. Theoretical evaluation of rate constants for elementary reaction steps
employing the transition state theory is very much useful for getting quantitative
idea about the kinetic rates associated with those steps. In addition, the recomputed
activation energies as discussed in section 2.8.n become more effective to explain
the product ratios.
Although the 1,3DC reactions have been a well-studied field of organic
cycloadditions but it always evokes interest among researchers for its better
understanding. In addition to having interesting problems in understanding
mechanism, those reactions have enormous applications10,11
in the synthesis of
Page 121
Theoretical studies on cyclization of azomethine imines with electron deficient dipolarophiles
112
pharmaceuticals and intermediates. The requirement for stereo-specific synthesis of
organic compounds, commonly known as asymmetric synthesis, has encouraged the
growth of this particular branch of 1,3DC chemistry. The different classes of
compounds under this category comprising the nitrones, ylides, imines, azimines
principally known as the dipoles undergo ring cyclization with unsaturated
compounds known as the dipolarophiles. In the present study, we have considered
the reactions 1, 2 and 3 between the azomethine imine (AI) and three electron
deficient alkenes E1, E2, E3 respectively; those have been presented in Table 6.1.
Considering the fact that the reactions are practically carried out in solutions, some
calculations are performed in solvents of different polarity to examine its influence
on the activation barrier or the reaction rate. For this conceptual clarity about this
matter, one model reaction involving the simple (methyl) substituted azomethine
imine (AI0) and the dipolarophile propene (E0) has been studied with varying
solvent of different polarity.
Table 6.1 Abbreviations for the reagents: -----------------------------------------------------------------
Reactant Abbreviation
CH3
O
NNH3C
Ph
+ -
12
3= AI
C=CH-CN
45
H
H= E1
C CHCOOMeH
H
45= E2
CHCOOMeZ-MeOOCCH
5 4= E3
CH
Me 3 2
NH+
NH1
= AI0
C CH2
H
45= E0 Me ___
AI0 and E0 refer to model reactants for looking
into aspects of planarity of transition states and
products of cycloaddition.
Page 122
Theoretical studies on cyclization of azomethine imines with electron deficient dipolarophiles
113
In spite of the fact that theoretically 1,3DC reactions are generally studied in the gas
phase, the question remains about how those reactions proceed in solution since all
such reactions are carried out experimentally in the solution phase. The theoretical
simplicity of gas phase model might be complicated by so many factors in the
solution. Keeping this in mind one can expect that the reaction barrier may be
different in solvents of varying polarity and moreover, the reaction mechanism can
be different which is obviously reflected through the calculated asynchronicity and
bond orders at the reacting sites. In this respect we have performed in-solvent
calculations using the SCI-PCM12
model employing the solvents like CCl4, ethanol
and acetonitrile considering polarity and solubility factors. The findings of those
calculations do not lead to any major deviation in the mechanism, but there are
significant changes in the barrier heights with almost no change in asynchronicity of
the reactions. The findings are discussed in the result section. All these reactions
involving imines are much less explored compared to the nitrones counterpart. The
1,3DC reactions of AI have found potential application in the efficient regio- and
stereo- controlled synthesis of pyrazolidine rings using the appropriately substituted
alkenes, thus having the possibility to generate three new chiral centers at C-3, C-4
and C-5 as shown in Table 6.1. Although cases of azomethine imines entering
asymmetric cycloaddition reaction with alkenes are limited, we have focused our
attention to the chiral azomethine imines for the stereoselective synthesis of C-
nucleosides playing very important role in the synthesis of cyclic or bicyclic natural
and bio-organic compounds1 with a very high or complete selectivity. The present
work helps us to understand the processes of regio- and enantio- selectivity through
ground state Density Functional Theory (DFT)13
calculations. DFT can provide the
parameters like local electrophilicity ( k), local nucleophilicity (Nk), and
additionally potential energy barriers in good agreement with experimental results1.
Theoretically calculated rate constant values are obtained using the rate standard
Transition State Theory (TST) and are found to be in good agreement with
experiment. Over the last twenty years, success and popularity of DFT has
encouraged many groups in making use of the soft-hard-acid-base (SHAB)
principle14
, the DFT-based reactivity descriptors like condensed Fukui function15
and philicity indexes16
.
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Theoretical studies on cyclization of azomethine imines with electron deficient dipolarophiles
114
The calculation of Fukui functions of an atom in a molecule proves to be an useful
criterion to characterize the reactive sites within a chemical species and the local
electrophilicity index is very helpful to explain the regio-selectivity of the 1,3DC
reaction. To describe the site selectivity or reactivity of an atom in a molecule, it is
necessary to condense the values of Fukui function )(rf around each atomic site
into a single value that characterizes the atom in a molecule. This can be achieved
through electronic population analysis as described in section 2.8.d.
It is known that the control of stereochemistry in the addition step of a reaction leads
to enantioselectivity and diastereoselectivity of the product. Historitically, the
stereospecificity dispute was settled in favour of the concerted, asynchronous and
early transition state17
. The control for such reactions is indeed not solely perceptible
from the FMOs of the reactants, but certain other parameters like the DFT philicity
indices related to the IP and EA of the reagents18
could be indicative of the reactive
mode. The reactivity indices are based on molecular properties calculated in the
ground equilibrium states of reagents, but stereoselectivity predominantly depends
on the course of the reaction through the TS and thereby depends on the activation
energy. The philicity indices nevertheless having definite dependence on the HOMO
and LUMO energies but do not explicitly exhibit their connection with the frontier
(FMO) controlled reactions19-21
. The electrophilicity scale employed to classify
reagents in 1,3DC reactions was used for the first time by Domingo et al.21
.
Chattaraj et al.22
have extensively reviewed the diverse arena of reactive and
physicochemical processes with the help of electrophilicity index defined earlier by
Parr et al.23
Geerlings et al.24
have reviewed the conceptual aspects of DFT and have
shown how the various physicochemical parameters could be derived from theory
and applied successfully to chemical systems. Chemical reactivity has been
correlated25
in terms of local softness, hardness, Fukui functions and certain other
response functions. Among these new concepts are the perturbative perspectives26
on chemical reactivity. The thermodynamic analog such as the electronic chemical
potential (μ), although not an observable physical quantity, has its origin buried
under the electron density which is pivotal in bearing most information about the
ground state.
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Theoretical studies on cyclization of azomethine imines with electron deficient dipolarophiles
115
Table 6.2
Global and local properties of the isolated dipole (AI) and dipolarophiles (E1, E2, E3) [k is the atom site in the molecules in accordance with Figs. 6.4, 6.5 and 6.6 where the local property
is evaluated]
Global properties Local properties _____________________________________________________________ ___________________________________
Reagents Optimized
energy HOMO Nmax N k f k+ fk k Nk
(a.u) (eV) (eV) (eV) (eV) (eV)
AI -572.961695 -5.526 -3.808 3.435 2.111 1.108 3.574 1 -0.176 -0.250 -0.371 -0.629
2 0.180 -0.442 0.380 0.643
3 -0.201 -0.132 -0.424 -0.718
E1 -170.834988 -7.740 -4.558 6.364 1.632 0.716 1.472 4 -0.372 -0.205 -0.607 -0.547
5 -0.706 -0.152 -1.152 -1.039
E2 -306.466612 -7.399 -4.314 6.169 1.508 0.699 1.813 4 -0.462 0.079 -0.696 -0.838
5 -0.699 0.115 -1.054 -1.267
E3 -534.333724 -7.386 -4.578 5.616 1.866 0.797 1.826 4 -0.491 0.008 -0.916 -0.896
5 -0.491 0.008 -0.916 -0.896
AI0 -189.242652 -4.742 -2.318 4.847 0.554 0.478 4.379 1 -0.179 -0.295 -0.100 -0.784
2 -0.053 0.561 -0.030 -0.232
3 -0.415 -0.164 -0.230 -1.817
E0 -117.907556 -6.797 -3.013 7.567 0.599 0.398 2.324 4 -0.142 -0.167 -0.085 -0.330
5 -0.087 -0.098 -0.052 -0.202
On the basis of DFT we have computed the chemical potential, hardness,
global and local electrophilicity and nucleophilicity for our reagents have been
presented in Table 6.2. The bond orders in TS(s) of the corresponding reactions have
been presented in Table 6.3. The transition state (TS) according to Huisgen27
is
concerted for pericylic reactions which Dewar28
has suggested to be asynchronous
and aromatic. Fukui attributed the control of 1,3DC to the Frontier Molecular
Orbitals (FMOs) of the substrates.
The inadequacy of FMO theory vis-à-vis the global and local reactivity indices has
become obvious from our results. It appears from Table 6.4 that in the reaction
system 3sn to p3sn the activation energy is 4.6 kcal.mol-1
while the HOMO-LUMO
energy gap in Fig. 6.3 for this reaction 3 is calculated 87 kcal.mol-1
(3.76eV). Since
activation energy for the reaction is 4.6 kcal.mol-1
, the HOMO electrons of AI can
not reach the LUMO of the dipolarophile. Thus, the LUMO does not possess the
Page 125
Theoretical studies on cyclization of azomethine imines with electron deficient dipolarophiles
116
control of regioselectivity and in this respect FMO theory is not suitable for
explaining reactivity.
Table 6.3 Bond order and bond distances in transition states.
The notation –r in the transition state symbol represents regio- conformation.
Fig. 6.3 HOMO-LUMO energy gaps.
Transition
state Distances Pauling’s bond order Wiberg bond index
rC-C (Å) rC-N (Å) (PBO)C-C (PBO)C-N (NBO)C-C (NBO)C-N T1rx
T1rn
2.70089
2.76287
2.05097
2.02972
0.0251
0.0210
0.1546
0.1667
0.2137
0.1493
0.4342
0.3734
T1rx-r
T1rn-r
2.29191
2.29309
2.27272
2.23904
0.0881
0.0885
0.0762
0.0863
0.2498
0.3265
0.1849
0.2613
T2rx
T2rn
2.48585
2.53858
2.01906
1.98663
0.0477
0.0418
0.1697
0.1815
0.1651
0.1481
0.3183
0.3367
T2rx-r
T2rn-r
2.26241
2.10906
2.29290
2.34241
0.0974
0.1595
0.0705
0.0599
0.3206
0.4144
0.2484
0.2402
T3sx
T3sn
2.58475
2.54662
1.94548
1.99559
0.0393
0.0388
0.2058
0.1784
0.1534
0.1983
0.4538
0.4171
T0rx
T0rn
T0rxsol ccl4
T0rnsol ccl4
T0rxsol EtOH
T0rnsol EtOH
T0rxsol Acetonitrile
T0rnsol Acetonitrile
2.30458
2.30351
2.23672
2.35914
2.30548
2.30351
2.30548
2.30351
2.31213
2.29968
2.23730
2.28883
2.31213
2.29968
2.31213
2.29968
0.0877
0.0911
0.1079
0.0752
0.0874
0.0911
0.0875
0.0911
0.0684
0.0686
0.0866
0.0727
0.0684
0.0686
0.0684
0.0712
0.3272
0.3281
0.3624
0.2727
0.3223
0.3231
0.3222
0.3230
0.3128
0.3165
0.3504
0.2859
0.3092
0.3132
0.3090
0.3130
0
Energy
-7.386eV
-1.770eV
-7.399eV
-1.230eV
-7.740eV
-1.376eV
-5.526eV
-2.091eV
Diff of
&LUMO
HOMO
energy
4.15eV
5.649eV 5.295eV5.308eV
HOMO
HOMOHOMO HOMO
LUMO
LUMO LUMOLUMO
E1 E2 E3
4.296eV 3.756eV
AI
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Theoretical studies on cyclization of azomethine imines with electron deficient dipolarophiles
117
In our present work we have considered C- and N- substituted AI as the dipole
which was prepared1 form addition of an aldehyde with 1,2-disubstituted hydrazine
resulting in the formation of an aminol, that loses the elements of water to form the
dipole. This further produced the pyrazolidine rings via 1,3DC reaction of the
dipole: AI with the unsymmetrically substituted ethylenes: acrylonitrile,
methylpropenoate and the symmetrically substituted dimethylmaleate2. This type of
intermolecular cycloadditions can be controlled to exhibit regio- and stereo-
chemistry of the products. Experimental results for the reaction of azomethine imine
AI with E1, E2, and E3 are available in literature1. A diagrammatic scheme for such
cycloaddition reactions has been very concisely presented by Belzecki et al.29,30
We
have carried out theoretical calculations based on their schematic approach and
enumerated results which are given in the subsequent sections.
Several workers31-37
have explored the 1,3DC reactions by DFT employing the
associated tools of hardness and softness. It is attractive from the point of an organic
chemist to examine the proximity of TS to the reactant or product over the reaction
coordinate during the course of reaction. In this respect the Hammond postulate38
tells that TS for exothermic reactions are reactant-like, and those for endothermic
ones are product-like. Global electrophilicity ( ), nucleophilicity (N), chemical
potential ( ), hardness ( ) indices for the reagents AI, E1, E2 and E3 are calculated
and presented in Table 6.2 to assess their reactivity. We have presented the Pauling’s
partial bond order (PBO)9 and Wiberg bond indices
7 of the TSs in Table 6.3 and also
the thermo-chemical parameters like energy of activation ( E ) in Table-6.4, the
free energy ( G ) and enthalpy ( H ) of activation, the free energy ( rG) and
enthalpy ( rH) of reaction in Table 6.5. All these data enable to acquire precise
knowledge about the TS. The values of rate constants for the different reactions on
different faces (re- or si-) through the different channels (exo- or endo-) and also the
regio- course at different temperatures are calculated from TST rate equation using
total partition functions and the results are presented in Table 6.6. The schemes 6.1-
6.3 are employed to define the various reaction channels describing paths from
reactants to the selected products.
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Theoretical studies on cyclization of azomethine imines with electron deficient dipolarophiles
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Table 6.4 Optimized activation energy
Configuration of
approaching
reagents
Transition state parameters
Activation Activation
TS energy energy
(kcal.mol-1
) (kcal.mol-1
)
[6-31G(d)] [6-311+G(d,p)]
AI (re face) + E1 (exo)
[1rx]
AI (re face) + E1(endo)
[1rn]
AI (re face) + E1 (exo)
[1rx-r]
AI (re face) + E1(endo)
[1rn-r]
AI (re face) + E2 (exo)
[2rx]
AI (re face) + E2 (endo)
[2rn]
AI (re face) + E2(exo)
[2rx-r]
AI (re face) + E2(endo)
[2rn-r]
AI (si face) + E3 (exo)
[3sx]
AI (si face) + E3 (endo)
[3sn]
AI0 (re face) + E0 (exo)
[0rx]
AI0(re face) + E0 (endo)
[0rn]
AI0 (re face) + E0 (exo)
[0rx] in sol ccl4.
AI0(re face) + E0 (endo)
[0rn] in sol ccl4.
AI0 (re face) + E0 (exo)
[0rx] in sol EtOH.
AI0(re face) + E0 (endo)
[0rn] in sol EtOH.
AI0 (re face) + E0 (exo)
[0rx] in sol Acetonitrile.
AI0(re face) + E0 (endo)
[0rx] in sol Acetonitrile
T1rx
T1rn
T1rx-r
T1rn-r
T2rx
T2rn
T2rx-r
T2rn-r
T3sx
T3sn
T0rx
T0rn
T0rxsol ccl4
T0rnsol ccl4
T0rxsol EtOH
T0rnsol EtOH
T0rxsol Acetonitrile
T0rnsol Acetonitrile
13.7
11.6
19.7
18.5
7.0
6.3
18.1
7.9
9.7
4.6
12.4
12.1
13.6
13.2
15.0
14.6
15.1
14.7
16.0
14.3
22.2
21.3
9.8
9.6
21.1
12.4
13.9
8.8
16.3
15.6
17.6
16.9
19.0
18.4
19.0
18.5
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Theoretical studies on cyclization of azomethine imines with electron deficient dipolarophiles
119
6.3.1. Reaction of Azomethine Imine with Unsymmetrically
Substituted Alkenes (E1 and E2)
In Table 6.1 we have abbreviated the names of our reactants. This describes the
reactions between the azomethine imine (AI) and the ‘Alkenes’ (i) acrylonitrile (E1)
in scheme 6.1, (ii) methylpropenoate (E2) in scheme 6.2, (iii) dimethylmaleate (E3)
in scheme 6.3. For all these reacting systems we have explored the different
approaches (exo- and endo-) of dipolarophile towards the re- and si- faces of the
dipole and described the same as the four possible reactive channels. The systems
were labeled for the faces and channels of reaction according to schemes 6.1-6.2.
Structural symbols for the various products (psx, prx, psn, prn) and their
corresponding TSs (Tsx, Trx, Tsn, Trn) were mentioned in the schemes so as to
suitably describe the various stereochemical species involved in different channels
as like as discussed in chapter 3 section 3.3.2. Recently, we have explored the 1,3DC
reaction of some azomethine ylides with maleimide, maleic anhydride,
methylacrylate and some simple substituted alkenes39
and also the reaction of the
nitrone of 1-pyrroline-1-oxide with methyl cinnamate and benzylidene
acetophenone40
. We have also explored the 1,3DC of 1-phenylethyl-trans-2-methyl
nitrone to styrene and of 1-phenylethyl nitrone to allyl alcohol in order to rationalize
the product ratios41
calculated on the basis of their rate constants of reaction.
Schemes 6.1-6.3 Reagents: Azomethine imine (AI) and the dipolarophiles
(EN)a acrylonitrile, methyl propenoate and methyl maleate
Configuration of approaching Structure symbol, Structure symbol, Structure symbol,
reactants reactants products TS
si-face of imine + exo-ene Nsx pNsx TNsx
si-face of imine + endo-ene Nsn pNsn TNsn
re-face of imine + exo-ene Nrx pNrx TNrx
re-face of imine + endo-ene Nrn pNrn TNrn
a Chosen system: N=1 for scheme 6.1, N=2 for scheme 6.2 and N=3 for scheme 6.3, in the reacting
AI-EN systems. Both exo- and endo- approaches on a particular face give structurally
different products.
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Theoretical studies on cyclization of azomethine imines with electron deficient dipolarophiles
120
The simplest substituted azomethine imine AI0 chosen as a model is planar because
the 1,3-dipole is extended over the atoms 1-2-3 of the imine, shown in Table 6.1.
With increased substitution the overall molecular structure of the N2-methyl C3-
phenyl AI gets twisted. In this case the overall molecular symmetry plane is lost.
The C3 terminal end of AI is pro-chiral. Attack by the incoming ethylenic reagent to
the opposite faces of AI leads to distinctly different enantiomeric products with the
same energy and on this consideration we have opted for either si- or re- face
attacks. However, energetic identity between TSs in re- and si- face approaches
appeared in the idealized planar AI0 example. In this AI0 – E0 model reaction, a
particular enantio channel (exo- or endo-) over the different faces led to the same TS
energy in Table 6.4. In the higher substituted ethylenes and imines we might also get
equivalent TS energies, viz. the T1rn and T1sn from the two opposite facial attacks
by the reagents. The AI appears to be slightly twisted due to repulsion between the
bulky substituents generating chirality in the structure and consequently an obvious
energetic identity between the optimized enantiomeric pairs occurs. The
enantiometric pairs are energetically degenerate. The 1,3DC attack to a particular
face of AI by the dipolarophiles E1-E3 in either exo- or endo- channel would result
in stereoisomeric conformations with the same energy as with the other face (data
have been provided in Annexure 4). Hence, there will be no facial selectivity in
these reactions. If there is any scope for regioselectivity, there would have been four
isomers in total, two arising from exo- and endo- channels in the normal path and
two from the regio- path.
For the azomethine imine (AI) reacting with acrylonitrile (E1),
according to scheme 6.1, the dipole (AI) having only one prochiral center at C3 is
placed in the Figs. 6.4.1 and 6.4.2 to distinguish between the exo- and endo-
approaches by dipolarophile on the re- face of the dipole. It is found from
calculations that exo- and endo- attacks on the re- face led to different energies of
the TS as are given in Table 6.4.
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Theoretical studies on cyclization of azomethine imines with electron deficient dipolarophiles
121
Ph
N+H3C N COCH3
NNH3C
COCH3
Ph
CNCN
RR
11
2 2
33
4
45 5
p1rx
T1rx
Fig. 6.4.1 exo- attack of acrylonitrile (E1) on
re- face of azomethine imine (AI).
Ph
N+H3C N COCH3 NN
H3CCOCH3
Ph
CNNC
RS
1 122
3 34
4
5
5p1rn
T1rn
(major) .
Fig. 6.4.2 endo- attack of acrylonitrile (E1) on
re- face of azomethine imine (AI).
It may be noted from Table 5.3 that very low PBO values and larger interatomic
distances rC-C and rC-N for the newly forming bonds in the transition state indicate the
formation of an early transition state, as has been similarly reported by Domingo42
in
connection with azomethine ylides as in chapter 3. The control for such reactions is
not lying with the FMOs, but certain other parameters such as hardness,
electrophilicity and nucleophilicity albeit having definite dependence on the HOMO
and LUMO energies have more direct influence on the control. From the results of
calculation presented in Tables 6.4, 6.5 we observe that in presence of electron
withdrawing groups on the alkene moiety in all the three systems in schemes 6.1-
6.3, the endo- path always involves lesser energy and enthalpy of activation on re-
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Theoretical studies on cyclization of azomethine imines with electron deficient dipolarophiles
122
face than in the exo- path, as shown in Tables 6.4, 6.5. The products (p1rx) and
(p1rn) differing (yield: p1rn>p1rx) in chirality, are obtained as the major yields from
activation energy calculation and presented in Figs. 6.4.1 and 6.4.1, which are also
corroborated form the values of calculated rate constants in Table 6.6. For reaction
of acrylonitrile (E1) with azomethine imine (AI) we have calculated the TS in which
both the C-C distances are around 2.68Å and C-N distances around 2.02Å, which
suggest that the transition states are early and asynchronous. Similar findings are
also indicated form the results of Wiberg bond index7 and bond orders of the
transition states in Table 6.3, which further confirm the early and asynchronous
nature of transition states.
Moreover, from the value of local electrophilicity ( k), values in Table 6.2 indicate
that the bimolecular addition takes place through linking the N1 atom of the dipole
AI to C5 atom of the dipolarophile E1 and simultaneously the C3 atom of AI to C4
atom of E1 as described in Table 6.1. Experimental results1 reveal that 4-substituted
products are obtained and there is no regio- product.
According to reaction scheme 6.2, calculations for the reaction 2 reveal that the
endo- path on both the faces involve lesser extents of energy and enthalpy of
activation than in the exo- path, given in Tables 6.4, 6.5. On consideration of
activation energies, the product p2rn should thus be obtained with greater yields.
However, since the differences between activation energies are very little for p2rn
and p2rx, these two isomers are obtainable almost in similar amounts which are
supported from their calculated rate constants in Table 6.6. For more consistent
values of activation energy are recomputed as previously discussed and the data
obtained is presented in Table 6.6. From that result the reactions of scheme 6.2 are
pictorially exemplified in Figs. 6.5.1 and 6.5.2. Similar to the previous reaction
system 1 the present system also exhibits an early and asynchronous TS concluded
in terms of C-C, C-N distances and bond orders, given in Table 6.3.
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Theoretical studies on cyclization of azomethine imines with electron deficient dipolarophiles
123
Ph
N+H3C N COCH3
CO2CH3
NNH3C
COCH3
Ph
CO2CH3
RR
1
2
3
4
5
12
34
5
p2rx
T2rx
Fig. 6.5.1 exo- attack of methylpropenoate (E2)
on re- face of azomethine imine (AI).
Ph
N+
H3C N COCH3
NNH3C
COCH3
Ph
CO2CH3
H3CO2C
RS
12
34
5
12
3
4
5
p2rn
T2rn
(major)
Fig. 6.5.2 endo- attack of methylpropenoate (E2)
on re- face of azomethine imine (AI).
6.3.2. Reaction of Azomethine Imine (AI) with the Symmetrically
Ssubstituted Alkene ( E3)
In this section we present the results of calculation for the reaction of the
dipolarophile: dimethyl maleate (E3) with azeomethine imine (AI) for which
experimental reports from Jones et al.1 were available. The different approaches
(exo- and endo-) of the dipolarophile towards any of the faces re- and si- of the AI
are labeled according to schemes 6.3 and depicted in Figs. 6.6.1 and 6.6.2.
Structures of the various products (p3sx, p3sn) together with their corresponding
TSs (T3sx, T3sn) are shown in the figures to identify the different stereochemical
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Theoretical studies on cyclization of azomethine imines with electron deficient dipolarophiles
124
species. We have followed a naming system as used in the previous section 3.2.1, as
in scheme 6.1-6.3. In the reaction 3 we observe that the endo- path on both the si- or
re- faces involve lesser amounts of energy and enthalpy of activation than in the
exo- channel, given in Tables 6.4, 6.5. Thus, the product p3rn should be obtainable
with major yields. All these results are supported by the calculated rate constants
presented in Table 6.6. Similar observation and conclusions can be made concerning
geometry of the TS as described previously for the two previous systems 1 and 2.
Ph
N+H3C N COCH3
NNH3C
COCH3
Ph
CO2CH3
CO2CH3
CO2CH3
CO2CH3
Rs s
1
45
1
2
2
3
3
4
5
p3sx
T3sx
Fig. 6.6.1 exo- attack of dimethylmaleate (E3)
on si- face of azomethine imine (AI)
Ph
N+H3C N COCH3
NNH3C
COCH3
Ph
CO2CH3
CO2CH3
H3CO2C
H3CO2C
SS
R
1
2
3
4
512
34
5
p3sn
T3sn
(major)
Fig. 6.6.2 endo- attack of dimethylmaleate (E3)
on si- face of azomethine imine (AI)
From a consideration of local electrophilicity ( k) and nucleophilicity (Nk) values in
Table 6.2, it is evident that the bimolecular addition takes place through linking each
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Theoretical studies on cyclization of azomethine imines with electron deficient dipolarophiles
125
of N1 and C3 atoms of the dipole to any one of the C4 and C5 of the dipolarophile,
because these latter ones have similar local electrophilicity (0.92) and local
nucleophilicity (0.896) values. E3 has both ends substituted by methyl ester group
and hence it makes no difference between the normal and regio- adducts.
6.4. Reactivity in Terms of Global and Local Electrophilicity and
Nucleophilicity of the Reactants
The electronic chemical potential is an index pointing to the direction of the
electronic flux during the cycloaddition i.e. the Charge Transfer (CT) within the
system in the ground state. This can be represented by a very simple operational
formulation given by an expression in terms of the one-electron FMO energies,
particularly the HOMO and LUMO energies, within the Kohn Sham6 orbital
approximation. Since the play field of the highest energy electrons within the
occupied subspace of a molecule in ground state is generally the HOMO, we have
presented in Table 6.2 the HOMO energies only of the reagents N1, E1, E2 and E3
together with their electronic chemical potential, chemical hardness, the global
electrophilicity and the nucleophilicity. According to the absolute scale of
electrophilicity based on the index, AI can be classified as a good electrophile
whereas all the dipolarophiles belong to the realm of weak electrophiles. The
electronic chemical potential of AI (-3.808eV) is higher than those of E1 (-4.558eV),
E2 (-4.314eV) and E3 (-4.578eV) implying that the CT would take place from the
dipole to the dipolarophiles in these cycloadditions resulting in normal electron
demand (NED) 1,3DC. The extents of charge transfer have been presented in Table
6.5. The 1,3DC reaction can be classified for the computed value of Charge Transfer
from Natural Bond Order analysis8 at transition states. From the calculated value of
CT (as discussed in chapter 2 in section 2.8.r) presented in Table 6.5, we can classify
our reactions as: the reaction 1 & 2 for the scheme 1 & 2 are nonpolar and the
reaction 3 for scheme 3 is polar.
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Theoretical studies on cyclization of azomethine imines with electron deficient dipolarophiles
126
Table 6.5 Free energy and enthalpy changes in the different reaction channels
Reacting systems Free energy Enthalpy of Free energy Enthalpy of N Charge
along different of activation activation of reaction reaction (eV) (eV) (eV) Transfer
reactive channels G ∆H rG ∆rH (e)
(reagent to product) (kcal.mol-1) (kcal.mol-1) (kcal.mol-1) (kcal.mol-1)
1rx to p1rx 27.469 14.566 -16.170 -30.549 0.134
1rn to p1rn 26.128 12.440 -13.743 -28.776 2.929 0.468 2.102 0.153
1rx-r to p1rx-r 33.724 20.248 -12.815 -24.848 0.066
1rn-r to p1rn-r 45.220 19.083 -15.908 -30.277 0.077
2rx to p2rx 21.998 7.972 -18.031 -35.448 0.132
2rn to p2rn 21.857 7.379 -14.526 -29.583 2.734 0.603 1.761 0.152
2rx-r to p2rx-r 32.270 18.700 -17.450 -32. 670 0.032
2rn-r to p2rn-r 23.369 8.870 -13.852 -28.229 0.068
3sx to p3sx 25.361 10.447 -14.768 -30.930 0.225
3sn to p3sn 21.273 5.577 -7.143 -19.886 2.181 0.245 1.748 0.193
We have calculated the Gibb’s free energies of the reactants and TS in
each case and also the corresponding free energies of activation G≠ at 298K.
Moreover, the heats of reaction rH and free energies of reaction rG at 298K are
calculated by taking difference of the product energy from the sum of those of the
corresponding reactants. As we look to the reactions 1 and 2, we find that Δω in
Table 6.5 increases although the individual ω values in Table 6.2 decrease from E1
to E2. Also the reaction gets faster from E1 to E2 due to decrease in activation
energy and consequential increase in the rate constants, as may be seen from Table
6.6. Similarly in passing from E3 to E2 reacting with AI, Δω increases accompanied
with increase in the rate constant k in Table-6.6 and decrease in average activation
energy Ea in kcal/mol (12.65 for 1, 6.65 for 2 and 7.15 for 3). It may be noted that
switching the dipolarophile from E1 to E2 is tantamount to replacing the more
electron withdrawing -CN by the lesser withdrawing –COOMe group. Similar
observation is made in changing the reagent from E3 to E2 where also the more
withdrawing –COOMe group is introduced in E3 by replacing one hydrogen of E2.
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Theoretical studies on cyclization of azomethine imines with electron deficient dipolarophiles
127
Table 6.6 Gas phase rate constants in different facial (re/si-) attacks in
different enantio (exo/endo-) channels at various temperatures
Activation
Temp Rate constant 1000/T -log(k) slope Energy
K (cm3 molecule
-1s
-1) ( kcal. mol
-1 )
T1rx
298.00 0.13410E-25 3.356 25.8726
323.00 0.88353E-25 3.096 25.0538
348.00 0.44935E-24 2.874 24.3474 3.18383 14.66
373.00 0.18574E-23 2.681 23.7311
398.00 0.64861E-23 2.513 23.1880
T1rx-r
298.00 0.74259E-32 3.356 32.1292
323.00 0.15099E-30 3.096 30.8210
348.00 0.20189E-29 2.874 29.6949 5.0724 23.4
373.00 0.19301E-28 2.681 28.7144
398.00 0.14046E-27 2.513 27.8524
T1rn-r
298.00 0.24398E-31 3.356 31.6126
323.00 0.43336E-30 3.096 30.3632
348.00 0.51597E-29 2.874 29.2874 4.84577 22.3
373.00 0.44605E-28 2.681 28.3506
398.00 0.29724E-27 2.513 27.5269
T2rx
298.00 0.47515E-21 3.356 21.3232
323.00 0.12657E-20 3.096 20.8977
348.00 0.29673E-20 2.874 20.5276 1.67192 7.5
373.00 0.62776E-20 2.681 20.2022
398.00 0.12213E-19 2.513 19.9132
T2rn
298.00 0.35269E-21 3.356 21.4526
323.00 0.88334E-21 3.096 21.0539
348.00 0.19640E-20 2.874 20.7069 1.56836 7.2
373.00 0.39682E-20 2.681 20.4014
398.00 0.74150E-20 2.513 20.1299
T2rx-r
298.00 0.18262E-31 3.356 31.7384
323.00 0.32234E-30 3.096 30.4917
348.00 0.38206E-29 2.874 29.4179 4.8374 22.3
373.00 0.32925E-28 2.681 28.4825
398.00 0.21894E-27 2.513 27.6597
T2rn-r
298.00 0.11859E-25 3.356 25.9260
323.00 0.65739E-25 3.096 25.1822
348.00 0.28857E-24 2.874 24.5397 2.89685 13.3
373.00 0.10507E-23 2.681 23.9785
398.00 0.32859E-23 2.513 23.4833
T3sx
298.00 0.45184E-24 3.356 24.3450
323.00 0.18152E-23 3.096 23.7411
348.00 0.60563E-23 2.874 23.2178 2.36161 10.9
373.00 0.17408E-22 2.681 22.7593
398.00 0.44307E-22 2.513 22.3535
T3sn
298.00 0.75099E-21 3.356 21.1244
323.00 0.15341E-20 3.096 20.8142
348.00 0.28672E-20 2.874 20.5425 1.22978 5.7
373.00 0.49882E-20 2.681 20.3021
398.00 0.81833E-20 2.513 20.0871
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Theoretical studies on cyclization of azomethine imines with electron deficient dipolarophiles
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The condensed Fukui functions (electrophilic and nucleophilic) of the reactants
helps us to understand the reactivity and are calculated for the atomic sites in order
to rationalize the observed regioselectivity in respect of the cycloadditions. The local
nucleophilicity Nk has been calculated on the basis of global nucleophilicity N and
Fukui function fk+. In this respect the atom N1 in AI prefers to attach with C5 of E1
or E2. Since the molecule E3 is symmetrical, the attachment can take place to either
end. The nucleophilicity guidance to regioselective attack suggests that
regioisomeric cyclization will not be favoured in the present case as may be seen
from the corresponding higher activation energies in Table 6.4.
The dipole AI may be classified as a strong electrophile since its site N1 shows
greater local electrophilicity than that at C3 in Table 6.2. Therefore, N1 should be
the preferred site for nucleophilic attack by the dipolarophile site C5 in both the
schemes 6.1 and 6.2. In the reaction scheme 6.3, the dipolarophile E3 is
symmetrically substituted and it will have no preferred selectivity for site. This
observation in terms of local electrophilicity and nucleophilicity indices is found in
conformity with the experimental findings.
6.5. Nature of the Transition State:
Although the mechanistic interpretations by Huisgen43
and Firestone44
as discussed
in chapter 3 had invoked controversies, numerous experimental and theoretical
studies have established that the four-center concerted pathway is very promising to
explain the reactivities and selectivities of a wide range of 1,3DC. Huisgen
discovered the most convincing exceptions to the concerted path. On these grounds,
we hold it reasonably safe to attempt the transition state optimizations on the basis
of a concerted mechanistic pathway. A similar theoretical investigation of
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Theoretical studies on cyclization of azomethine imines with electron deficient dipolarophiles
129
mechanism and regioselectivity for 1,3DC of diazomethane with methylacrylate has
concluded the process to be asynchronous and concerted. The work has also
attempted to rationalize regioselectivity by FMO model and density derived philicity
indexes
Our calculated results show remarkable agreement with the experimental findings.
We are successful in characterizing the proper transition states through frequency
analysis, because each such transition state corresponds to a single imaginary
frequency. Finally, we conclude that these reactions proceed through an early and
asynchronous transition state in the gas phase calculations. It will be interesting to
observe the situation when the reaction is occurring in solution. Theoretical
calculations of a reaction process in solvent media having definite polarity and
dielectric property, certainly involve complicated mechanism which demands either
a simulation study with solvent dynamics or a simple TS type calculation within a
solvent continuum. The latter approach might be non-relevant, however it is
straightforward to implement. Test optimization calculation on the small model
system AI0-E0 has been carried out in the solvents CCl4, ethanol, and acetonitrile in
order to explore whether the asynchronicity and reaction rates will be very different
in solution from the gas phase. It is observed from Table 6.3 that there is almost no
change in the rC-C and rC-N distances as also in the PBO and NBO bond orders for any
particular mode (exo- and endo-) of the reaction over the various solvents, indicating
that asynchronicity of the reaction is insensitive towards solvent change. Had there
been considerable effect on asynchronicity, this might help in elucidating whether
the reaction in solution involves a concerted or a two-step mechanism. The
calculated results in Table 6.4 indicate that the activation barriers have increased
with increasing polarity of the solvent indicating that the reaction would become
slower in polar solvent media than in the gas phase. The trend of endoselectivity is
obvious from the values of activation barriers calculated in gas phase and in the
different solvents. It appears that the endoselectivity remains almost unchanged in
solution as compared to the gas phase, the exo-endo difference in barriers is about
0.4 kcal/mol.
Page 139
Theoretical studies on cyclization of azomethine imines with electron deficient dipolarophiles
130
6.6. Selectivity and Reactivity of the Cycloadditions
From the knowledge of selectivity obtained from the local electrophilicity and
nucleophilicity data, the corresponding regio- modes of attack are not considered for
saving unnecessary computational labour. Still, we take up computing the regio-
modes to show that those are unviable due to their higher energy of activation. Some
times the results are not in agreement with the experimental findings for the
cycloaddition. In several calculations, DFT results predicted a different regioisomer
due to very small differences in calculated energy. M. Carda and coworkers45
also
reported the inability for transition state calculations to predict accurately the
observed regioselectivities of 1,3DC reactions. On the other hand the
regioselectivities predicted by local electrophilicity and nucleophilicity indices in
Table 6.2 are found to be in accurate agreement with experimental observations
which are discussed in section 6.4.
6.7. Conclusion
The 1,3-dipolar cycloaddition reactions of the well-known azomethine imine with
three selected alkenes have been studied using the DFT/B3LYP/6-31G(d) method.
The experimentally obtained products, their relative selectivity of addition have been
rationalized utilizing calculated potential energy barriers, theoretical rate constants
and reactivity parameters. We have noted that with increasing electron withdrawing
power of the dipolarophile substituents, the activation barrier increases and thus rate
of reactions with the same imine become slower. This type of investigation can be
easily extended to larger natural systems of stereochemical significance and be used
in asymmetric synthesis and stereoselective synthesis of C-nucleosides. The
reactions become slower in polar solvent media, but the asynchronicity of
cycloaddition is not changed appreciably from the gas phase.
Page 140
Theoretical studies on cyclization of azomethine imines with electron deficient dipolarophiles
131
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11. K. V. Gothelf and K.A. Jorgensen, Chem. Rev. 98 (1998) 863.
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Chemical Reactivity, ed. A. Toro-Labbe, Elsevier Science, New York, 2007.
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132
20. R. Domingo, E. Chamorro, P. Perez, J. Phys. Chem. A 112 (2008) 4946.
21. L. R. Domingo, M. J. Aurell, P. Pérez, R. Contreras, Tetrahedron 58 (2002)
4417.
22. R. G. Parr, Pratim K Chattaraj, J. Am. Chem. Soc. 113 (1991) 185.
23. R. G. Parr, R. G. Pearson, J. Am. Chem. Soc. 105 (1983) 7512.
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25. H. Chermette, J. Comput. Chem. 20 (1999) 129.
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27. R. Huisgen, J. Org. Chem. 33 (1968) 2291.
28. M. J. S. Dewar, J. Am. Chem. Soc. 106 (1984) 209.
29. C. Belzecki and I. Panfil, J. Chem. Soc. Chem. Commun. (1977) 302.
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31. P. Merino, T.Tejero, U. Chiaccio, G. Romeo, A. Rescifina, Tetrahedron 63
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32. L. R. Domingo, M.J. Aurell, M. Arnó, J.A. Sáez, J. Mol. Struct.:
THEOCHEM852 (2008) 46-53.
33. M. T. Nguyen, A.K. Chandra, S. Sakai, K. Morokuma, J. Org. Chem. 64
(1999) 65.
34. M. A. Silva, J. M. Goodman, Tetrahedron 56 (2002) 3667.
35. C. Di Valentin, M. Freccero, R. Gandolfi, A.Rastelli, J. Org. Chem. 65
(2000) 6112.
36. J. Liu, S. Niwayama, Y. You, K.N. Houk, J. Org. Chem. 63 (1998) 1064.
37. F. P. Cossio, I. Morao, H. Jiao, P.V.R. Scheleyer, J. Am. Chem. Soc. 121
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38. G. S. Hammond, J. Am. Chem.Soc. 77 (1955) 334.
39. T. K. Das, M. Banerjee, J. Phys. Org. Chem. 23 (2009) 148.
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42. L. R. Domingo, J. Org. Chem. 64 (1999) 3922.
43. R. Huisgen, J. Org. Chem., 33 (1968) 2291.
Page 142
Theoretical studies on cyclization of azomethine imines with electron deficient dipolarophiles
133
44. R.A. Firestone, Heterocycles, 25 (1987) 61.
45. M. Carda, R. Portolés, J. Murga, S. Uriel, J. A. Marco, L. R. Domingo, R. J.
Zaragoźa, H. Röper, J. Org. Chem. 65 (2000) 7000.
Page 143
List of Publications
Page 144
List of Publications
135
1. DFT study of the 1,3-dipolar cycloaddition of azomethine ylides
with maleimide, maleic anhydride, methylacrylate and some simple
substituted alkenes
Tapas Kumar Das, Manas Banerjee,
J. Phys. Org. Chem. 23 (2010) 148-155
2. A DFT-based exploration augmented by X-ray and NMR of the
stereoselectivity in the 1,3-dipolar cycloaddition of 1-pyrroline-1-
oxide to methyl cinnamate and benzylidene acetophenon
Nivedita Acharjee, Tapas Kumar Das, Avijit Banerji, Manas Banerjee and
Theirry prangé,
J. Phys. Org. Chem. 23 (2010) 1187-1195
3. Computational DFT study of the 1,3-dipolar cycloadditions of 1-
phenylethyltrans-2-methyl nitrone to styrene and 1-phenylethyl
nitrone to allyl alcohol
Tapas Kumar Das, Sneha Salampuria, Manas Banerjee,
J. Mol. Struct.: THEOCHEM: 959 (2010) 22–29
Page 145
List of Publications
136
4. DFT study of 1,3-dipolar cycloaddition of azomethine imines with
electron deficient dipolarophiles acrylonitrile, methylpropenoate,
and dimethylmaleate
Tapas Kumar Das, Sneha Salampuria, Manas Banerjee,
Comput. Theor. Chem. 979 (2012) 102–111
5. 1,3-Dipolar cycloadditions. Part XVII: Experimental and
theoretical spectroscopic investigations of C-aryl-N-methyl nitrones
Nivedita Acharjee, Avijit Banerji, Manas Banerjee and
Tapas Kumar Das,
Ind. J. Chem. 48A (2009) 1627- 1637*
*Serial no. 5 is not included in this thesis.
Page 148
Annexure 1
1
Molecule= 1EN, Final optimized geometry with frequency analysis.
----------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------
Total Energy=E(RB+HF-LYP) = -78.5874581821 A.U.
------------------------------------------------------------------------
Standard orientation:
------------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.000000 0.665544 0.000000
2 1 0 0.923524 1.239972 0.000000
3 1 0 -0.923520 1.239976 0.000000
4 6 0 0.000000 -0.665544 0.000000
5 1 0 -0.923524 -1.239972 0.000000
6 1 0 0.923520 -1.239976 0.000000
-----------------------------------------------------------------------------
Rotational constants (GHZ): 146.9865319 30.0302047 24.9356966
-----------------------------------------------------------------------------
Zero-point correction= 0.051221 (Hartree/Particle)
Thermal correction to Energy= 0.054263
Thermal correction to Enthalpy= 0.055207
Thermal correction to Gibbs Free Energy= 0.029691
Sum of electronic and zero-point Energies= -78.536237
Sum of electronic and thermal Energies= -78.533195
Sum of electronic and thermal Enthalpies= -78.532251
Sum of electronic and thermal Free Energies= -78.557767
----------------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
---------------------------------------------------------------------------
E(RB+HF-LYP) = -78.6083461552 A.U.
______________________________________________________________________________________
Molecule= 1P, Final optimized geometry with frequency analysis.
----------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------------------------
E(RB+HF-LYP) = -212.582016908 A.U.
----------------------------------------------------------------
Standard orientation:
------------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
------------------------------------------------------------------------
1 6 0 -1.156844 -0.452787 0.193004
2 1 0 -1.335673 -0.610888 1.264795
3 1 0 -2.056733 -0.776242 -0.339391
4 7 0 -0.000708 -1.273887 -0.200237
5 1 0 -0.000649 -1.354698 -1.217986
6 1 0 2.055924 -0.778812 -0.338715
7 6 0 1.156234 -0.454091 0.193245
8 1 0 1.334465 -0.612074 1.265154
9 1 0 -1.164631 1.362857 -1.040107
10 6 0 -0.777128 1.030946 -0.070156
11 6 0 0.778390 1.029995 -0.070484
12 1 0 -1.196078 1.701410 0.687845
13 1 0 1.198468 1.700236 0.687107
14 1 0 1.165951 1.361036 -1.040694
------------------------------------------------------------------------------
Rotational constants (GHZ): 6.8272669 6.6373612 3.8625092
-------------------------------------------------------------------------------
Zero-point correction= 0.130388 (Hartree/Particle)
Thermal correction to Energy= 0.135361
Thermal correction to Enthalpy= 0.136305
Thermal correction to Gibbs Free Energy= 0.101979
Sum of electronic and zero-point Energies= -212.451629
Sum of electronic and thermal Energies= -212.446656
Sum of electronic and thermal Enthalpies= -212.445712
Sum of electronic and thermal Free Energies= -212.480038
_____________________________________________________________________________________
Molecule= 1TS, Final optimized geometry with frequency analysis.
------------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
-----------------------------------------------------------
E(RB+HF-LYP) = -212.470832931 A.U.
Page 149
Annexure 1
2
--------------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -0.907885 1.206045 0.198217
2 1 0 -0.741048 1.289713 1.263214
3 1 0 -1.264005 2.072322 -0.344187
4 7 0 -1.266933 0.000034 -0.277887
5 1 0 -1.568562 0.000052 -1.247116
6 1 0 -1.264214 -2.072254 -0.344199
7 6 0 -0.908016 -1.206015 0.198214
8 1 0 -0.741151 -1.289703 1.263204
9 1 0 1.564499 1.248223 -0.986035
10 6 0 1.556890 0.679994 -0.061138
11 6 0 1.556900 -0.680062 -0.061142
12 1 0 1.765607 1.247850 0.840728
13 1 0 1.765542 -1.247923 0.840737
14 1 0 1.564535 -1.248292 -0.986039
---------------------------------------------------------------------
Rotational constants (GHZ): 6.7556557 3.9187632 2.7654813
------------------------------------------------------------------------------
Zero-point correction= 0.122436 (Hartree/Particle)
Thermal correction to Energy= 0.128660
Thermal correction to Enthalpy= 0.129604
Thermal correction to Gibbs Free Energy= 0.093536
Sum of electronic and zero-point Energies= -212.348397
Sum of electronic and thermal Energies= -212.342173
Sum of electronic and thermal Enthalpies= -212.341229
Sum of electronic and thermal Free Energies= -212.377297
----------------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
----------------------------------------------------------------------------
E(RB+HF-LYP) = -212.528602786 A.U. after
______________________________________________________________________________________
Molecule = 1AY, Final optimized geometry with frequency analysis.
----------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
-------------------------------------------
E(RB+HF-LYP) = -133.885273876 A.U.
---------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 1.229011 0.183763 0.000012
2 1 0 1.342722 1.258169 0.000016
3 1 0 2.072345 -0.487823 -0.000038
4 7 0 0.000000 -0.341090 0.000002
5 1 0 -0.000001 -1.358227 -0.000003
6 1 0 -2.072339 -0.487830 0.000116
7 6 0 -1.229014 0.183765 -0.000035
8 1 0 -1.342713 1.258172 0.000034
---------------------------------------------------------------------
Rotational constants (GHZ): 63.4221347 10.4112251 8.9431407
---------------------------------------------------------------------------
Zero-point correction= 0.067454 (Hartree/Particle)
Thermal correction to Energy= 0.071739
Thermal correction to Enthalpy= 0.072683
Thermal correction to Gibbs Free Energy= 0.042639
Sum of electronic and zero-point Energies= -133.817819
Sum of electronic and thermal Energies= -133.813535
Sum of electronic and thermal Enthalpies= -133.812591
Sum of electronic and thermal Free Energies= -133.842635
------------------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
-------------------------------------------------------------------------------
E(RB+HF-LYP) = -133.924900450 A.U.
______________________________________________________________________________________
Molecule= 2EN, Final optimised geometry with frequency analysis.
-----------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
---------------------------------------
Page 150
Annexure 1
3
Total Energy=E(RB+HF-LYP) = -117.907556164 A.U.
-------------------------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -1.283017 0.220426 -0.000060
2 1 0 -1.305444 1.308653 0.000126
3 1 0 -2.245239 -0.284685 0.000345
4 6 0 -0.133775 -0.455618 -0.000142
5 1 0 -0.164062 -1.546334 0.000286
6 6 0 1.234975 0.162915 0.000013
7 1 0 1.811896 -0.150024 0.880802
8 1 0 1.812558 -0.150704 -0.880076
9 1 0 1.181189 1.256755 -0.000348
---------------------------------------------------------------------
Rotational constants (GHZ): 46.7720468 9.2464777 8.1072629
-----------------------------------------------------------------------------
Zero-point correction= 0.080082 (Hartree/Particle)
Thermal correction to Energy= 0.084160
Thermal correction to Enthalpy= 0.085104
Thermal correction to Gibbs Free Energy= 0.055079
Sum of electronic and zero-point Energies= -117.827474
Sum of electronic and thermal Energies= -117.823397
Sum of electronic and thermal Enthalpies= -117.822452
Sum of electronic and thermal Free Energies= -117.852477
------------------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
------------------------------------------------------------------------------
E(RB+HF-LYP) = -117.936126780 A.U.
_____________________________________________________________________________________
Molecule =2PRN. Final optimized geometry with frequency analysis.
------------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------
E(RB+HF-LYP) = -291.209969094 A.U
-----------------------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -0.742476 1.308684 -0.082974
2 1 0 -1.279140 1.704454 0.786570
3 1 0 -0.947027 1.981488 -0.921596
4 6 0 -1.192564 -0.146928 -0.412606
5 1 0 -1.326360 -0.230243 -1.497999
6 6 0 -2.485591 -0.581996 0.277516
7 1 0 -3.329476 0.047986 -0.027758
8 1 0 -2.741922 -1.619806 0.031267
9 1 0 -2.394094 -0.510651 1.368777
10 1 0 0.118763 -1.921037 -0.595454
11 6 0 0.040005 -0.984285 -0.030474
12 7 0 1.158447 -0.099724 -0.337809
13 1 0 0.002437 -1.247895 1.049099
14 6 0 0.772139 1.202259 0.208472
15 6 0 2.450772 -0.573393 0.114000
16 1 0 1.364544 2.001219 -0.253177
17 1 0 0.953270 1.250557 1.301699
18 1 0 2.507189 -0.699827 1.214707
19 1 0 2.677166 -1.539650 -0.350790
20 1 0 3.231802 0.135429 -0.184286
---------------------------------------------------------------------
Rotational constants (GHZ): 5.1893223 1.8899467 1.5168729
-------------------------------------------------------------------------------
Zero-point correction= 0.186130 (Hartree/Particle)
Thermal correction to Energy= 0.193778
Thermal correction to Enthalpy= 0.194722
Thermal correction to Gibbs Free Energy= 0.154312
Sum of electronic and zero-point Energies= -291.023839
Sum of electronic and thermal Energies= -291.016191
Sum of electronic and thermal Enthalpies= -291.015247
Sum of electronic and thermal Free Energies= -291.055657
_____________________________________________________________________________________
Molecule = 2PRX. Final optimised geometry with frequency analysis.
Page 151
Annexure 1
4
--------------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------
E(RB+HF-LYP) = -291.209968959 A.U.
-----------------------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -0.742446 1.308456 -0.080873
2 1 0 -1.277108 1.701511 0.791125
3 1 0 -0.950065 1.983130 -0.917249
4 6 0 -1.192352 -0.146711 -0.412189
5 1 0 -1.324775 -0.229219 -1.497803
6 6 0 -2.486318 -0.581871 0.276081
7 1 0 -3.329544 0.048830 -0.029521
8 1 0 -2.742900 -1.619317 0.028593
9 1 0 -2.395955 -0.511574 1.367499
10 1 0 0.002002 -1.246457 1.050632
11 6 0 0.039682 -0.984130 -0.029294
12 7 0 1.158417 -0.100330 -0.337756
13 1 0 0.118260 -1.921601 -0.593089
14 6 0 0.773053 1.202911 0.206397
15 6 0 2.450701 -0.574011 0.113992
16 1 0 0.957494 1.254185 1.298917
17 1 0 1.363868 2.000833 -0.259091
18 1 0 2.676183 -1.541221 -0.349249
19 1 0 3.231961 0.133818 -0.186049
20 1 0 2.507744 -0.698471 1.214900
---------------------------------------------------------------------
Rotational constants (GHZ): 5.1903001 1.8897639 1.5164907
-----------------------------------------------------------------------------
Zero-point correction= 0.186133 (Hartree/Particle)
Thermal correction to Energy= 0.193780
Thermal correction to Enthalpy= 0.194725
Thermal correction to Gibbs Free Energy= 0.154318
Sum of electronic and zero-point Energies= -291.023836
Sum of electronic and thermal Energies= -291.016189
Sum of electronic and thermal Enthalpies= -291.015244
Sum of electronic and thermal Free Energies= -291.055651
_____________________________________________________________________________________
Molecule = 2PSN. Final optimized geometry with frequency analysis.
----------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------
E(RB+HF-LYP) = -291.209969038 A.U.
---------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.742422 1.308623 -0.081503
2 1 0 1.277550 1.702760 0.789738
3 1 0 0.949212 1.982572 -0.918662
4 6 0 1.192373 -0.146726 -0.412062
5 1 0 1.324684 -0.229622 -1.497687
6 6 0 2.486348 -0.581823 0.276189
7 1 0 3.329597 0.048784 -0.029574
8 1 0 2.396148 -0.511419 1.367622
9 1 0 2.742856 -1.619306 0.028750
10 1 0 -0.118004 -1.921587 -0.593164
11 6 0 -0.039791 -0.984222 -0.029123
12 7 0 -1.158360 -0.100290 -0.337952
13 1 0 -0.002464 -1.246600 1.050726
14 6 0 -0.772858 1.202494 0.207104
15 6 0 -2.450828 -0.573698 0.113767
16 1 0 -1.364439 2.000693 -0.256931
17 1 0 -0.956202 1.252556 1.299888
18 1 0 -2.507790 -0.698963 1.214566
19 1 0 -3.231769 0.134737 -0.185678
20 1 0 -2.676860 -1.540457 -0.350156
---------------------------------------------------------------------
Rotational constants (GHZ): 5.1906365 1.8896706 1.5165242
----------------------------------------------------------------------------
Zero-point correction= 0.178932 (Hartree/Particle)
Thermal correction to Energy= 0.187967
Page 152
Annexure 1
5
Thermal correction to Enthalpy= 0.188911
Thermal correction to Gibbs Free Energy= 0.145924
Sum of electronic and zero-point Energies= -290.917689
Sum of electronic and thermal Energies= -290.908653
Sum of electronic and thermal Enthalpies= -290.907709
Sum of electronic and thermal Free Energies= -290.950696
_____________________________________________________________________________________
Molecule = 2PSX. Final optimized geometry with frequency analysis.
-----------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
---------------------------------------------------------------------------
Total energy = E(RB+HF-LYP) = -291.209969018 A.U.
----------------------------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.742411 1.308547 -0.080848
2 1 0 1.276931 1.701760 0.791183
3 1 0 0.950135 1.983128 -0.917266
4 6 0 1.192322 -0.146635 -0.412024
5 1 0 1.324258 -0.229266 -1.497712
6 6 0 2.486527 -0.581831 0.275744
7 1 0 3.329646 0.048939 -0.030026
8 1 0 2.396578 -0.511766 1.367215
9 1 0 2.743044 -1.619217 0.027920
10 1 0 -0.002115 -1.246045 1.051248
11 6 0 -0.039675 -0.984109 -0.028736
12 7 0 -1.158328 -0.100466 -0.337832
13 1 0 -0.117875 -1.921748 -0.592331
14 6 0 -0.773166 1.202761 0.206472
15 6 0 -2.450797 -0.573956 0.113701
16 1 0 -0.957466 1.253766 1.299020
17 1 0 -1.364198 2.000663 -0.258771
18 1 0 -2.676387 -1.541082 -0.349670
19 1 0 -2.508098 -0.698555 1.214574
20 1 0 -3.231895 0.134021 -0.186414
---------------------------------------------------------------------
Rotational constants (GHZ): 5.1908154 1.8896431 1.5164133
----------------------------------------------------------------------------------------
Zero-point correction= 0.186133 (Hartree/Particle)
Thermal correction to Energy= 0.193779
Thermal correction to Enthalpy= 0.194723
Thermal correction to Gibbs Free Energy= 0.154328
Sum of electronic and zero-point Energies= -291.023836
Sum of electronic and thermal Energies= -291.016190
Sum of electronic and thermal Enthalpies= -291.015246
Sum of electronic and thermal Free Energies= -291.055641
_____________________________________________________________________________________
Molecule = 2TRN. Final optimised geometry with frequency analysis.
-------------------------------------------------------------------
# opt=qst3 freq b3lyp/6-31g(d) geom=connectivity
------------------------------------------------
E(RB+HF-LYP) = -291.096620558 A.U.
-------------------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 1.119281 1.340774 -0.448437
2 1 0 1.018409 1.255799 -1.527660
3 1 0 1.078789 2.349496 -0.051056
4 6 0 1.591288 0.297398 0.298577
5 1 0 1.921698 0.496606 1.316441
6 6 0 2.108099 -0.987352 -0.309370
7 1 0 1.668804 -1.166163 -1.298580
8 1 0 3.199308 -0.942655 -0.450168
9 1 0 1.902082 -1.864588 0.313262
10 1 0 -0.418952 0.185487 2.120578
11 6 0 -0.563282 -0.501378 1.297312
12 7 0 -1.301859 -0.059566 0.257696
13 1 0 -0.598391 -1.561522 1.513615
14 6 0 -1.344607 1.236125 -0.107269
15 6 0 -1.632293 -1.042080 -0.783250
Page 153
Annexure 1
6
16 1 0 -1.239060 1.973675 0.676102
17 1 0 -1.937034 1.488666 -0.977080
18 1 0 -0.797126 -1.136080 -1.484565
19 1 0 -1.832102 -2.009631 -0.319863
20 1 0 -2.524332 -0.713054 -1.320277
---------------------------------------------------------------------
Rotational constants (GHZ): 3.4130858 1.8673474 1.6020358
---------------------------------------------------------------------------
Zero-point correction= 0.178931 (Hartree/Particle)
Thermal correction to Energy= 0.187967
Thermal correction to Enthalpy= 0.188911
Thermal correction to Gibbs Free Energy= 0.145922
Sum of electronic and zero-point Energies= -290.917690
Sum of electronic and thermal Energies= -290.908654
Sum of electronic and thermal Enthalpies= -290.907709
Sum of electronic and thermal Free Energies= -290.950698
-----------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
-------------------------------------------------------------------
E(RB+HF-LYP) = -291.167982342 A.U.
______________________________________________________________________________________
Molecule =2TRX. Final optimized geometry with frequency analysis.
-------------------------------------------------------------------
# opt=qst3 freq b3lyp/6-31g(d) geom=connectivity
-------------------------------------------------------------------
E(RB+HF-LYP) = -291.097819026 A.U.
----------------------------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -0.977273 1.343696 -0.406035
2 1 0 -1.380750 1.954353 0.397652
3 1 0 -0.382706 1.872413 -1.144543
4 6 0 -1.445889 0.082629 -0.636559
5 1 0 -1.203742 -0.401761 -1.580350
6 6 0 -2.585417 -0.528032 0.144778
7 1 0 -2.649032 -0.100729 1.153359
8 1 0 -3.551506 -0.336535 -0.346504
9 1 0 -2.490306 -1.615094 0.247442
10 1 0 -0.193979 -1.337160 1.302510
11 6 0 0.425173 -1.268891 0.418594
12 7 0 1.298660 -0.244725 0.354270
13 1 0 0.688692 -2.180254 -0.102414
14 6 0 1.082464 0.945201 0.947122
15 6 0 2.228710 -0.249045 -0.782244
16 1 0 0.483427 0.948197 1.847076
17 1 0 1.838730 1.709089 0.823688
18 1 0 2.586136 -1.265797 -0.955177
19 1 0 1.716942 0.117786 -1.678541
20 1 0 3.080865 0.395220 -0.558033
---------------------------------------------------------------------
Rotational constants (GHZ): 4.0905057 1.6110768 1.4496628
----------------------------------------------------------------------------
Zero-point correction= 0.178843 (Hartree/Particle)
Thermal correction to Energy= 0.187901
Thermal correction to Enthalpy= 0.188846
Thermal correction to Gibbs Free Energy= 0.145803
Sum of electronic and zero-point Energies= -290.918976
Sum of electronic and thermal Energies= -290.909918
Sum of electronic and thermal Enthalpies= -290.908973
Sum of electronic and thermal Free Energies= -290.952016
------------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
-------------------------------------------------------------------------
E(RB+HF-LYP) = -291.169557780 A.U.
______________________________________________________________________________________
Molecule = 2TSN. Final optimised geometry with frequency analysis.
------------------------------------------------------------------
# opt=qst3 freq b3lyp/6-31g(d) geom=connectivity
------------------------------------------------
E(RB+HF-LYP) = -291.096620435 A.U.
-------------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Page 154
Annexure 1
7
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -1.118881 1.340829 -0.448931
2 1 0 -1.017395 1.255208 -1.528048
3 1 0 -1.079410 2.349888 -0.052282
4 6 0 -1.591070 0.297721 0.298372
5 1 0 -1.922230 0.497250 1.315927
6 6 0 -2.106318 -0.987837 -0.309143
7 1 0 -3.197411 -0.943872 -0.451243
8 1 0 -1.665945 -1.167026 -1.297810
9 1 0 -1.900520 -1.864479 0.314367
10 1 0 0.418695 0.186982 2.120562
11 6 0 0.562616 -0.500490 1.297720
12 7 0 1.301291 -0.059562 0.257837
13 1 0 0.597677 -1.560476 1.514817
14 6 0 1.344411 1.236015 -0.107556
15 6 0 1.631166 -1.042542 -0.782975
16 1 0 1.239708 1.973805 0.675652
17 1 0 1.936526 1.488001 -0.977735
18 1 0 1.827001 -2.011015 -0.319851
19 1 0 0.797338 -1.133613 -1.486270
20 1 0 2.525384 -0.715893 -1.317865
---------------------------------------------------------------------
Rotational constants (GHZ): 3.4123515 1.8688410 1.6031148
-------------------------------------------------------------------------------
Zero-point correction= 0.178932 (Hartree/Particle)
Thermal correction to Energy= 0.187967
Thermal correction to Enthalpy= 0.188911
Thermal correction to Gibbs Free Energy= 0.145924
Sum of electronic and zero-point Energies= -290.917689
Sum of electronic and thermal Energies= -290.908653
Sum of electronic and thermal Enthalpies= -290.907709
Sum of electronic and thermal Free Energies= -290.950696
--------------------------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
------------------------------------------------------------------------------------
E(RB+HF-LYP) = -291.167978321 A.U
______________________________________________________________________________________
Molecule=2TSX. Final optimised geometry with frequency analysis.
-------------------------------------------------------------------
# freq b3lyp/6-31g(d) geom=connectivity
---------------------------------------
E(RB+HF-LYP) = -291.097818386 A.U.
-------------------------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.976520 1.342960 -0.405911
2 1 0 1.380024 1.953802 0.397609
3 1 0 0.381879 1.871456 -1.144536
4 6 0 1.446043 0.082171 -0.636767
5 1 0 1.206064 -0.401192 -1.581693
6 6 0 2.586000 -0.527410 0.144865
7 1 0 3.551108 -0.342459 -0.350792
8 1 0 2.654031 -0.093349 1.150253
9 1 0 2.487682 -1.613463 0.255232
10 1 0 0.194421 -1.337637 1.300935
11 6 0 -0.425868 -1.269408 0.417819
12 7 0 -1.299010 -0.244802 0.354448
13 1 0 -0.691019 -2.180977 -0.102049
14 6 0 -1.081516 0.944634 0.947603
15 6 0 -2.229070 -0.248016 -0.781998
16 1 0 -0.482528 0.946899 1.847573
17 1 0 -1.836227 1.709950 0.823709
18 1 0 -2.589564 -1.263978 -0.953330
19 1 0 -3.079264 0.399186 -0.558831
20 1 0 -1.716196 0.115799 -1.678885
---------------------------------------------------------------------
Rotational constants (GHZ): 4.0917722 1.6108028 1.4496245
------------------------------------------------------------------------------------------------------------
Zero-point correction= 0.178841 (Hartree/Particle)
Thermal correction to Energy= 0.187901
Thermal correction to Enthalpy= 0.188845
Thermal correction to Gibbs Free Energy= 0.145798
Sum of electronic and zero-point Energies= -290.918977
Sum of electronic and thermal Energies= -290.909918
Page 155
Annexure 1
8
Sum of electronic and thermal Enthalpies= -290.908973
Sum of electronic and thermal Free Energies= -290.952020
------------------------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
-------------------------------------------------------------------------
E(RB+HF-LYP) = -291.169553545 A.U. after
______________________________________________________________________________________
Molecule =2AY. Final optimised geometry with frequency analysis.
------------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------------
Total Energy = E(RB+HF-LYP) = -173.195280634 A.U.
---------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -0.709202 1.207845 -0.003256
2 1 0 -1.786677 1.270924 0.048229
3 1 0 -0.084261 2.085703 -0.010755
4 7 0 -0.132895 0.000059 -0.019264
5 1 0 -0.086577 -2.085640 -0.009807
6 6 0 -0.710548 -1.207087 -0.003480
7 1 0 -1.788095 -1.268956 0.048001
8 6 0 1.346118 -0.000722 0.009985
9 1 0 1.714324 0.887692 -0.504258
10 1 0 1.689952 -0.000108 1.046919
11 1 0 1.713392 -0.890251 -0.502975
---------------------------------------------------------------------
Rotational constants (GHZ): 10.0612963 9.9223083 5.1616720
------------------------------------------------------------------------------
Zero-point correction= 0.095452 (Hartree/Particle)
Thermal correction to Energy= 0.101163
Thermal correction to Enthalpy= 0.102107
Thermal correction to Gibbs Free Energy= 0.067630
Sum of electronic and zero-point Energies= -173.099829
Sum of electronic and thermal Energies= -173.094118
Sum of electronic and thermal Enthalpies= -173.093174
Sum of electronic and thermal Free Energies= -173.127650
------------------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
------------------------------------------------------------------------------
E(RB+HF-LYP) = -173.241496957 A.U.
______________________________________________________________________________________
Molecule =3EN. Final potimised geometry with frequency analysis.
----------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------
E(RB+HF-LYP) = -157.220381370 A.U.
----------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -1.536274 -0.586518 -0.000014
2 1 0 -1.044748 -1.555780 0.000265
3 1 0 -2.622864 -0.598532 0.000041
4 6 0 -0.855799 0.560642 -0.000051
5 1 0 -1.415826 1.497508 -0.000169
6 6 0 0.643430 0.721675 0.000072
7 1 0 0.926421 1.331603 -0.871803
8 1 0 0.926309 1.331423 0.872096
9 6 0 1.454217 -0.575794 -0.000045
10 1 0 2.527996 -0.360074 -0.000190
11 1 0 1.234744 -1.183078 0.885421
12 1 0 1.234526 -1.183099 -0.885440
---------------------------------------------------------------------
Rotational constants (GHZ): 15.4002874 5.5045302 4.2683243
----------------------------------------------------------------------------------
Zero-point correction= 0.109231 (Hartree/Particle)
Thermal correction to Energy= 0.114346
Thermal correction to Enthalpy= 0.115291
Thermal correction to Gibbs Free Energy= 0.082038
Sum of electronic and zero-point Energies= -157.111150
Sum of electronic and thermal Energies= -157.106035
Page 156
Annexure 1
9
Sum of electronic and thermal Enthalpies= -157.105091
Sum of electronic and thermal Free Energies= -157.138344
-------------------------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
---------------------------------------
E(RB+HF-LYP) = -157.257081159 A.U.
______________________________________________________________________________________
Molecule = 3PRN. Final optimized geometry with frequency analysis.
-------------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------
E(RB+HF-LYP) = -369.836112375 A.U.
-------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 1.137614 1.518488 -0.297742
2 1 0 1.636447 1.244235 -1.232841
3 1 0 1.565801 2.470768 0.030865
4 6 0 1.310451 0.393833 0.768481
5 1 0 1.681281 0.829193 1.704061
6 6 0 2.308477 -0.710044 0.360155
7 1 0 3.293975 -0.246235 0.209751
8 1 0 2.427291 -1.397429 1.209869
9 6 0 1.937878 -1.521847 -0.886937
10 1 0 2.691148 -2.295734 -1.075287
11 1 0 0.967081 -2.015030 -0.775071
12 1 0 1.878219 -0.893781 -1.782196
13 1 0 -3.903749 -1.297625 -0.028166
14 6 0 -2.808565 -1.269576 -0.005090
15 6 0 -2.311379 0.171413 -0.126896
16 1 0 -2.428500 -1.876982 -0.833499
17 1 0 -2.486653 -1.733607 0.933485
18 7 0 -0.860744 0.269087 -0.214234
19 1 0 -2.725992 0.616873 -1.040318
20 1 0 -2.701869 0.772171 0.721901
21 6 0 -0.380189 1.617836 -0.514776
22 6 0 -0.134548 -0.117111 0.997167
23 1 0 -0.819002 2.369843 0.173882
24 1 0 -0.658075 1.906577 -1.535350
25 1 0 -0.179675 -1.199993 1.155654
26 1 0 -0.570944 0.365194 1.896721
---------------------------------------------------------------------
Rotational constants (GHZ): 2.3723492 1.1146409 0.9135125
---------------------------------------------------------------------------
Zero-point correction= 0.243774 (Hartree/Particle)
Thermal correction to Energy= 0.253929
Thermal correction to Enthalpy= 0.254873
Thermal correction to Gibbs Free Energy= 0.208312
Sum of electronic and zero-point Energies= -369.592338
Sum of electronic and thermal Energies= -369.582184
Sum of electronic and thermal Enthalpies= -369.581240
Sum of electronic and thermal Free Energies= -369.627800
____________________________________________________________________________________
Molecule=3PRX. Final optimized geometry with frequency analysis.
-----------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------
E(RB+HF-LYP) = -369.830034635 A.U.
-----------------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.494473 1.189081 0.649017
2 1 0 1.292839 1.894728 0.395930
3 1 0 0.119783 1.479223 1.636366
4 6 0 0.985151 -0.288496 0.659081
5 1 0 0.662095 -0.747957 1.602423
6 6 0 2.510272 -0.495466 0.571141
7 1 0 2.971056 -0.054849 1.466102
8 1 0 2.718430 -1.573461 0.631230
9 6 0 3.207650 0.072691 -0.672534
Page 157
Annexure 1
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10 1 0 4.288560 -0.098709 -0.614038
11 1 0 2.853589 -0.396962 -1.596719
12 1 0 3.054083 1.153604 -0.771126
13 1 0 -4.277850 -0.424361 0.638338
14 6 0 -3.512470 -0.057686 -0.055895
15 6 0 -2.132705 -0.582873 0.342838
16 1 0 -3.552840 1.037394 -0.041776
17 1 0 -3.765843 -0.389681 -1.067878
18 7 0 -1.091457 -0.172116 -0.610157
19 1 0 -1.910320 -0.280742 1.384586
20 1 0 -2.160410 -1.679001 0.338772
21 6 0 -0.638463 1.216856 -0.418169
22 6 0 0.156250 -0.938246 -0.485215
23 1 0 -0.241665 1.583749 -1.373686
24 1 0 -1.474748 1.866615 -0.145969
25 1 0 -0.054729 -1.999078 -0.315287
26 1 0 0.697224 -0.860872 -1.437745
---------------------------------------------------------------------
Rotational constants (GHZ): 3.8929138 0.8425642 0.8037224
--------------------------------------------------------------------------------
Zero-point correction= 0.243805 (Hartree/Particle)
Thermal correction to Energy= 0.254053
Thermal correction to Enthalpy= 0.254997
Thermal correction to Gibbs Free Energy= 0.207849
Sum of electronic and zero-point Energies= -369.586229
Sum of electronic and thermal Energies= -369.575982
Sum of electronic and thermal Enthalpies= -369.575037
Sum of electronic and thermal Free Energies= -369.622186
______________________________________________________________________________________
Molecule = 3PSN. Final optimized geometry with frequency analysis.
------------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------
E(RB+HF-LYP) = -369.836112376 A.U.
------------------------------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -1.137615 1.518488 -0.297741
2 1 0 -1.636449 1.244235 -1.232841
3 1 0 -1.565801 2.470768 0.030867
4 6 0 -1.310451 0.393833 0.768482
5 1 0 -1.681282 0.829192 1.704061
6 6 0 -2.308476 -0.710045 0.360155
7 1 0 -2.427290 -1.397430 1.209868
8 1 0 -3.293974 -0.246237 0.209749
9 6 0 -1.937876 -1.521848 -0.886938
10 1 0 -2.691144 -2.295735 -1.075288
11 1 0 -1.878215 -0.893782 -1.782196
12 1 0 -0.967079 -2.015030 -0.775071
13 1 0 3.903749 -1.297624 -0.028166
14 6 0 2.808565 -1.269575 -0.005089
15 6 0 2.311379 0.171413 -0.126897
16 1 0 2.486654 -1.733606 0.933487
17 1 0 2.428499 -1.876983 -0.833498
18 7 0 0.860744 0.269087 -0.214234
19 1 0 2.701869 0.772172 0.721899
20 1 0 2.725990 0.616872 -1.040319
21 6 0 0.134548 -0.117110 0.997168
22 6 0 0.380188 1.617836 -0.514777
23 1 0 0.570944 0.365197 1.896721
24 1 0 0.179676 -1.199992 1.155656
25 1 0 0.658073 1.906576 -1.535352
26 1 0 0.819002 2.369843 0.173880
---------------------------------------------------------------------
Rotational constants (GHZ): 2.3723485 1.1146414 0.9135129
--------------------------------------------------------------------------------
Zero-point correction= 0.243774 (Hartree/Particle)
Thermal correction to Energy= 0.253929
Thermal correction to Enthalpy= 0.254873
Thermal correction to Gibbs Free Energy= 0.208312
Sum of electronic and zero-point Energies= -369.592338
Sum of electronic and thermal Energies= -369.582184
Sum of electronic and thermal Enthalpies= -369.581240
Sum of electronic and thermal Free Energies= -369.627800
_____________________________________________________________________________________
Page 158
Annexure 1
11
Molecule = 3PSX. Final optimised geometry with frequency analysis.
---------------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------
E(RB+HF-LYP) = -369.832677529 A.U
------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.575317 1.226132 -0.095552
2 1 0 1.288459 1.840856 0.466696
3 1 0 0.499614 1.664560 -1.095878
4 6 0 1.028089 -0.260440 -0.158847
5 1 0 0.918315 -0.621447 -1.191146
6 6 0 2.471217 -0.525075 0.287172
7 1 0 2.607998 -0.128071 1.304113
8 1 0 2.629206 -1.610838 0.361523
9 6 0 3.532471 0.071065 -0.644123
10 1 0 4.544852 -0.151073 -0.287362
11 1 0 3.440273 -0.336094 -1.658738
12 1 0 3.437122 1.160942 -0.715745
13 1 0 -4.093732 -0.358195 -1.351269
14 6 0 -3.512283 -0.046250 -0.475565
15 6 0 -2.070780 -0.544658 -0.584944
16 1 0 -3.985517 -0.451434 0.424678
17 1 0 -3.563545 1.047048 -0.418694
18 7 0 -1.280135 -0.207487 0.607308
19 1 0 -2.083286 -1.638042 -0.666353
20 1 0 -1.620331 -0.167477 -1.523348
21 6 0 -0.033652 -0.973131 0.720594
22 6 0 -0.809382 1.188761 0.624427
23 1 0 0.291560 -0.951118 1.771978
24 1 0 -0.193228 -2.021818 0.449372
25 1 0 -1.548730 1.854053 0.170056
26 1 0 -0.694065 1.502128 1.669980
---------------------------------------------------------------------
Rotational constants (GHZ): 3.9208915 0.7952969 0.7572803
----------------------------------------------------------------------------
Zero-point correction= 0.243516 (Hartree/Particle)
Thermal correction to Energy= 0.253848
Thermal correction to Enthalpy= 0.254792
Thermal correction to Gibbs Free Energy= 0.207346
Sum of electronic and zero-point Energies= -369.589162
Sum of electronic and thermal Energies= -369.578830
Sum of electronic and thermal Enthalpies= -369.577886
Sum of electronic and thermal Free Energies= -369.625332
_____________________________________________________________________________________
Molecule =3TRN. Final optimized geometry with frequency analysis.
-----------------------------------------------------------------
# opt=qst3 freq b3lyp/6-31g(d) geom=connectivity
------------------------------------------------
E(RB+HF-LYP) = -369.723444969 A.U.
------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -1.433093 -1.314494 -0.820814
2 1 0 -1.411320 -0.753326 -1.749801
3 1 0 -1.425199 -2.393571 -0.932427
4 6 0 -1.805723 -0.733794 0.363978
5 1 0 -2.058600 -1.396276 1.190738
6 6 0 -2.378721 0.666164 0.511356
7 1 0 -3.477158 0.577444 0.566523
8 1 0 -2.076421 1.093967 1.475563
9 6 0 -2.045191 1.658670 -0.606339
10 1 0 -2.510835 2.631344 -0.409251
11 1 0 -0.965137 1.818380 -0.698034
12 1 0 -2.412220 1.309172 -1.577784
13 1 0 3.662146 0.064113 -0.698449
14 6 0 3.205463 0.842117 -0.078689
15 6 0 1.682074 0.823725 -0.204556
16 1 0 3.597214 1.812817 -0.403003
Page 159
Annexure 1
12
17 1 0 3.511556 0.676538 0.959438
18 7 0 1.103695 -0.460002 0.239927
19 1 0 1.374861 0.988755 -1.242274
20 1 0 1.235554 1.617627 0.398587
21 6 0 1.005957 -1.447226 -0.673890
22 6 0 0.428721 -0.487727 1.410953
23 1 0 0.889244 -2.456378 -0.302930
24 1 0 1.543959 -1.310525 -1.604314
25 1 0 0.571149 0.355077 2.076989
26 1 0 0.268428 -1.459758 1.858952
---------------------------------------------------------------------
Rotational constants (GHZ): 2.2434964 0.9582575 0.8325705
-----------------------------------------------------------------------------------
Zero-point correction= 0.236776 (Hartree/Particle)
Thermal correction to Energy= 0.248204
Thermal correction to Enthalpy= 0.249148
Thermal correction to Gibbs Free Energy= 0.199807
Sum of electronic and zero-point Energies= -369.486669
Sum of electronic and thermal Energies= -369.475241
Sum of electronic and thermal Enthalpies= -369.474297
Sum of electronic and thermal Free Energies= -369.523638
-------------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
---------------------------------------
E(RB+HF-LYP) = -369.809866179 A.U
_____________________________________________________________________________________
Molecule =3TRX. Final optimised geometry with frequency analysis.
-----------------------------------------------------------------
# opt=qst3 freq b3lyp/6-31g(d) geom=connectivity
------------------------------------------------
E(RB+HF-LYP) = -369.725103279 A.U.
--------------------------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 1.141290 1.370045 0.657532
2 1 0 1.708363 1.916659 -0.089321
3 1 0 0.511820 1.978535 1.298477
4 6 0 1.444639 0.078478 0.994051
5 1 0 1.027605 -0.320832 1.916619
6 6 0 2.626927 -0.705851 0.453009
7 1 0 3.442188 -0.664950 1.194457
8 1 0 2.362471 -1.769252 0.377801
9 6 0 3.181330 -0.232865 -0.895074
10 1 0 4.011900 -0.870948 -1.218101
11 1 0 2.415331 -0.259833 -1.679572
12 1 0 3.557976 0.794374 -0.837952
13 1 0 -4.487495 -0.367428 0.513679
14 6 0 -3.623485 -0.430203 -0.157416
15 6 0 -2.362695 0.046406 0.563308
16 1 0 -3.826873 0.187055 -1.038441
17 1 0 -3.517272 -1.469347 -0.484903
18 7 0 -1.167453 -0.021076 -0.301824
19 1 0 -2.472922 1.081460 0.898495
20 1 0 -2.165685 -0.564036 1.449447
21 6 0 -0.754874 1.119776 -0.891066
22 6 0 -0.385971 -1.117047 -0.204308
23 1 0 -0.057411 1.030050 -1.712718
24 1 0 -1.451595 1.949030 -0.902558
25 1 0 -0.801235 -1.971364 0.316663
26 1 0 0.312033 -1.304072 -1.009516
---------------------------------------------------------------------
Rotational constants (GHZ): 3.2684610 0.7420102 0.7178936
------------------------------------------------------------------------------
Zero-point correction= 0.236523 (Hartree/Particle)
Thermal correction to Energy= 0.248099
Thermal correction to Enthalpy= 0.249043
Thermal correction to Gibbs Free Energy= 0.196848
Sum of electronic and zero-point Energies= -369.488580
Sum of electronic and thermal Energies= -369.477004
Sum of electronic and thermal Enthalpies= -369.476060
Sum of electronic and thermal Free Energies= -369.528255
----------------------------------------------------------------------------
b3lyp/6-311+g(d) geom=connectivity sp
---------------------------------------------------
E(RB+HF-LYP) = -369.811787491 A.U
Page 160
Annexure 1
13
_____________________________________________________________________________________
Molecule = 3TSN. Final optimised geometry with frequency analysis.
-----------------------------------------------------------------
# opt=qst3 freq b3lyp/6-31g(d) geom=connectivity
------------------------------------------------
E(RB+HF-LYP) = -369.723445063 A.U.
---------------------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 1.433296 -1.314648 -0.820910
2 1 0 1.410977 -0.753410 -1.749842
3 1 0 1.425244 -2.393714 -0.932576
4 6 0 1.805635 -0.733819 0.363879
5 1 0 2.058652 -1.396191 1.190687
6 6 0 2.378761 0.666135 0.511013
7 1 0 2.077038 1.093892 1.475420
8 1 0 3.477221 0.577336 0.565507
9 6 0 2.044648 1.658699 -0.606463
10 1 0 2.509602 2.631644 -0.409075
11 1 0 2.412007 1.309704 -1.577967
12 1 0 0.964499 1.817704 -0.698230
13 1 0 -3.597440 1.812431 -0.403005
14 6 0 -3.205472 0.841837 -0.078635
15 6 0 -1.682104 0.823639 -0.204821
16 1 0 -3.662204 0.063679 -0.698165
17 1 0 -3.511295 0.676369 0.959592
18 7 0 -1.103499 -0.459833 0.240122
19 1 0 -1.375110 0.988216 -1.242678
20 1 0 -1.235571 1.617856 0.397886
21 6 0 -0.427899 -0.486914 1.410801
22 6 0 -1.006390 -1.447632 -0.673124
23 1 0 -0.267833 -1.458661 1.859483
24 1 0 -0.569714 0.356423 2.076291
25 1 0 -1.545384 -1.311756 -1.603098
26 1 0 -0.889044 -2.456472 -0.301530
---------------------------------------------------------------------
Rotational constants (GHZ): 2.2437061 0.9583460 0.8326049
---------------------------------------------------------------------------------
Zero-point correction= 0.236779 (Hartree/Particle)
Thermal correction to Energy= 0.248205
Thermal correction to Enthalpy= 0.249150
Thermal correction to Gibbs Free Energy= 0.199815
Sum of electronic and zero-point Energies= -369.486666
Sum of electronic and thermal Energies= -369.475240
Sum of electronic and thermal Enthalpies= -369.474295
Sum of electronic and thermal Free Energies= -369.523630
------------------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
------------------------------------------------------------------------------
E(RB+HF-LYP) = -369.809915704 A.U.
_____________________________________________________________________________________
Molecule =3TSX. Final optimised geometry with frequency analysis.
# opt=qst3 freq b3lyp/6-31g(d) geom=connectivity
------------------------------------------------
E(RB+HF-LYP) = -369.725101985 A.U
------------------------------------------------------
Standard orientation: ---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -1.129806 1.366136 0.663550
2 1 0 -1.685178 1.923173 -0.084373
3 1 0 -0.496609 1.964089 1.310788
4 6 0 -1.452583 0.077666 0.993912
5 1 0 -1.046212 -0.330525 1.917286
6 6 0 -2.641838 -0.688962 0.442771
7 1 0 -2.390750 -1.755418 0.364750
8 1 0 -3.460863 -0.640539 1.179593
9 6 0 -3.182187 -0.203589 -0.906625
10 1 0 -4.020345 -0.828425 -1.235872
Page 161
Annexure 1
14
11 1 0 -3.544013 0.828878 -0.848148
12 1 0 -2.412747 -0.239386 -1.687408
13 1 0 4.500741 -0.324589 0.491838
14 6 0 3.636448 -0.372637 -0.180109
15 6 0 2.361848 0.002863 0.575573
16 1 0 3.567537 -1.389309 -0.580241
17 1 0 3.811963 0.312812 -1.015346
18 7 0 1.165930 -0.050205 -0.289605
19 1 0 2.193725 -0.674868 1.416941
20 1 0 2.434031 1.016062 0.981977
21 6 0 0.370085 -1.136188 -0.198204
22 6 0 0.769931 1.097790 -0.876723
23 1 0 -0.330139 -1.308786 -1.004669
24 1 0 0.772495 -1.999006 0.318618
25 1 0 1.476438 1.918888 -0.880009
26 1 0 0.077027 1.019898 -1.703361
---------------------------------------------------------------------
Rotational constants (GHZ): 3.2979139 0.7390023 0.7167551
---------------------------------------------------------------------------------
Zero-point correction= 0.236601 (Hartree/Particle)
Thermal correction to Energy= 0.248123
Thermal correction to Enthalpy= 0.249067
Thermal correction to Gibbs Free Energy= 0.198868
Sum of electronic and zero-point Energies= -369.488501
Sum of electronic and thermal Energies= -369.476979
Sum of electronic and thermal Enthalpies= -369.476035
Sum of electronic and thermal Free Energies= -369.526234
---------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
---------------------------------------
E(RB+HF-LYP) = -369.811800183 A.U.
______________________________________________________________________________________
Molecule = 3AY. Final optimization geometry with frequency analysis.
--------------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
----------------------------------------------------------------------------
E(RB+HF-LYP) = -212.511793935 A.U.
----------------------------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 1.145804 1.208052 -0.122240
2 1 0 2.123084 1.273981 -0.578650
3 1 0 0.574703 2.085435 0.134645
4 7 0 0.619461 0.000152 0.114054
5 1 0 0.581308 -2.085293 0.134273
6 6 0 1.148858 -1.206064 -0.124131
7 1 0 2.126481 -1.268718 -0.580264
8 6 0 -0.768717 -0.001954 0.653359
9 1 0 -0.867919 0.878532 1.292339
10 1 0 -0.866896 -0.885462 1.288279
11 6 0 -1.818097 -0.000111 -0.456346
12 1 0 -2.822062 -0.002619 -0.017510
13 1 0 -1.717166 0.889249 -1.085206
14 1 0 -1.714856 -0.885709 -1.090138
---------------------------------------------------------------------
Rotational constants (GHZ): 7.8039262 4.0921078 3.1777804
----------------------------------------------------------------------------
Zero-point correction= 0.124045 (Hartree/Particle)
Thermal correction to Energy= 0.130994
Thermal correction to Enthalpy= 0.131938
Thermal correction to Gibbs Free Energy= 0.093730
Sum of electronic and zero-point Energies= -212.387749
Sum of electronic and thermal Energies= -212.380800
Sum of electronic and thermal Enthalpies= -212.379856
Sum of electronic and thermal Free Energies= -212.418064
--------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
---------------------------------------
E(RB+HF-LYP) = -212.565082771 A.U.
_____________________________________________________________________________________
Molecule = 4EN. Final optimised geometry with frequency analysis.
----------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------
Page 162
Annexure 1
15
E(RB+HF-LYP) = -235.848215453 A.U.
----------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 2.208551 -0.081691 -0.000074
2 1 0 2.335466 0.997402 0.000239
3 1 0 3.121562 -0.671461 -0.000346
4 6 0 1.009955 -0.666345 -0.000266
5 1 0 0.967645 -1.758163 -0.000632
6 6 0 -0.353480 0.001384 -0.000021
7 6 0 -0.256389 1.535235 -0.000007
8 1 0 -1.258294 1.980112 -0.000498
9 1 0 0.271760 1.902796 0.887202
10 1 0 0.272635 1.902686 -0.886747
11 6 0 -1.120956 -0.465318 1.258787
12 1 0 -2.136376 -0.050061 1.269638
13 1 0 -1.206397 -1.558367 1.289711
14 1 0 -0.610054 -0.142589 2.172972
15 6 0 -1.121505 -0.465213 -1.258459
16 1 0 -2.137217 -0.050646 -1.268423
17 1 0 -0.611515 -0.141712 -2.172902
18 1 0 -1.206268 -1.558310 -1.289977
---------------------------------------------------------------------
Rotational constants (GHZ): 4.3815310 2.6625327 2.6089311
------------------------------------------------------------------------------
Zero-point correction= 0.165513 (Hartree/Particle)
Thermal correction to Energy= 0.173167
Thermal correction to Enthalpy= 0.174111
Thermal correction to Gibbs Free Energy= 0.134943
Sum of electronic and zero-point Energies= -235.682702
Sum of electronic and thermal Energies= -235.675049
Sum of electronic and thermal Enthalpies= -235.674104
Sum of electronic and thermal Free Energies= -235.713272
------------------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
---------------------------------------
E(RB+HF-LYP) = -235.901116513 A.U.
______________________________________________________________________________________
Molecule = 4TRN. Final optimised geometry with frequency analysis.
--------------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------
E(RB+HF-LYP) = -527.086247293 A.U
-----------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.796038 1.621856 -0.139263
2 1 0 1.060729 1.904857 -1.177976
3 1 0 1.326390 2.305299 0.531092
4 7 0 1.096412 0.228225 0.184404
5 1 0 -0.147766 -1.476124 0.185462
6 6 0 0.042820 -0.591133 -0.430618
7 1 0 0.316899 -0.960993 -1.434703
8 6 0 2.493704 -0.241122 0.054974
9 6 0 3.391667 0.630140 0.955452
10 1 0 4.407881 0.221226 0.984332
11 1 0 3.464496 1.660158 0.591098
12 1 0 2.997599 0.653778 1.977251
13 6 0 3.026455 -0.185778 -1.397715
14 1 0 4.056508 -0.558177 -1.443168
15 1 0 2.423682 -0.802367 -2.073799
16 1 0 3.029113 0.838814 -1.785696
17 6 0 2.567517 -1.692010 0.569144
18 1 0 2.012215 -2.383046 -0.073598
19 1 0 3.608870 -2.031668 0.594810
20 1 0 2.156491 -1.758921 1.582544
21 1 0 -4.617175 0.408257 0.180902
22 6 0 -3.653919 0.805466 -0.161820
23 6 0 -2.531922 -0.234015 0.039539
24 1 0 -3.457893 1.726823 0.398083
25 1 0 -3.761900 1.071980 -1.220889
26 6 0 -1.204825 0.336172 -0.543039
Page 163
Annexure 1
16
27 6 0 -2.425775 -0.567463 1.541376
28 6 0 -2.910239 -1.515493 -0.732839
29 6 0 -0.720496 1.681864 0.050012
30 1 0 -1.394575 0.502002 -1.612820
31 1 0 -3.372168 -0.990472 1.899831
32 1 0 -1.639642 -1.302428 1.746230
33 1 0 -2.215509 0.321631 2.145704
34 1 0 -3.867074 -1.916380 -0.376507
35 1 0 -3.011983 -1.314755 -1.806845
36 1 0 -2.157111 -2.302257 -0.608939
37 1 0 -0.945723 1.747062 1.119689
38 1 0 -1.173395 2.547237 -0.444130
---------------------------------------------------------------------
Rotational constants (GHZ): 1.5205473 0.4285443 0.3990738
------------------------------------------------------------------------------
Zero-point correction= 0.355673 (Hartree/Particle)
Thermal correction to Energy= 0.370350
Thermal correction to Enthalpy= 0.371295
Thermal correction to Gibbs Free Energy= 0.316269
Sum of electronic and zero-point Energies= -526.730574
Sum of electronic and thermal Energies= -526.715897
Sum of electronic and thermal Enthalpies= -526.714953
Sum of electronic and thermal Free Energies= -526.769978
_____________________________________________________________________________________
Molecule = 4PRX. Final optimised geometry with frequency analysis.
--------------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------
E(RB+HF-LYP) = -527.085766223 A.U
----------------------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -0.768240 -1.566360 0.151598
2 1 0 -0.892453 -1.650990 1.248049
3 1 0 -1.360639 -2.365962 -0.302887
4 7 0 -1.178186 -0.255419 -0.363354
5 1 0 -0.127245 1.554851 -0.675589
6 6 0 -0.042277 0.630021 -0.098900
7 1 0 0.040189 0.911212 0.968135
8 6 0 -2.533325 0.229282 -0.008626
9 6 0 -2.714639 0.516334 1.501708
10 1 0 -3.737116 0.854737 1.705897
11 1 0 -2.537831 -0.378738 2.108473
12 1 0 -2.033218 1.301050 1.848624
13 6 0 -3.559525 -0.833424 -0.448468
14 1 0 -4.577397 -0.445669 -0.331191
15 1 0 -3.408532 -1.096739 -1.501130
16 1 0 -3.486899 -1.748183 0.148991
17 6 0 -2.813208 1.518751 -0.806268
18 1 0 -2.627451 1.353216 -1.873027
19 1 0 -3.857915 1.823446 -0.678588
20 1 0 -2.187652 2.353803 -0.473811
21 1 0 4.647127 -0.361483 -0.276063
22 6 0 3.647837 -0.676776 -0.600528
23 6 0 2.561120 0.230908 0.012545
24 1 0 3.517357 -1.722979 -0.300783
25 1 0 3.624867 -0.637173 -1.696782
26 6 0 1.173775 -0.212559 -0.535671
27 6 0 2.657657 0.150921 1.550070
28 6 0 2.833290 1.685490 -0.425310
29 6 0 0.729690 -1.669862 -0.211760
30 1 0 1.233923 -0.124542 -1.628466
31 1 0 3.660933 0.447559 1.879601
32 1 0 1.941219 0.817577 2.042167
33 1 0 2.481097 -0.864454 1.922652
34 1 0 3.838275 2.002935 -0.120792
35 1 0 2.767125 1.790228 -1.515587
36 1 0 2.117421 2.384379 0.022809
37 1 0 1.295869 -2.104733 0.617484
38 1 0 0.883309 -2.321781 -1.077043
---------------------------------------------------------------------
Rotational constants (GHZ): 1.5430179 0.4200197 0.3918247
-------------------------------------------------------------------------
Zero-point correction= 0.349104 (Hartree/Particle)
Thermal correction to Energy= 0.365602
Page 164
Annexure 1
17
Thermal correction to Enthalpy= 0.366546
Thermal correction to Gibbs Free Energy= 0.307120
Sum of electronic and zero-point Energies= -526.623684
Sum of electronic and thermal Energies= -526.607186
Sum of electronic and thermal Enthalpies= -526.606241
Sum of electronic and thermal Free Energies= -526.665667
______________________________________________________________________________________
Molecule =4PSN. Final optimised geometry with frequency analysis.
--------------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
---------------------------------------
E(RB+HF-LYP) = -527.086219299 A.U.
---------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -0.793149 1.626981 -0.134554
2 1 0 -1.075323 1.922887 -1.164831
3 1 0 -1.317217 2.296779 0.554067
4 7 0 -1.081404 0.225737 0.170381
5 1 0 0.141437 -1.490269 0.059631
6 6 0 -0.043542 -0.568650 -0.500952
7 1 0 -0.330790 -0.874279 -1.523142
8 6 0 -2.481172 -0.244019 0.060703
9 6 0 -3.054096 -0.141085 -1.373942
10 1 0 -4.081768 -0.521241 -1.404320
11 1 0 -3.076690 0.896777 -1.724221
12 1 0 -2.465480 -0.727011 -2.088608
13 6 0 -3.354893 0.593887 1.014902
14 1 0 -4.370064 0.183762 1.057177
15 1 0 -2.932823 0.582485 2.025652
16 1 0 -3.437593 1.635968 0.688783
17 6 0 -2.538549 -1.711943 0.526448
18 1 0 -2.095419 -1.814289 1.523268
19 1 0 -3.578802 -2.052373 0.574150
20 1 0 -2.005300 -2.380523 -0.157426
21 1 0 3.863203 -1.915561 -0.358034
22 6 0 2.918735 -1.506052 -0.736924
23 6 0 2.518631 -0.238148 0.046529
24 1 0 2.161447 -2.293897 -0.652082
25 1 0 3.055029 -1.285919 -1.803300
26 6 0 1.213769 0.350449 -0.569460
27 6 0 2.357996 -0.599407 1.536948
28 6 0 3.651756 0.798745 -0.097799
29 6 0 0.725692 1.691819 0.033169
30 1 0 1.436937 0.526861 -1.630665
31 1 0 3.284530 -1.046320 1.917569
32 1 0 2.143253 0.280950 2.152216
33 1 0 1.551992 -1.323082 1.700510
34 1 0 4.600310 0.391857 0.273502
35 1 0 3.799396 1.080683 -1.148101
36 1 0 3.439821 1.712571 0.468513
37 1 0 0.965479 1.755598 1.099602
38 1 0 1.167192 2.561960 -0.462990
------------------------------------------------------------------------------
Rotational constants (GHZ): 1.5134610 0.4316331 0.4018811
--------------------------------------------------------------------------------
Zero-point correction= 0.355742 (Hartree/Particle)
Thermal correction to Energy= 0.370405
Thermal correction to Enthalpy= 0.371349
Thermal correction to Gibbs Free Energy= 0.316345
Sum of electronic and zero-point Energies= -526.730478
Sum of electronic and thermal Energies= -526.715815
Sum of electronic and thermal Enthalpies= -526.714871
Sum of electronic and thermal Free Energies= -526.769874
______________________________________________________________________________________
Molecule = 4PSX. Final optimised geometry with frequency analysis.
-------------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
-------------------------------------------------------------------
E(RB+HF-LYP) = -527.079024562 A.U
---------------------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Page 165
Annexure 1
18
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -0.756464 -1.571622 -0.549013
2 1 0 -0.476494 -1.964082 -1.537511
3 1 0 -1.532812 -2.231551 -0.157283
4 7 0 -1.244945 -0.194435 -0.719221
5 1 0 -0.230544 1.656966 -0.443357
6 6 0 -0.019201 0.614893 -0.684797
7 1 0 0.417923 0.608333 -1.693726
8 6 0 -2.422353 0.234641 0.081740
9 6 0 -2.228784 0.130982 1.614235
10 1 0 -3.136133 0.445264 2.144743
11 1 0 -2.008432 -0.897877 1.920952
12 1 0 -1.408400 0.771999 1.955691
13 6 0 -3.626299 -0.635545 -0.338567
14 1 0 -4.540487 -0.273689 0.145535
15 1 0 -3.763623 -0.590959 -1.423811
16 1 0 -3.505030 -1.685600 -0.054241
17 6 0 -2.771470 1.691950 -0.284340
18 1 0 -2.821654 1.810160 -1.371843
19 1 0 -3.746268 1.957645 0.139038
20 1 0 -2.045558 2.411756 0.107568
21 1 0 3.819618 1.932176 -0.086958
22 6 0 2.749058 1.724307 0.031284
23 6 0 2.484557 0.203711 0.047062
24 1 0 2.224480 2.219970 -0.793673
25 1 0 2.420854 2.192885 0.967874
26 6 0 0.970324 -0.043152 0.322264
27 6 0 2.958058 -0.396144 -1.292958
28 6 0 3.309998 -0.422542 1.190174
29 6 0 0.501387 -1.525595 0.360300
30 1 0 0.774242 0.396983 1.309302
31 1 0 4.029316 -0.205356 -1.431716
32 1 0 2.813570 -1.481695 -1.332288
33 1 0 2.435922 0.042229 -2.150427
34 1 0 4.380105 -0.221867 1.054153
35 1 0 3.014406 -0.010322 2.163198
36 1 0 3.179989 -1.509869 1.234736
37 1 0 1.266623 -2.220403 -0.000628
38 1 0 0.260144 -1.827365 1.384919
------------------------------------------------------------------------------
Rotational constants (GHZ): 1.5201443 0.4407954 0.4165665
-------------------------------------------------------------------------------
Zero-point correction= 0.356017 (Hartree/Particle)
Thermal correction to Energy= 0.371476
Thermal correction to Enthalpy= 0.372420
Thermal correction to Gibbs Free Energy= 0.314869
Sum of electronic and zero-point Energies= -526.723007
Sum of electronic and thermal Energies= -526.707549
Sum of electronic and thermal Enthalpies= -526.706605
Sum of electronic and thermal Free Energies= -526.764155
______________________________________________________________________________________
Molecule = 4TRN. Final optimised geometry with frequency analysis.
------------------------------------------------------------------
# opt=qst3 freq b3lyp/6-31g(d) geom=connectivity
------------------------------------------------
E(RB+HF-LYP) = -526.969146429 A.U.
------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 1.288710 1.855592 -0.193374
2 1 0 1.005292 2.582842 -0.942421
3 1 0 1.989475 2.187157 0.560092
4 7 0 1.371686 0.571416 -0.614180
5 1 0 0.619264 -0.885427 -1.918698
6 6 0 0.514767 0.125682 -1.561054
7 1 0 0.163912 0.863606 -2.268491
8 6 0 2.272361 -0.375468 0.156365
9 6 0 2.048574 -1.839726 -0.253660
10 1 0 2.704089 -2.469820 0.355457
11 1 0 1.018547 -2.164094 -0.083422
12 1 0 2.305792 -2.017059 -1.302365
13 6 0 2.019877 -0.244139 1.670838
14 1 0 2.648573 -0.966218 2.203051
15 1 0 2.267858 0.749654 2.050755
Page 166
Annexure 1
19
16 1 0 0.975478 -0.451049 1.915136
17 6 0 3.726382 0.009499 -0.181467
18 1 0 3.951330 1.035098 0.124262
19 1 0 4.421534 -0.661925 0.334955
20 1 0 3.904568 -0.072454 -1.258994
21 1 0 -4.498594 -0.654089 0.674597
22 6 0 -3.849481 0.194307 0.418487
23 6 0 -2.420009 -0.286746 0.049102
24 1 0 -3.820555 0.877710 1.274184
25 1 0 -4.312922 0.729823 -0.419021
26 6 0 -1.628137 0.954908 -0.368720
27 6 0 -1.826751 -1.013000 1.266577
28 6 0 -2.543684 -1.280088 -1.122858
29 6 0 -1.003686 1.843474 0.472442
30 1 0 -1.956909 1.346161 -1.333226
31 1 0 -2.472771 -1.847559 1.566798
32 1 0 -0.837387 -1.422729 1.040059
33 1 0 -1.730795 -0.347476 2.132010
34 1 0 -3.219469 -2.106845 -0.868671
35 1 0 -2.946564 -0.785057 -2.015686
36 1 0 -1.568879 -1.700370 -1.387271
37 1 0 -0.845535 1.615545 1.523205
38 1 0 -0.960660 2.898897 0.226898
---------------------------------------------------------------------------
Rotational constants (GHZ): 1.2880531 0.4513155 0.4229226
-----------------------------------------------------------------------------
Zero-point correction= 0.349377 (Hartree/Particle)
Thermal correction to Energy= 0.365816
Thermal correction to Enthalpy= 0.366761
Thermal correction to Gibbs Free Energy= 0.307453
Sum of electronic and zero-point Energies= -526.619769
Sum of electronic and thermal Energies= -526.603330
Sum of electronic and thermal Enthalpies= -526.602386
Sum of electronic and thermal Free Energies= -526.661693
------------------------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
---------------------------------------
E(RB+HF-LYP) = -527.085884551 A.U.
_____________________________________________________________________________________
Molecule = 4TRX. Final optimised geometry with frequency analysis.
------------------------------------------------------------------
# opt=qst3 freq b3lyp/6-31g(d) geom=connectivity
-------------------------------------------------------
E(RB+HF-LYP) = -526.972787616 A.U.
---------------------------------------------------------------
Standard orientation:
------------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
------------------------------------------------------------------------
1 6 0 0.995392 -1.359630 -1.016765
2 1 0 0.245305 -1.456599 -1.789370
3 1 0 1.730947 -2.143256 -0.939837
4 7 0 1.341002 -0.097303 -0.684714
5 1 0 0.748013 1.906436 -0.557004
6 6 0 0.452107 0.908724 -0.845806
7 1 0 -0.250134 0.807713 -1.660117
8 6 0 2.570716 0.175872 0.162111
9 6 0 3.429885 1.218216 -0.579417
10 1 0 4.350936 1.407464 -0.017210
11 1 0 3.703363 0.852338 -1.574794
12 1 0 2.907226 2.170700 -0.699713
13 6 0 3.414902 -1.091961 0.364547
14 1 0 4.290708 -0.827701 0.965369
15 1 0 2.865460 -1.870506 0.901410
16 1 0 3.775105 -1.502019 -0.584153
17 6 0 2.140841 0.702359 1.544410
18 1 0 1.513206 -0.030751 2.059602
19 1 0 3.030438 0.884096 2.157708
20 1 0 1.581865 1.637969 1.472938
21 1 0 -4.779336 0.060708 0.702234
22 6 0 -3.789370 -0.262730 1.051919
23 6 0 -2.677080 0.170524 0.061386
24 1 0 -3.803415 -1.351893 1.168423
25 1 0 -3.623702 0.175474 2.043611
26 6 0 -1.334456 -0.261500 0.658088
27 6 0 -2.960571 -0.480089 -1.305453
28 6 0 -2.741744 1.704845 -0.079620
Page 167
Annexure 1
20
29 6 0 -0.816671 -1.526309 0.593781
30 1 0 -0.975394 0.395871 1.447839
31 1 0 -3.939140 -0.160993 -1.685425
32 1 0 -2.207630 -0.200199 -2.050799
33 1 0 -2.977634 -1.573550 -1.239292
34 1 0 -3.741794 2.025067 -0.398453
35 1 0 -2.526180 2.193771 0.878830
36 1 0 -2.018452 2.075794 -0.812004
37 1 0 -1.294123 -2.314773 0.019221
38 1 0 -0.096355 -1.869984 1.328895
----------------------------------------------------------------------------
Rotational constants (GHZ): 1.4748852 0.3902317 0.3772372
------------------------------------------------------------------------------
Zero-point correction= 0.349104 (Hartree/Particle)
Thermal correction to Energy= 0.365602
Thermal correction to Enthalpy= 0.366546
Thermal correction to Gibbs Free Energy= 0.307120
Sum of electronic and zero-point Energies= -526.623684
Sum of electronic and thermal Energies= -526.607186
Sum of electronic and thermal Enthalpies= -526.606241
Sum of electronic and thermal Free Energies= -526.665667
---------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
---------------------------------------------------------
E(RB+HF-LYP) = -527.090380751 A.U.
______________________________________________________________________________________
Molecule = 4TSN. Final optimised geometry with frequency analysis.
------------------------------------------------------------------
# opt=qst3 freq b3lyp/6-31g(d) geom=connectivity
-------------------------------------------------
E(RB+HF-LYP) = -526.969146807 A.U.
------------------------------------------------------------
Standard orientation:
--------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
-----------------------------------------------------------------------
1 6 0 -1.289600 1.856081 -0.192046
2 1 0 -1.006298 2.584062 -0.940397
3 1 0 -1.990343 2.186619 0.561860
4 7 0 -1.371511 0.572164 -0.613634
5 1 0 -0.618739 -0.883251 -1.919610
6 6 0 -0.514695 0.127596 -1.561113
7 1 0 -0.163974 0.866272 -2.267831
8 6 0 -2.271711 -0.375784 0.156185
9 6 0 -3.725914 0.007850 -0.182334
10 1 0 -4.420683 -0.664797 0.333004
11 1 0 -3.952184 1.032935 0.124152
12 1 0 -3.903254 -0.073339 -1.260057
13 6 0 -2.020252 -0.244615 1.670857
14 1 0 -2.648535 -0.967525 2.202432
15 1 0 -0.975808 -0.450490 1.915785
16 1 0 -2.269539 0.748771 2.050970
17 6 0 -2.046137 -1.839695 -0.254033
18 1 0 -1.015981 -2.163150 -0.082798
19 1 0 -2.701793 -2.470566 0.354125
20 1 0 -2.301943 -2.017118 -1.303023
21 1 0 3.220031 -2.106051 -0.869312
22 6 0 2.543481 -1.279824 -1.123194
23 6 0 2.419343 -0.286833 0.049029
24 1 0 1.569047 -1.701080 -1.387503
25 1 0 2.945743 -0.784302 -2.016023
26 6 0 1.628157 0.955323 -0.368819
27 6 0 1.825002 -1.013528 1.265754
28 6 0 3.848763 0.193497 0.419499
29 6 0 1.004493 1.844114 0.472529
30 1 0 1.956986 1.346296 -1.333407
31 1 0 2.469825 -1.849323 1.565097
32 1 0 1.729908 -0.348803 2.131904
33 1 0 0.835090 -1.421595 1.038639
34 1 0 4.496371 -0.654993 0.679096
35 1 0 4.314303 0.726034 -0.418752
36 1 0 3.819241 0.879355 1.273193
37 1 0 0.846647 1.616381 1.523379
38 1 0 0.960891 2.899419 0.226631
-----------------------------------------------------------------------------
Rotational constants (GHZ): 1.2877801 0.4514830 0.4230323
-------------------------------------------------------------------------------
Page 168
Annexure 1
21
Zero-point correction= 0.349369 (Hartree/Particle)
Thermal correction to Energy= 0.365813
Thermal correction to Enthalpy= 0.366757
Thermal correction to Gibbs Free Energy= 0.307433
Sum of electronic and zero-point Energies= -526.619777
Sum of electronic and thermal Energies= -526.603334
Sum of electronic and thermal Enthalpies= -526.602389
Sum of electronic and thermal Free Energies= -526.661714
-----------------------------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
------------------------------------------------------------------------------------
E(RB+HF-LYP) = -527.085889096 A.U.
__________________________________________________________________________________
Molecule = 4TSX. Final optimised geometry with frequency analysis.
------------------------------------------------------------------
# opt=qst3 freq b3lyp/6-31g(d) geom=connectivity
--------------------------------------------------------------------
E(RB+HF-LYP) = -526.972788296 A.U
---------------------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -0.993514 -1.356131 -1.018992
2 1 0 -0.242463 -1.450924 -1.790878
3 1 0 -1.727989 -2.140919 -0.943678
4 7 0 -1.340716 -0.094952 -0.684571
5 1 0 -0.750794 1.909345 -0.552593
6 6 0 -0.453077 0.912679 -0.843161
7 1 0 0.249677 0.814724 -1.657399
8 6 0 -2.571296 0.174933 0.162179
9 6 0 -2.142722 0.697963 1.546190
10 1 0 -3.032957 0.879639 2.158584
11 1 0 -1.516811 -0.037065 2.060759
12 1 0 -1.582321 1.632916 1.477452
13 6 0 -3.414597 -1.094123 0.360576
14 1 0 -4.291257 -0.832081 0.961138
15 1 0 -3.773458 -1.502139 -0.589512
16 1 0 -2.865122 -1.873538 0.896138
17 6 0 -3.430982 1.218532 -0.576968
18 1 0 -3.704941 0.854457 -1.572874
19 1 0 -4.351754 1.406566 -0.013903
20 1 0 -2.908593 2.171332 -0.695805
21 1 0 3.743577 2.025569 -0.392064
22 6 0 2.742693 1.704766 -0.076448
23 6 0 2.677618 0.170228 0.061787
24 1 0 2.021468 2.076549 -0.810447
25 1 0 2.524349 2.192261 0.882091
26 6 0 1.335279 -0.262250 0.658702
27 6 0 2.959510 -0.477457 -1.306780
28 6 0 3.790569 -0.265823 1.050329
29 6 0 0.816759 -1.526543 0.591944
30 1 0 0.975964 0.394387 1.448907
31 1 0 3.937894 -0.157999 -1.686936
32 1 0 2.976087 -1.571083 -1.243211
33 1 0 2.206007 -0.195341 -2.050699
34 1 0 4.780362 0.058068 0.700581
35 1 0 3.625909 0.169995 2.043239
36 1 0 3.804281 -1.355274 1.164152
37 1 0 1.294202 -2.314271 0.016332
38 1 0 0.096265 -1.871150 1.326474
-----------------------------------------------------------------------------------------------
Rotational constants (GHZ): 1.4752666 0.3901289 0.3771482
------------------------------------------------------------------------------------------------
Zero-point correction= 0.349116 (Hartree/Particle)
Thermal correction to Energy= 0.365611
Thermal correction to Enthalpy= 0.366555
Thermal correction to Gibbs Free Energy= 0.307143
Sum of electronic and zero-point Energies= -526.623672
Sum of electronic and thermal Energies= -526.607178
Sum of electronic and thermal Enthalpies= -526.606233
Sum of electronic and thermal Free Energies= -526.665645
---------------------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
------------------------------------------------------------------------
E(RB+HF-LYP) = -527.090385241 A.U.
_____________________________________________________________________________________
Page 169
Annexure 1
22
Molecule =4AY.Final optimised geometry with frequency analysis.
--------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------------------------
E(RB+HF-LYP) = -291.133618961 A.U
-------------------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -1.582940 1.236907 0.024822
2 1 0 -2.664974 1.233556 0.052822
3 1 0 -1.053229 2.131411 -0.246035
4 7 0 -0.974033 0.041510 -0.023855
5 1 0 -1.066892 -2.043577 0.184766
6 6 0 -1.606921 -1.142084 -0.051357
7 1 0 -2.688324 -1.134093 -0.059790
8 6 0 0.555453 -0.012326 -0.001353
9 6 0 0.981795 -0.632382 1.342856
10 1 0 2.074424 -0.623498 1.422873
11 1 0 0.570686 -0.050156 2.174033
12 1 0 0.643939 -1.666158 1.447738
13 6 0 1.183024 1.385664 -0.108839
14 1 0 2.270813 1.271153 -0.072370
15 1 0 0.932521 1.876489 -1.054202
16 1 0 0.884282 2.033405 0.719375
17 6 0 1.038169 -0.857763 -1.192519
18 1 0 0.692513 -0.422732 -2.136046
19 1 0 2.133565 -0.877652 -1.203727
20 1 0 0.677425 -1.886814 -1.144112
----------------------------------------------------------------------------------------
Rotational constants (GHZ): 3.2325943 2.4027464 1.9989612
----------------------------------------------------------------------------------------------
Zero-point correction= 0.181036 (Hartree/Particle)
Thermal correction to Energy= 0.189948
Thermal correction to Enthalpy= 0.190892
Thermal correction to Gibbs Free Energy= 0.148897
Sum of electronic and zero-point Energies= -290.952583
Sum of electronic and thermal Energies= -290.943671
Sum of electronic and thermal Enthalpies= -290.942727
Sum of electronic and thermal Free Energies= -290.984722
-----------------------------------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
---------------------------------------------------------------------------------------------
E(RB+HF-LYP) = -291.202185447 A.U.
_____________________________________________________________________________________
Molecule = 5EN. Final optimised geometry with frequency analysis.
--------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
----------------------------------------------------------
E(RB+HF-LYP) = -306.466612335 A.U
----------------------------------------------------------
Standard orientation:
------------------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
-----------------------------------------------------------------------------
1 6 0 2.174514 -0.764248 -0.000122
2 1 0 1.671026 -1.725656 -0.000375
3 1 0 3.260892 -0.771163 -0.000212
4 6 0 1.490291 0.382451 0.000116
5 1 0 1.988501 1.347531 0.000254
6 6 0 0.010336 0.485109 0.000079
7 8 0 -0.588403 1.542773 -0.000121
8 8 0 -0.605434 -0.720382 0.000252
9 6 0 -2.039590 -0.671968 -0.000106
10 1 0 -2.367601 -1.711992 -0.001373
11 1 0 -2.407989 -0.154031 0.889677
12 1 0 -2.407437 -0.151881 -0.888829
-----------------------------------------------------------------------------------
Rotational constants (GHZ): 6.8994590 2.7891060 2.0113889
-------------------------------------------------------------------------------------
Zero-point correction= 0.095853 (Hartree/Particle)
Thermal correction to Energy= 0.102488
Thermal correction to Enthalpy= 0.103432
Thermal correction to Gibbs Free Energy= 0.065386
Page 170
Annexure 1
23
Sum of electronic and zero-point Energies= -306.370759
Sum of electronic and thermal Energies= -306.364125
Sum of electronic and thermal Enthalpies= -306.363180
Sum of electronic and thermal Free Energies= -306.401226
-----------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
------------------------------------------------------------------------
E(RB+HF-LYP) = -306.553540194 A.U.
_____________________________________________________________________________________
Molecule = 5PRN-R. Final optimised geometry.
----------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------
: E(RB+HF-LYP) = -706.427688181 A.U.
-----------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.483754 -0.094859 1.723084
2 1 0 1.057785 0.816342 1.910079
3 1 0 0.409452 -0.641142 2.670459
4 7 0 -0.864946 0.242712 1.256901
5 6 0 -1.264308 -0.879759 0.399240
6 1 0 -1.584911 -1.712423 1.038551
7 6 0 -2.422492 -0.618788 -0.558892
8 8 0 -2.880075 -1.511248 -1.231989
9 8 0 -2.899940 0.639829 -0.697336
10 6 0 -2.442354 1.694051 0.176102
11 1 0 -3.072694 1.697685 1.072340
12 1 0 -2.606014 2.618937 -0.382287
13 6 0 -0.986285 1.520460 0.557827
14 1 0 -0.347091 1.602559 -0.337814
15 1 0 -0.700710 2.326746 1.242858
16 6 0 0.019742 -1.310694 -0.369043
17 1 0 -0.025916 -2.353109 -0.690398
18 1 0 0.147735 -0.691018 -1.261297
19 6 0 1.153588 -1.039595 0.652966
20 1 0 1.471779 -1.969187 1.130017
21 6 0 2.406676 -0.458049 0.030874
22 8 0 3.507494 -0.961779 0.076149
23 8 0 2.159998 0.725485 -0.587512
24 1 0 2.927525 2.271978 -1.645381
25 1 0 4.074612 1.553013 -0.465365
26 6 0 3.299644 1.345211 -1.207713
27 1 0 3.715464 0.694461 -1.981237
---------------------------------------------------------------------
Rotational constants (GHZ): 1.2784729 0.4366385 0.4061387
---------------------------------------------------------------------------
Zero-point correction= 0.224595 (Hartree/Particle)
Thermal correction to Energy= 0.237444
Thermal correction to Enthalpy= 0.238388
Thermal correction to Gibbs Free Energy= 0.183908
Sum of electronic and zero-point Energies= -706.203094
Sum of electronic and thermal Energies= -706.190244
Sum of electronic and thermal Enthalpies= -706.189300
Sum of electronic and thermal Free Energies= -706.243780
_____________________________________________________________________________________
Molecule = 5PRN. Final optimised geometry with frequency analysis.
-----------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
----------------------------------------
E(RB+HF-LYP) = -706.426627511 A.U.
--------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -0.050777 2.278099 0.270453
2 1 0 -0.343159 2.037320 1.297166
3 1 0 -0.452100 3.267046 0.031002
4 6 0 -0.569947 1.187772 -0.706133
5 1 0 -0.901909 1.635464 -1.644217
6 6 0 -1.781306 0.453090 -0.164105
7 8 0 -2.899236 0.529002 -0.618412
Page 171
Annexure 1
24
8 8 0 -1.468967 -0.276096 0.936972
9 6 0 -2.544626 -1.065823 1.473799
10 1 0 -2.125824 -1.583471 2.337207
11 1 0 -3.377547 -0.424742 1.773323
12 1 0 -2.890954 -1.782963 0.725821
13 8 0 -0.410998 -1.696035 -1.625769
14 6 0 0.457661 -1.204824 -0.943894
15 6 0 0.720418 0.301076 -0.983475
16 8 0 1.214404 -1.994925 -0.153066
17 7 0 1.801629 0.790300 -0.117088
18 1 0 1.004406 0.499848 -2.024647
19 6 0 2.276315 -1.433443 0.645713
20 6 0 1.483931 2.200914 0.120694
21 6 0 1.958289 -0.019750 1.087984
22 1 0 2.383588 -2.110388 1.496836
23 1 0 3.198675 -1.448216 0.054305
24 1 0 2.029832 2.575938 0.991708
25 1 0 1.807544 2.784559 -0.751791
26 1 0 1.070452 -0.030349 1.742957
27 1 0 2.804237 0.369617 1.665923
---------------------------------------------------------------------
Rotational constants (GHZ): 0.9530324 0.6942529 0.5440803
-------------------------------------------------------------------------------------------
Zero-point correction= 0.224577 (Hartree/Particle)
Thermal correction to Energy= 0.237319
Thermal correction to Enthalpy= 0.238263
Thermal correction to Gibbs Free Energy= 0.184836
Sum of electronic and zero-point Energies= -706.202050
Sum of electronic and thermal Energies= -706.189308
Sum of electronic and thermal Enthalpies= -706.188364
Sum of electronic and thermal Free Energies= -706.241791
______________________________________________________________________________________
Molecule = 5PRX-R. Final optimised geometry with frequency analysis.
---------------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
----------------------------------------
E(RB+HF-LYP) = -706.427815403 A.U.
----------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.421119 -1.286266 -0.672788
2 1 0 0.492979 -2.376249 -0.620319
3 1 0 0.956873 -0.949268 -1.567056
4 7 0 -0.973289 -0.859900 -0.779829
5 6 0 -0.938838 0.559991 -0.401096
6 1 0 -0.600595 1.136208 -1.269729
7 6 0 -2.268795 1.174922 0.018724
8 8 0 -2.360727 2.357825 0.243681
9 8 0 -3.345235 0.372472 0.199883
10 6 0 -3.288276 -1.021282 -0.166835
11 1 0 -3.572096 -1.114763 -1.220972
12 1 0 -4.041563 -1.512800 0.453551
13 6 0 -1.908372 -1.607829 0.055379
14 1 0 -1.667540 -1.584135 1.135136
15 1 0 -1.908904 -2.656997 -0.260730
16 6 0 0.139745 0.703633 0.730207
17 1 0 -0.324958 0.740751 1.719412
18 1 0 0.706658 1.626675 0.601799
19 6 0 1.018002 -0.571000 0.588126
20 1 0 0.909670 -1.212056 1.465747
21 6 0 2.503490 -0.305150 0.457371
22 8 0 3.367809 -0.819975 1.132980
23 8 0 2.763695 0.573711 -0.541213
24 1 0 4.175387 1.596107 -1.570166
25 1 0 4.587506 1.316178 0.154609
26 6 0 4.152793 0.879844 -0.748419
27 1 0 4.710062 -0.023795 -1.009138
---------------------------------------------------------------------
Rotational constants (GHZ): 1.5310256 0.3864552 0.3416751
-----------------------------------------------------------------------------------
Zero-point correction= 0.224602 (Hartree/Particle)
Thermal correction to Energy= 0.237474
Thermal correction to Enthalpy= 0.238419
Thermal correction to Gibbs Free Energy= 0.183569
Sum of electronic and zero-point Energies= -706.203213
Page 172
Annexure 1
25
Sum of electronic and thermal Energies= -706.190341
Sum of electronic and thermal Enthalpies= -706.189397
Sum of electronic and thermal Free Energies= -706.244246
_____________________________________________________________________________________
Molecule =5PRX. Final optimised geometry with frequency analysis.
-----------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------
E(RB+HF-LYP) = -706.426976672 A.U
-----------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.640554 2.239691 -0.453240
2 1 0 1.295766 3.087019 -0.230181
3 1 0 0.117681 2.459525 -1.391556
4 7 0 1.429882 1.018401 -0.647332
5 6 0 0.457132 -0.062297 -0.464503
6 1 0 -0.139491 -0.152478 -1.377652
7 6 0 1.032507 -1.445280 -0.189291
8 8 0 0.315786 -2.416815 -0.155769
9 8 0 2.352770 -1.572439 0.081717
10 6 0 3.243025 -0.447664 -0.073928
11 1 0 3.602933 -0.433649 -1.108621
12 1 0 4.081814 -0.650983 0.596136
13 6 0 2.564483 0.866789 0.259054
14 1 0 3.271023 1.686379 0.086337
15 1 0 2.292053 0.882186 1.331579
16 6 0 -0.395258 1.943717 0.667824
17 1 0 -0.051723 2.310502 1.639459
18 1 0 -1.354474 2.424307 0.457382
19 6 0 -0.510076 0.389751 0.697181
20 1 0 -0.160644 -0.000601 1.655378
21 6 0 -1.929626 -0.120119 0.548372
22 8 0 -2.560184 -0.683152 1.413980
23 8 0 -2.432325 0.165878 -0.677538
24 6 0 -3.777966 -0.284257 -0.907942
25 1 0 -3.841182 -1.368978 -0.791655
26 1 0 -4.013435 0.007857 -1.931823
27 1 0 -4.466526 0.190348 -0.203749
-------------------------------------------------------------------------------------
Rotational constants (GHZ): 1.1837441 0.5266945 0.4216203
------------------------------------------------------------------------------------
Zero-point correction= 0.224531 (Hartree/Particle)
Thermal correction to Energy= 0.237437
Thermal correction to Enthalpy= 0.238381
Thermal correction to Gibbs Free Energy= 0.183608
Sum of electronic and zero-point Energies= -706.202446
Sum of electronic and thermal Energies= -706.189540
Sum of electronic and thermal Enthalpies= -706.188595
Sum of electronic and thermal Free Energies= -706.243369
_____________________________________________________________________________________
Molecule = 5PSN-R. Final optimised geometry with frequency analysis .
---------------------------------------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------------------
E(RB+HF-LYP) = -706.422633389 A.U.
-----------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -0.452477 -0.762220 1.607922
2 1 0 -1.039626 0.049288 2.047891
3 1 0 -0.456520 -1.591699 2.327163
4 7 0 0.917598 -0.321585 1.353447
5 6 0 1.375595 -0.984040 0.128817
6 1 0 1.788973 -1.971538 0.365869
7 6 0 2.465362 -0.250388 -0.645939
8 8 0 3.309959 -0.833327 -1.281025
9 8 0 2.422333 1.105742 -0.659055
10 6 0 1.403397 1.772146 0.117777
11 1 0 0.458986 1.771390 -0.437499
12 1 0 1.753514 2.802778 0.220131
Page 173
Annexure 1
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13 6 0 1.247781 1.095079 1.472019
14 1 0 2.189919 1.213373 2.027232
15 1 0 0.469659 1.603814 2.050239
16 6 0 0.107403 -1.166590 -0.761475
17 1 0 0.190973 -2.045582 -1.405585
18 1 0 -0.032321 -0.294557 -1.406449
19 6 0 -1.058622 -1.281225 0.253032
20 1 0 -1.375256 -2.320638 0.361384
21 6 0 -2.300580 -0.519860 -0.165255
22 8 0 -3.402159 -1.001702 -0.308376
23 8 0 -2.043072 0.803004 -0.347849
24 1 0 -2.797248 2.618683 -0.835501
25 1 0 -3.586995 1.247684 -1.683288
26 6 0 -3.175796 1.601123 -0.734374
27 1 0 -3.956106 1.554212 0.029563
-------------------------------------------------------------------------------------
Rotational constants (GHZ): 1.2413501 0.4645122 0.4338639
---------------------------------------------------------------------------------------
Zero-point correction= 0.224584 (Hartree/Particle)
Thermal correction to Energy= 0.237494
Thermal correction to Enthalpy= 0.238438
Thermal correction to Gibbs Free Energy= 0.183225
Sum of electronic and zero-point Energies= -706.198049
Sum of electronic and thermal Energies= -706.185139
Sum of electronic and thermal Enthalpies= -706.184195
Sum of electronic and thermal Free Energies= -706.239408
____________________________________________________________________________________
Molecule = 5PSN. Final optimised geometry with frequency analysis.
------------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
------------------------------------------------------------
E(RB+HF-LYP) = -706.426558082 A.U.
-------------------------------------------------------------
Standard orientation:
------------------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
----------------------------------------------------------------------------------
1 6 0 -1.045877 2.291273 0.278584
2 1 0 -1.311777 2.801586 1.210319
3 1 0 -1.618049 2.761811 -0.545908
4 7 0 -1.303099 0.862106 0.375486
5 6 0 -0.622003 0.286010 -0.774969
6 1 0 -1.157434 0.557043 -1.713848
7 6 0 -0.637319 -1.234183 -0.767873
8 8 0 0.179677 -1.906569 -1.348212
9 8 0 -1.713105 -1.826670 -0.189125
10 6 0 -2.577351 -1.119471 0.729182
11 1 0 -2.187266 -1.288027 1.738379
12 1 0 -3.553363 -1.603133 0.636341
13 6 0 -2.662917 0.378127 0.459726
14 1 0 -3.244136 0.581106 -0.463100
15 1 0 -3.185558 0.856769 1.295901
16 6 0 0.467059 2.325758 -0.021420
17 1 0 0.759990 3.211947 -0.589711
18 1 0 1.026632 2.325286 0.917502
19 6 0 0.749415 1.003698 -0.819038
20 1 0 1.031936 1.217752 -1.850241
21 6 0 1.915934 0.224863 -0.233052
22 8 0 3.019089 0.176433 -0.728605
23 8 0 1.592467 -0.361204 0.940632
24 1 0 2.212386 -1.542821 2.462079
25 1 0 2.896641 -1.984380 0.862383
26 6 0 2.630923 -1.161144 1.530306
27 1 0 3.519473 -0.555188 1.725318
----------------------------------------------------------------------------------------
Rotational constants (GHZ): 1.0075831 0.6367818 0.4969926
----------------------------------------------------------------------------
Zero-point correction= 0.224199 (Hartree/Particle)
Thermal correction to Energy= 0.236997
Thermal correction to Enthalpy= 0.237942
Thermal correction to Gibbs Free Energy= 0.184259
Sum of electronic and zero-point Energies= -706.202359
Sum of electronic and thermal Energies= -706.189561
Sum of electronic and thermal Enthalpies= -706.188616
Sum of electronic and thermal Free Energies= -706.242299
______________________________________________________________________________________
Page 174
Annexure 1
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Molecule = 5PSX-R. Final optimised geometry with frequency analysis.
--------------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
-------------------------------------------------------
E(RB+HF-LYP) = -706.428692875 A.U.
--------------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.396432 -1.448024 -0.301063
2 1 0 0.473769 -2.391616 -0.850692
3 1 0 0.790603 -1.606670 0.719026
4 7 0 -0.979861 -0.966675 -0.282623
5 6 0 -0.877062 0.438553 0.099289
6 1 0 -0.555363 0.533921 1.160025
7 6 0 -2.214998 1.151938 0.022661
8 8 0 -2.324510 2.336596 -0.177566
9 8 0 -3.316975 0.409827 0.315037
10 6 0 -3.304849 -1.034197 0.256607
11 1 0 -3.627549 -1.320640 -0.750212
12 1 0 -4.059023 -1.359946 0.977906
13 6 0 -1.943377 -1.653474 0.551891
14 1 0 -1.697299 -1.574293 1.630030
15 1 0 -1.979938 -2.718504 0.294937
16 6 0 0.242206 0.965432 -0.805276
17 1 0 -0.167622 1.287784 -1.765286
18 1 0 0.760583 1.813903 -0.356816
19 6 0 1.164679 -0.284459 -1.000703
20 1 0 1.284938 -0.504937 -2.062438
21 6 0 2.567550 -0.106504 -0.452597
22 8 0 3.589380 -0.294668 -1.075283
23 8 0 2.548558 0.288950 0.843784
24 1 0 3.637580 0.793404 2.474000
25 1 0 4.414066 -0.445577 1.431488
26 6 0 3.838485 0.483664 1.448090
27 1 0 4.398265 1.256688 0.915237
------------------------------------------------------------------------------------
Rotational constants (GHZ): 1.4495360 0.3864378 0.3515802
------------------------------------------------------------------------------
Zero-point correction= 0.224182 (Hartree/Particle)
Thermal correction to Energy= 0.237124
Thermal correction to Enthalpy= 0.238068
Thermal correction to Gibbs Free Energy= 0.183008
Sum of electronic and zero-point Energies= -706.204511
Sum of electronic and thermal Energies= -706.191569
Sum of electronic and thermal Enthalpies= -706.190625
Sum of electronic and thermal Free Energies= -706.245685
__________________________________________________________________________________
Molecule =5PSX. Final optimised geometry with frequency analysis.
----------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
-------------------------------------------
E(RB+HF-LYP) = -706.428218165 A.U.
-------------------------------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.838302 2.283982 0.120522
2 1 0 1.411409 3.108883 -0.316134
3 1 0 0.710223 2.494155 1.199210
4 7 0 1.518580 1.010645 -0.101751
5 6 0 0.485919 0.000074 0.101738
6 1 0 0.156151 -0.027925 1.161219
7 6 0 0.970713 -1.404282 -0.206208
8 8 0 0.228910 -2.296816 -0.537598
9 8 0 2.284013 -1.663206 0.025471
10 6 0 3.261935 -0.604370 0.141743
11 1 0 3.679294 -0.436940 -0.856950
12 1 0 4.044173 -1.003854 0.792458
13 6 0 2.694026 0.702123 0.684346
14 1 0 2.466783 0.616094 1.766307
15 1 0 3.448434 1.488348 0.563886
16 6 0 -0.545668 2.077425 -0.551570
17 1 0 -0.612091 2.593433 -1.512247
Page 175
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18 1 0 -1.346198 2.459468 0.087390
19 6 0 -0.670237 0.529087 -0.760140
20 1 0 -0.486616 0.276594 -1.805965
21 6 0 -2.048764 -0.008388 -0.432169
22 8 0 -2.885187 -0.299775 -1.256440
23 8 0 -2.262374 -0.072257 0.903913
24 1 0 -3.551955 -0.566957 2.383708
25 1 0 -4.345471 0.088174 0.911741
26 6 0 -3.555726 -0.564494 1.293256
27 1 0 -3.710107 -1.574502 0.905761
---------------------------------------------------------------------------------------
Rotational constants (GHZ): 1.1533464 0.5145378 0.4162658
------------------------------------------------------------------------------------
Zero-point correction= 0.224084 (Hartree/Particle)
Thermal correction to Energy= 0.237079
Thermal correction to Enthalpy= 0.238023
Thermal correction to Gibbs Free Energy= 0.183397
Sum of electronic and zero-point Energies= -706.204134
Sum of electronic and thermal Energies= -706.191140
Sum of electronic and thermal Enthalpies= -706.190195
Sum of electronic and thermal Free Energies= -706.244821
_____________________________________________________________________________________
Molecule = 5TRN-R. Final optimised geometry with frequency analysis.
---------------------------------------------------------------------
# opt=(calcfc,qst3) freq b3lyp/6-31g(d) geom=connectivity
-------------------------------------------------------------------------
E(RB+HF-LYP) = -706.350489248 A.U.
----------------------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.259445 -0.392034 1.963687
2 1 0 0.881663 0.348424 2.448660
3 1 0 0.217980 -1.394531 2.364573
4 7 0 -0.752066 0.025861 1.204892
5 6 0 -1.485820 -0.859218 0.458684
6 1 0 -1.606622 -1.850727 0.872054
7 6 0 -2.515386 -0.428574 -0.482247
8 8 0 -3.161203 -1.207839 -1.149317
9 8 0 -2.691120 0.924406 -0.672915
10 6 0 -2.188978 1.788930 0.348113
11 1 0 -2.846961 1.745165 1.226363
12 1 0 -2.224090 2.799897 -0.064269
13 6 0 -0.767180 1.423178 0.729610
14 1 0 -0.092019 1.499751 -0.128191
15 1 0 -0.402672 2.065915 1.534873
16 6 0 0.268124 -1.607900 -0.823614
17 1 0 -0.240549 -2.555901 -0.959977
18 1 0 0.128883 -0.885174 -1.620077
19 6 0 1.360387 -1.514824 0.013975
20 1 0 1.663701 -2.363043 0.619410
21 6 0 2.400244 -0.481572 -0.075199
22 8 0 3.483205 -0.530501 0.479546
23 8 0 2.046097 0.572558 -0.879976
24 1 0 2.651185 2.294655 -1.750790
25 1 0 3.338805 2.028066 -0.113651
26 6 0 3.070831 1.557280 -1.064400
27 1 0 3.969323 1.105902 -1.493591
---------------------------------------------------------------------
Rotational constants (GHZ): 1.1729477 0.4421402 0.4104846
----------------------------------------------------------------------------
Zero-point correction= 0.218878 (Hartree/Particle)
Thermal correction to Energy= 0.232568
Thermal correction to Enthalpy= 0.233512
Thermal correction to Gibbs Free Energy= 0.177848
Sum of electronic and zero-point Energies= -706.131611
Sum of electronic and thermal Energies= -706.117921
Sum of electronic and thermal Enthalpies= -706.116977
Sum of electronic and thermal Free Energies= -706.172641
--------------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
---------------------------------------
E(RB+HF-LYP) = -706.543415540 A.U.
_____________________________________________________________________________________
Page 176
Annexure 1
29
Molecule = 5TRN. Final optimised geometry with frequency analysis.
-----------------------------------------------------------------
# opt=qst3 freq b3lyp/6-31g(d) geom=connectivity
---------------------------------------------------------------
E(RB+HF-LYP) = -706.348951712 A.U.
------------------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -1.134451 2.377195 -0.011083
2 1 0 -1.226000 2.319176 1.068642
3 1 0 -1.170857 3.375787 -0.436195
4 6 0 -1.477401 1.295705 -0.786357
5 1 0 -1.626361 1.402138 -1.856068
6 6 0 -1.909688 -0.011387 -0.275869
7 8 0 -2.462110 -0.863793 -0.943113
8 8 0 -1.662948 -0.178237 1.064714
9 6 0 -2.080161 -1.446413 1.592218
10 1 0 -1.514456 -2.259228 1.128489
11 1 0 -1.875580 -1.400935 2.663587
12 1 0 -3.146120 -1.609044 1.414295
13 6 0 1.126944 2.449586 -0.028353
14 1 0 1.452850 3.022492 0.831263
15 1 0 1.135759 2.936676 -0.994711
16 7 0 1.386305 1.130739 -0.016001
17 6 0 1.064049 0.325271 -1.055481
18 1 0 0.933528 0.780019 -2.026113
19 6 0 1.112090 -1.125568 -0.993791
20 8 0 0.763058 -1.842259 -1.905738
21 8 0 1.539204 -1.699710 0.189525
22 6 0 2.289758 -0.857180 1.062657
23 1 0 3.293622 -0.691677 0.648221
24 1 0 2.388233 -1.400073 2.005592
25 6 0 1.583869 0.466816 1.289186
26 1 0 2.184441 1.124370 1.922869
27 1 0 0.599108 0.312961 1.740272
---------------------------------------------------------------------
Rotational constants (GHZ): 0.8222907 0.6676547 0.5421366
---------------------------------------------------------------------------------
Zero-point correction= 0.218767 (Hartree/Particle)
Thermal correction to Energy= 0.232514
Thermal correction to Enthalpy= 0.233458
Thermal correction to Gibbs Free Energy= 0.177563
Sum of electronic and zero-point Energies= -706.130185
Sum of electronic and thermal Energies= -706.116438
Sum of electronic and thermal Enthalpies= -706.115494
Sum of electronic and thermal Free Energies= -706.171389
------------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
------------------------------------------------------------------------------------
E(RB+HF-LYP) = -706.540830420 A.U.
_____________________________________________________________________________________
Molecule = 5TRX-R. Final optimised geometry with frequency analysis.
-----------------------------------------------------------------
# opt=(calcfc,qst3) freq b3lyp/6-31g(d) geom=connectivity
---------------------------------------------------------
E(RB+HF-LYP) = -706.349727498 A.U.
---------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.249056 -1.406969 -0.919469
2 1 0 0.313002 -2.487130 -0.917077
3 1 0 0.974924 -0.827441 -1.471527
4 7 0 -0.926297 -0.841691 -0.649703
5 6 0 -1.042514 0.517679 -0.516502
6 1 0 -0.362778 1.117560 -1.104891
7 6 0 -2.279623 1.161567 -0.092568
8 8 0 -2.390306 2.362339 0.029666
9 8 0 -3.338353 0.352784 0.269375
10 6 0 -3.310283 -0.994879 -0.200284
11 1 0 -3.558379 -1.022112 -1.269788
12 1 0 -4.087817 -1.528043 0.351728
13 6 0 -1.955442 -1.634544 0.041429
Page 177
Annexure 1
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14 1 0 -1.719004 -1.650941 1.112725
15 1 0 -1.929985 -2.655948 -0.345856
16 6 0 0.398407 0.693473 1.279789
17 1 0 -0.389872 0.662628 2.025661
18 1 0 0.692985 1.682456 0.950330
19 6 0 1.251085 -0.381456 1.138885
20 1 0 1.115553 -1.280401 1.731409
21 6 0 2.568495 -0.303611 0.493184
22 8 0 3.465722 -1.115385 0.627870
23 8 0 2.688738 0.793735 -0.316075
24 1 0 3.903086 1.868129 -1.524439
25 1 0 4.751701 1.077900 -0.155910
26 6 0 3.977914 0.962780 -0.920156
27 1 0 4.231701 0.103152 -1.546980
---------------------------------------------------------------------
Rotational constants (GHZ): 1.3827243 0.3810115 0.3375394
--------------------------------------------------------------------------------
Zero-point correction= 0.218840 (Hartree/Particle)
Thermal correction to Energy= 0.232578
Thermal correction to Enthalpy= 0.233522
Thermal correction to Gibbs Free Energy= 0.177382
Sum of electronic and zero-point Energies= -706.130887
Sum of electronic and thermal Energies= -706.117149
Sum of electronic and thermal Enthalpies= -706.116205
Sum of electronic and thermal Free Energies= -706.172346
---------------------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
---------------------------------------
E(RB+HF-LYP) = -706.543130453 A.U.
_____________________________________________________________________________________
Molecule = 5TRX. Final optimised geometry with frequency analysis.
----------------------------------------------------------------
# opt=(calcfc,qst3) freq b3lyp/6-31g(d) geom=connectivity
---------------------------------------------------------
E(RB+HF-LYP) = -706.348242225 A.U
--------------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.486034 2.081388 -0.828249
2 1 0 0.982832 3.042895 -0.789460
3 1 0 -0.351696 1.956148 -1.501046
4 7 0 1.236582 0.993750 -0.589459
5 6 0 0.729762 -0.260863 -0.653882
6 1 0 -0.169275 -0.407296 -1.233287
7 6 0 1.446768 -1.440769 -0.203758
8 8 0 0.973544 -2.556063 -0.220082
9 8 0 2.722721 -1.261260 0.301596
10 6 0 3.371310 -0.039008 -0.038506
11 1 0 3.686760 -0.060887 -1.090700
12 1 0 4.262213 0.024488 0.590765
13 6 0 2.463060 1.150991 0.211305
14 1 0 2.950805 2.085900 -0.075447
15 1 0 2.176387 1.202847 1.268840
16 6 0 -0.916264 1.937129 0.966196
17 1 0 -0.300138 2.544814 1.623055
18 1 0 -1.674059 2.467610 0.400554
19 6 0 -1.059377 0.595034 1.218259
20 1 0 -0.507099 0.105263 2.012798
21 6 0 -2.123357 -0.234710 0.635334
22 8 0 -2.529627 -1.280730 1.100177
23 8 0 -2.635289 0.309406 -0.514673
24 6 0 -3.725996 -0.424812 -1.089040
25 1 0 -3.418689 -1.444126 -1.337831
26 1 0 -4.007561 0.122202 -1.990343
27 1 0 -4.568981 -0.473217 -0.393789
---------------------------------------------------------------------------------
Rotational constants (GHZ): 1.0890640 0.4727452 0.3868614
----------------------------------------------------------------------------------
Zero-point correction= 0.218616 (Hartree/Particle)
Thermal correction to Energy= 0.232466
Thermal correction to Enthalpy= 0.233410
Thermal correction to Gibbs Free Energy= 0.176672
Sum of electronic and zero-point Energies= -706.129626
Sum of electronic and thermal Energies= -706.115776
Sum of electronic and thermal Enthalpies= -706.114832
Page 178
Annexure 1
31
Sum of electronic and thermal Free Energies= -706.171571
--------------------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
---------------------------------------
E(RB+HF-LYP) = -706.540891433 A.U.
______________________________________________________________________________________
Molecule = 5TSN-R. Final optimised geometry with frequency analysis.
-------------------------------------------------------------------
# opt=(calcfc,qst3) freq b3lyp/6-31g(d) geom=connectivity
---------------------------------------------------------
E(RB+HF-LYP) = -706.349931470 A.U.
---------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -0.248379 -1.005752 1.788717
2 1 0 -0.905661 -0.480426 2.469341
3 1 0 -0.162506 -2.080126 1.865057
4 7 0 0.750469 -0.330909 1.223433
5 6 0 1.540576 -0.911722 0.264021
6 1 0 1.742026 -1.966966 0.387769
7 6 0 2.598229 -0.157484 -0.409224
8 8 0 3.525890 -0.682713 -0.985492
9 8 0 2.494467 1.213587 -0.408982
10 6 0 1.254520 1.761243 0.049291
11 1 0 0.473465 1.614307 -0.703354
12 1 0 1.426901 2.832042 0.181234
13 6 0 0.830814 1.135933 1.367031
14 1 0 1.562048 1.360225 2.151569
15 1 0 -0.147397 1.513259 1.671329
16 6 0 -0.143441 -1.388134 -1.217233
17 1 0 0.383040 -2.263736 -1.582114
18 1 0 -0.013561 -0.489036 -1.808248
19 6 0 -1.261353 -1.538810 -0.419380
20 1 0 -1.569846 -2.523478 -0.083952
21 6 0 -2.303637 -0.522564 -0.244027
22 8 0 -3.410729 -0.722980 0.221960
23 8 0 -1.915983 0.724016 -0.675445
24 1 0 -2.493817 2.633326 -1.016176
25 1 0 -3.812381 1.430719 -1.191651
26 6 0 -2.938768 1.725732 -0.604370
27 1 0 -3.256122 1.890316 0.429885
---------------------------------------------------------------------
Rotational constants (GHZ): 1.1899279 0.4678729 0.4280752
------------------------------------------------------------------------------------------
Zero-point correction= 0.219057 (Hartree/Particle)
Thermal correction to Energy= 0.232700
Thermal correction to Enthalpy= 0.233645
Thermal correction to Gibbs Free Energy= 0.178232
Sum of electronic and zero-point Energies= -706.130874
Sum of electronic and thermal Energies= -706.117231
Sum of electronic and thermal Enthalpies= -706.116287
Sum of electronic and thermal Free Energies= -706.171700
-------------------------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
---------------------------------------
E(RB+HF-LYP) = -706.542478294 A.U.
______________________________________________________________________________________
Molecule = 5TSN. Final optimised geometry with frequency analysis.
-----------------------------------------------------------------
# opt=(calcfc,qst3) freq b3lyp/6-31g(d) geom=connectivity
---------------------------------------------------------
E(RB+HF-LYP) = -706.347056669 A.U.
----------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -1.134545 2.430430 0.070955
2 1 0 -1.341468 3.026388 0.951951
3 1 0 -1.251281 2.909269 -0.892820
4 7 0 -1.458176 1.124475 0.134705
5 6 0 -1.279228 0.282719 -0.907871
6 1 0 -1.211634 0.711996 -1.896006
Page 179
Annexure 1
32
7 6 0 -1.573500 -1.142657 -0.826932
8 8 0 -1.710736 -1.849733 -1.801259
9 8 0 -1.715586 -1.686655 0.430246
10 6 0 -1.239103 -0.886989 1.515836
11 1 0 -0.145552 -0.851735 1.504225
12 1 0 -1.579273 -1.378748 2.430191
13 6 0 -1.798427 0.522358 1.439653
14 1 0 -2.890075 0.514761 1.532133
15 1 0 -1.378939 1.147499 2.231488
16 6 0 1.082679 2.315235 -0.198141
17 1 0 1.049610 3.305533 -0.642230
18 1 0 1.343048 2.279974 0.854681
19 6 0 1.331446 1.221593 -0.995272
20 1 0 1.294792 1.301528 -2.076950
21 6 0 1.930093 -0.035391 -0.536853
22 8 0 2.387456 -0.892582 -1.268835
23 8 0 1.989498 -0.141220 0.832996
24 1 0 2.674204 -1.230023 2.395594
25 1 0 2.213766 -2.217591 0.967207
26 6 0 2.696580 -1.296880 1.306329
27 1 0 3.729011 -1.291170 0.946192
---------------------------------------------------------------------------------------
Rotational constants (GHZ): 0.8234535 0.5955743 0.5060167
---------------------------------------------------------------------------------
Zero-point correction= 0.218906 (Hartree/Particle)
Thermal correction to Energy= 0.232664
Thermal correction to Enthalpy= 0.233609
Thermal correction to Gibbs Free Energy= 0.177416
Sum of electronic and zero-point Energies= -706.128150
Sum of electronic and thermal Energies= -706.114392
Sum of electronic and thermal Enthalpies= -706.113448
Sum of electronic and thermal Free Energies= -706.169641
-------------------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
---------------------------------------
E(RB+HF-LYP) = -706.539281510 A.U.
______________________________________________________________________________________
Molecule= 5TSX-R. Final optimised geometry with frequency analysis.
-------------------------------------------------------------------
# opt=(calcfc,qst3) freq b3lyp/6-31g(d) geom=connectivity
---------------------------------------------------------
E(RB+HF-LYP) = -706.347938933 A.U.
--------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -0.284202 -1.220998 -1.142996
2 1 0 -0.366296 -2.284807 -1.326105
3 1 0 -1.026207 -0.553164 -1.556847
4 7 0 0.917105 -0.720211 -0.859549
5 6 0 1.063256 0.599998 -0.510961
6 1 0 0.400976 1.297732 -1.004407
7 6 0 2.362564 1.140256 -0.117002
8 8 0 2.633622 2.320476 -0.137784
9 8 0 3.305532 0.244704 0.344173
10 6 0 2.852356 -1.085375 0.595170
11 1 0 2.254815 -1.110996 1.514911
12 1 0 3.748775 -1.691417 0.746315
13 6 0 2.049140 -1.621461 -0.577798
14 1 0 2.677458 -1.675147 -1.473726
15 1 0 1.661078 -2.619221 -0.357854
16 6 0 -0.332999 0.561620 1.301763
17 1 0 0.462001 0.450686 2.032438
18 1 0 -0.654137 1.579809 1.116129
19 6 0 -1.188996 -0.495948 1.056281
20 1 0 -1.028657 -1.460279 1.526858
21 6 0 -2.535427 -0.342827 0.491882
22 8 0 -3.427621 -1.167890 0.567327
23 8 0 -2.691141 0.845705 -0.169817
24 1 0 -3.959065 2.058028 -1.175775
25 1 0 -4.286089 0.308481 -1.410477
26 6 0 -4.006066 1.082229 -0.689954
27 1 0 -4.745289 1.092849 0.115889
---------------------------------------------------------------------
Rotational constants (GHZ): 1.3547267 0.3833620 0.3431052
--------------------------------------------------------------------------------------
Page 180
Annexure 1
33
Zero-point correction= 0.218968 (Hartree/Particle)
Thermal correction to Energy= 0.232657
Thermal correction to Enthalpy= 0.233601
Thermal correction to Gibbs Free Energy= 0.177646
Sum of electronic and zero-point Energies= -706.128971
Sum of electronic and thermal Energies= -706.115282
Sum of electronic and thermal Enthalpies= -706.114338
Sum of electronic and thermal Free Energies= -706.170293
-------------------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
---------------------------------------
E(RB+HF-LYP) = -706.541011260 A.U.
_____________________________________________________________________________________
Molecule = 5TSX. Final optimised geometry with frequency analysis.
-----------------------------------------------------------------
# opt=(calcfc,qst3) freq b3lyp/6-31g(d) geom=connectivity
---------------------------------------------------------
E(RB+HF-LYP) = -706.347681616 A.U.
----------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.399974 -2.001791 -0.971414
2 1 0 0.873640 -2.974207 -1.035607
3 1 0 -0.477833 -1.819241 -1.577334
4 7 0 1.203270 -0.946868 -0.745829
5 6 0 0.730146 0.320887 -0.697946
6 1 0 -0.192856 0.529130 -1.217765
7 6 0 1.561649 1.456151 -0.329281
8 8 0 1.269874 2.608344 -0.564152
9 8 0 2.749554 1.182688 0.322439
10 6 0 2.894832 -0.142804 0.826238
11 1 0 2.243241 -0.286707 1.697563
12 1 0 3.935016 -0.240110 1.146133
13 6 0 2.575246 -1.168069 -0.249022
14 1 0 3.267369 -1.064968 -1.091852
15 1 0 2.645131 -2.184520 0.145518
16 6 0 -0.860516 -1.942614 0.886664
17 1 0 -0.210428 -2.568780 1.491680
18 1 0 -1.648651 -2.461221 0.352015
19 6 0 -1.007838 -0.613005 1.206391
20 1 0 -0.428119 -0.151924 1.998115
21 6 0 -2.093911 0.231783 0.695877
22 8 0 -2.474006 1.270149 1.200928
23 8 0 -2.656649 -0.281192 -0.444932
24 1 0 -4.089874 -0.055143 -1.855687
25 1 0 -4.578984 0.506682 -0.223512
26 6 0 -3.767086 0.470380 -0.955464
27 1 0 -3.465707 1.493678 -1.194987
---------------------------------------------------------------------
Rotational constants (GHZ): 1.0493769 0.4740244 0.3945285
------------------------------------------------------------------------------------
Zero-point correction= 0.218749 (Hartree/Particle)
Thermal correction to Energy= 0.232568
Thermal correction to Enthalpy= 0.233512
Thermal correction to Gibbs Free Energy= 0.176922
Sum of electronic and zero-point Energies= -706.128932
Sum of electronic and thermal Energies= -706.115113
Sum of electronic and thermal Enthalpies= -706.114169
Sum of electronic and thermal Free Energies= -706.170760
--------------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
---------------------------------------
E(RB+HF-LYP) = -706.540099883 A.U.
_____________________________________________________________________________________
Molecule = 5Y. final optimised geometry with frequency analysis.
----------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
------------------------------------------------------------
E(RB+HF-LYP) = -399.885801981 A.U.
---------------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
Page 181
Annexure 1
34
---------------------------------------------------------------------
1 6 0 2.418479 -0.888885 0.069650
2 1 0 3.265665 -0.232835 -0.057050
3 1 0 2.540638 -1.949447 0.242063
4 7 0 1.197837 -0.388880 -0.012591
5 6 0 1.063608 1.053153 -0.342201
6 1 0 0.968658 1.136708 -1.428914
7 6 0 -0.171156 1.608895 0.343290
8 1 0 -0.303551 2.660879 0.076890
9 1 0 -0.063486 1.534645 1.434597
10 6 0 0.023932 -1.063850 0.112376
11 1 0 0.081396 -2.133682 0.257609
12 6 0 -1.273802 -0.464260 -0.022192
13 8 0 -2.312946 -1.092359 -0.085171
14 8 0 -1.338261 0.925893 -0.088386
15 1 0 1.969112 1.567299 -0.014144
---------------------------------------------------------------------
Rotational constants (GHZ): 3.7676883 1.8922710 1.3088209
--------------------------------------------------------------------------------
Zero-point correction= 0.120768 (Hartree/Particle)
Thermal correction to Energy= 0.127587
Thermal correction to Enthalpy= 0.128531
Thermal correction to Gibbs Free Energy= 0.089831
Sum of electronic and zero-point Energies= -399.765034
Sum of electronic and thermal Energies= -399.758215
Sum of electronic and thermal Enthalpies= -399.757271
Sum of electronic and thermal Free Energies= -399.795971
------------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
---------------------------------------
E(RB+HF-LYP) = -399.994786957 A.U.
______________________________________________________________________________________
Molecule = 6EN. Final optimised geometry with frequency analysis.
----------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------
E(RB+HF-LYP) = -359.428917113 A.U.
-------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.001591 1.265517 0.668616
2 1 0 0.002616 2.102147 1.355612
3 6 0 0.001591 1.265517 -0.668616
4 1 0 0.002616 2.102147 -1.355612
5 6 0 -0.000321 -0.157119 -1.157685
6 6 0 -0.000321 -0.157119 1.157685
7 8 0 -0.000321 -0.560822 -2.300086
8 8 0 -0.000321 -0.560822 2.300086
9 7 0 -0.001880 -0.940165 0.000000
10 1 0 -0.002170 -1.950763 0.000000
---------------------------------------------------------------------
Rotational constants (GHZ): 6.8147668 2.3414756 1.7427031
--------------------------------------------------------------------------------
Zero-point correction= 0.068462 (Hartree/Particle)
Thermal correction to Energy= 0.073898
Thermal correction to Enthalpy= 0.074842
Thermal correction to Gibbs Free Energy= 0.039183
Sum of electronic and zero-point Energies= -359.360455
Sum of electronic and thermal Energies= -359.355019
Sum of electronic and thermal Enthalpies= -359.354075
Sum of electronic and thermal Free Energies= -359.389734
---------------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
---------------------------------------
E(RB+HF-LYP) = -359.533246416 A.U.
_____________________________________________________________________________________
Molecule = 6PRN. Final optimised geometry with frequency analysis.
-----------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
-------------------------------------------------------------
: E(RB+HF-LYP) = -990.443115453 A.U.
--------------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Page 182
Annexure 1
35
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.084831 0.822097 1.665249
2 1 0 -0.802709 1.390835 1.381591
3 1 0 0.067923 0.695963 2.753926
4 7 0 0.090979 -0.507894 1.039748
5 6 0 -0.561443 -0.620731 -0.273073
6 1 0 -0.105835 0.035460 -1.035517
7 6 0 -0.376176 -2.067585 -0.734975
8 1 0 -0.779934 -2.203751 -1.739950
9 1 0 -0.897923 -2.742647 -0.047510
10 6 0 1.504977 -0.900356 1.019613
11 1 0 1.782634 -1.213946 2.032895
12 6 0 1.884906 -2.076214 0.121380
13 8 0 2.959081 -2.611816 0.225394
14 8 0 1.001331 -2.476958 -0.818780
15 6 0 -2.046767 -0.304693 -0.204305
16 6 0 -2.648868 0.461754 -1.208730
17 6 0 -2.844579 -0.815645 0.829500
18 6 0 -4.022256 0.710820 -1.187631
19 1 0 -2.038566 0.870687 -2.010956
20 6 0 -4.216222 -0.565229 0.852794
21 1 0 -2.379234 -1.395142 1.621511
22 6 0 -4.809295 0.196908 -0.156621
23 1 0 -4.473530 1.311555 -1.972506
24 1 0 -4.822896 -0.964166 1.661393
25 1 0 -5.877793 0.393235 -0.135910
26 7 0 1.944652 1.976768 -0.985952
27 6 0 1.245391 2.506309 0.094721
28 6 0 2.562596 0.747683 -0.747813
29 1 0 1.971438 2.427511 -1.893618
30 6 0 1.416297 1.533819 1.261372
31 8 0 0.612354 3.538996 0.081851
32 6 0 2.329010 0.406044 0.731630
33 8 0 3.171158 0.108555 -1.574645
34 1 0 1.832444 2.088338 2.106849
35 1 0 3.308762 0.343850 1.212007
--------------------------------------------------------------------------------
Rotational constants (GHZ): 0.4969776 0.2625717 0.2084654
------------------------------------------------------------------------------------------
Zero-point correction= 0.277898 (Hartree/Particle)
Thermal correction to Energy= 0.294187
Thermal correction to Enthalpy= 0.295132
Thermal correction to Gibbs Free Energy= 0.232630
Sum of electronic and zero-point Energies= -990.165217
Sum of electronic and thermal Energies= -990.148928
Sum of electronic and thermal Enthalpies= -990.147984
Sum of electronic and thermal Free Energies= -990.210485
_____________________________________________________________________________________
Molecule = 6PRX. Final optimised geometry with frequency analysis.
-------------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------
E(RB+HF-LYP) = -990.451358185 A.U.
-------------------------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -0.619252 -0.305441 -1.548644
2 1 0 -0.572635 0.450120 -2.353224
3 1 0 -0.053156 -1.182091 -1.878737
4 7 0 -0.085101 0.210914 -0.280598
5 6 0 1.191264 0.926028 -0.412342
6 1 0 1.295906 1.305720 -1.443686
7 6 0 1.154100 2.173085 0.479895
8 1 0 2.056029 2.772047 0.350134
9 1 0 1.068304 1.901165 1.538903
10 6 0 -1.168505 0.968809 0.386319
11 1 0 -1.036871 0.926300 1.475629
12 6 0 -1.164189 2.452243 -0.002094
13 8 0 -2.120831 3.090634 -0.366765
14 8 0 0.060761 3.030792 0.092952
15 6 0 2.405491 0.062825 -0.096203
16 6 0 3.634834 0.347160 -0.704430
17 6 0 2.333163 -0.982612 0.830754
Page 183
Annexure 1
36
18 6 0 4.773401 -0.394128 -0.388406
19 1 0 3.699640 1.149805 -1.437021
20 6 0 3.470756 -1.727133 1.146089
21 1 0 1.375092 -1.219683 1.282751
22 6 0 4.693716 -1.433740 0.540298
23 1 0 5.718939 -0.165370 -0.872706
24 1 0 3.400023 -2.540764 1.863121
25 1 0 5.577951 -2.016336 0.784116
26 7 0 -2.827032 -2.016894 0.527170
27 6 0 -2.920499 -0.735848 1.062396
28 6 0 -2.281949 -2.081968 -0.752325
29 1 0 -3.038119 -2.846437 1.070105
30 6 0 -2.461584 0.242928 -0.021449
31 8 0 -3.275231 -0.471836 2.189805
32 6 0 -2.084197 -0.641241 -1.233096
33 8 0 -2.023720 -3.100151 -1.353977
34 1 0 -3.250749 0.973552 -0.214338
35 1 0 -2.722568 -0.487484 -2.107752
---------------------------------------------------------------------
Rotational constants (GHZ): 0.4607154 0.2365410 0.1852673
---------------------------------------------------------------------------------
Zero-point correction= 0.277961 (Hartree/Particle)
Thermal correction to Energy= 0.294230
Thermal correction to Enthalpy= 0.295174
Thermal correction to Gibbs Free Energy= 0.231966
Sum of electronic and zero-point Energies= -990.173397
Sum of electronic and thermal Energies= -990.157128
Sum of electronic and thermal Enthalpies= -990.156184
Sum of electronic and thermal Free Energies= -990.219392
__________________________________________________________________________________
Molecule = 6TRN. Final optimised geometry with frequency analysis.
-----------------------------------------------------------------
# opt=qst3 freq b3lyp/6-31g(d) geom=connectivity
------------------------------------------------
E(RB+HF-LYP) = -990.364093502 A.U.
---------------------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -0.137606 0.398730 1.817188
2 1 0 -1.071798 0.924423 1.684324
3 1 0 0.293869 0.335015 2.807041
4 7 0 0.163775 -0.588111 0.962392
5 6 0 -0.571223 -0.692293 -0.348926
6 1 0 -0.081944 0.010965 -1.026776
7 6 0 -0.346438 -2.105905 -0.884737
8 1 0 -0.791805 -2.189693 -1.877734
9 1 0 -0.817825 -2.849118 -0.229128
10 6 0 1.347866 -1.247840 1.055756
11 1 0 1.834120 -1.258312 2.020024
12 6 0 1.834683 -2.192842 0.060604
13 8 0 2.908869 -2.744268 0.146369
14 8 0 1.037427 -2.412387 -1.038565
15 6 0 -2.039805 -0.343254 -0.231938
16 6 0 -2.523687 0.814103 -0.855264
17 6 0 -2.936138 -1.164956 0.468761
18 6 0 -3.880392 1.137141 -0.794328
19 1 0 -1.832927 1.478613 -1.367389
20 6 0 -4.290666 -0.841446 0.529269
21 1 0 -2.577536 -2.054764 0.979395
22 6 0 -4.766512 0.307852 -0.106704
23 1 0 -4.239754 2.040324 -1.278916
24 1 0 -4.974526 -1.486167 1.074215
25 1 0 -5.822556 0.558516 -0.058780
26 7 0 1.717772 1.821101 -1.027074
27 6 0 1.034329 2.432276 0.028145
28 6 0 2.786284 1.011099 -0.570303
29 1 0 1.631703 2.119202 -1.989666
30 6 0 1.620908 1.836086 1.272795
31 8 0 0.143789 3.254800 -0.088240
32 6 0 2.648910 0.992430 0.908957
33 8 0 3.621073 0.500650 -1.286807
34 1 0 1.477900 2.324692 2.227565
35 1 0 3.429914 0.577936 1.530900
---------------------------------------------------------------------
Rotational constants (GHZ): 0.4908450 0.2610341 0.2014852
Page 184
Annexure 1
37
-----------------------------------------------------------------------------------
Zero-point correction= 0.272154 (Hartree/Particle)
Thermal correction to Energy= 0.289514
Thermal correction to Enthalpy= 0.290458
Thermal correction to Gibbs Free Energy= 0.225344
Sum of electronic and zero-point Energies= -990.091940
Sum of electronic and thermal Energies= -990.074580
Sum of electronic and thermal Enthalpies= -990.073636
Sum of electronic and thermal Free Energies= -990.138749
-----------------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
------------------------------------------------
E(RB+HF-LYP) = -990.621779602 A.U.
______________________________________________________________________________________
Molecule = 6TRX. Final optimised geometry with frequency analysis.
--------------------------------------------------------------
# opt=qst3 freq b3lyp/6-31g(d) geom=connectivity
------------------------------------------------------------------
E(RB+HF-LYP) = -990.363529580 A.U.
------------------------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.074235 -0.968835 -0.837595
2 1 0 -0.774791 -1.619339 -0.688907
3 1 0 0.814028 -1.233446 -1.581098
4 7 0 -0.057852 0.329613 -0.541318
5 6 0 -1.143086 0.750200 0.398809
6 1 0 -0.770401 0.533620 1.407701
7 6 0 -1.318277 2.263725 0.263507
8 1 0 -2.048631 2.610329 0.997109
9 1 0 -1.690614 2.510440 -0.739643
10 6 0 0.985940 1.190865 -0.687078
11 1 0 1.749901 0.930910 -1.405516
12 6 0 1.002606 2.548786 -0.165807
13 8 0 1.956212 3.287868 -0.262968
14 8 0 -0.113392 2.972260 0.526748
15 6 0 -2.454508 0.028067 0.174584
16 6 0 -3.077936 -0.623507 1.245097
17 6 0 -3.096038 0.054706 -1.073093
18 6 0 -4.320960 -1.236155 1.077016
19 1 0 -2.589022 -0.651247 2.216138
20 6 0 -4.334705 -0.561850 -1.242474
21 1 0 -2.619771 0.545185 -1.918038
22 6 0 -4.950999 -1.206558 -0.167119
23 1 0 -4.791491 -1.739543 1.916701
24 1 0 -4.818856 -0.539042 -2.214639
25 1 0 -5.916264 -1.686576 -0.300837
26 7 0 3.485614 -1.619857 -0.452231
27 6 0 3.576601 -0.350589 0.156568
28 6 0 2.409783 -2.363369 0.043271
29 1 0 4.236211 -2.023652 -0.995944
30 6 0 2.344287 -0.229025 0.988358
31 8 0 4.495387 0.427272 0.009599
32 6 0 1.639635 -1.407907 0.900173
33 8 0 2.174131 -3.529717 -0.205913
34 1 0 2.236153 0.571663 1.706354
35 1 0 0.871033 -1.770369 1.570413
---------------------------------------------------------------------
Rotational constants (GHZ): 0.4815626 0.2162109 0.1637206
-------------------------------------------------------------------------------
Zero-point correction= 0.271784 (Hartree/Particle)
Thermal correction to Energy= 0.289279
Thermal correction to Enthalpy= 0.290223
Thermal correction to Gibbs Free Energy= 0.224177
Sum of electronic and zero-point Energies= -990.091745
Sum of electronic and thermal Energies= -990.074251
Sum of electronic and thermal Enthalpies= -990.073306
Sum of electronic and thermal Free Energies= -990.139352
------------------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
---------------------------------------
E(RB+HF-LYP) = -990.621355350 A.U.
_____________________________________________________________________________________
Molecul = 6AY. Final optimised geometry with frequency analysis.
Page 185
Annexure 1
38
--------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
------------------------------------------
E(RB+HF-LYP) = -630.935103560 A.U.
-------------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.383258 2.243802 -0.381132
2 1 0 -0.671946 2.232835 -0.594781
3 1 0 0.938454 3.167486 -0.288636
4 7 0 1.030868 1.103746 -0.221813
5 6 0 0.296654 -0.190499 -0.474002
6 1 0 0.464431 -0.410877 -1.533084
7 6 0 0.973620 -1.286681 0.353234
8 1 0 0.492655 -2.243132 0.135612
9 1 0 0.853628 -1.072976 1.424359
10 6 0 2.358452 0.980030 0.064834
11 1 0 2.921796 1.898911 0.154202
12 6 0 3.085479 -0.253784 0.085060
13 8 0 4.298003 -0.338222 0.141324
14 8 0 2.342140 -1.429775 0.024778
15 6 0 -1.188525 -0.128923 -0.194414
16 6 0 -2.096852 -0.449149 -1.210233
17 6 0 -1.679952 0.172840 1.085320
18 6 0 -3.469566 -0.472319 -0.957047
19 1 0 -1.727395 -0.683603 -2.205770
20 6 0 -3.050754 0.155114 1.337287
21 1 0 -0.990720 0.436984 1.882819
22 6 0 -3.948831 -0.169768 0.317453
23 1 0 -4.161093 -0.722709 -1.756565
24 1 0 -3.418133 0.394795 2.331206
25 1 0 -5.016799 -0.183932 0.516347
----------------------------------------------------------------------------------------
Rotational constants (GHZ): 1.8546706 0.3874175 0.3644420
-----------------------------------------------------------------------------------------
Zero-point correction= 0.201731 (Hartree/Particle)
Thermal correction to Energy= 0.213102
Thermal correction to Enthalpy= 0.214046
Thermal correction to Gibbs Free Energy= 0.163654
Sum of electronic and zero-point Energies= -630.733373
Sum of electronic and thermal Energies= -630.722002
Sum of electronic and thermal Enthalpies= -630.721058
Sum of electronic and thermal Free Energies= -630.771450
--------------------------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
---------------------------------------
E(RB+HF-LYP) = -631.092231900 A.U.
_____________________________________________________________________________________
Molecule =7EN. Final optimised geometry with frequency analysis.
--------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
-----------------------------------------------------------
E(RB+HF-LYP) = -379.289544507 A.U.
------------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -0.000755 1.258254 0.667804
2 1 0 -0.000695 2.089998 1.360223
3 6 0 -0.000755 1.258254 -0.667804
4 1 0 -0.000695 2.089998 -1.360223
5 6 0 0.000165 -0.158713 -1.131991
6 6 0 0.000165 -0.158713 1.131991
7 8 0 0.000165 -0.600004 -2.245452
8 8 0 0.000165 -0.600004 2.245452
9 8 0 0.000730 -0.971804 0.000000
---------------------------------------------------------------------
Rotational constants (GHZ): 6.8429883 2.4475853 1.8027733
-----------------------------------------------------------------------------
Zero-point correction= 0.055889 (Hartree/Particle)
Thermal correction to Energy= 0.061073
Thermal correction to Enthalpy= 0.062018
Thermal correction to Gibbs Free Energy= 0.026815
Page 186
Annexure 1
39
Sum of electronic and zero-point Energies= -379.233656
Sum of electronic and thermal Energies= -379.228471
Sum of electronic and thermal Enthalpies= -379.227527
Sum of electronic and thermal Free Energies= -379.262730
------------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
----------------------------------------------------------------------
E(RB+HF-LYP) = -379.399325820 A.U.
______________________________________________________________________________________
Molecule = 7PRN. Final optimised geometry with frequency analysis.
-----------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------
E(RB+HF-LYP) = -1010.30013390 A.U.
-------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.074878 0.785100 1.698358
2 1 0 -0.835198 1.333878 1.450391
3 1 0 0.098184 0.640239 2.784385
4 7 0 0.104571 -0.528881 1.047452
5 6 0 -0.541701 -0.619059 -0.272840
6 1 0 -0.090913 0.062676 -1.015276
7 6 0 -0.331721 -2.050547 -0.769195
8 1 0 -0.726444 -2.167221 -1.779872
9 1 0 -0.844649 -2.752231 -0.102466
10 6 0 1.523522 -0.891387 1.017395
11 1 0 1.815609 -1.213099 2.023572
12 6 0 1.928523 -2.037913 0.092615
13 8 0 3.018129 -2.544325 0.181862
14 8 0 1.054270 -2.435139 -0.855054
15 6 0 -2.030129 -0.321252 -0.202717
16 6 0 -2.629236 0.488319 -1.174707
17 6 0 -2.830874 -0.886772 0.800060
18 6 0 -4.004770 0.725577 -1.151946
19 1 0 -2.016090 0.940605 -1.950921
20 6 0 -4.204429 -0.647748 0.824403
21 1 0 -2.367860 -1.500110 1.567703
22 6 0 -4.795295 0.157160 -0.152745
23 1 0 -4.454575 1.359982 -1.910577
24 1 0 -4.814224 -1.089062 1.608195
25 1 0 -5.865401 0.344214 -0.131194
26 8 0 1.848542 1.975734 -1.023683
27 6 0 2.541060 0.803075 -0.718307
28 6 0 1.161710 2.460887 0.081102
29 6 0 2.321468 0.444049 0.749334
30 8 0 3.193594 0.236853 -1.543774
31 6 0 1.378663 1.538409 1.269694
32 8 0 0.500695 3.457464 0.022664
33 1 0 3.301454 0.396178 1.229291
34 1 0 1.776255 2.134037 2.095460
---------------------------------------------------------------------
Rotational constants (GHZ): 0.5064793 0.2638551 0.2104121
----------------------------------------------------------------------------------
Zero-point correction= 0.264933 (Hartree/Particle)
Thermal correction to Energy= 0.281078
Thermal correction to Enthalpy= 0.282022
Thermal correction to Gibbs Free Energy= 0.219732
Sum of electronic and zero-point Energies= -1010.035201
Sum of electronic and thermal Energies= -1010.019056
Sum of electronic and thermal Enthalpies= -1010.018111
Sum of electronic and thermal Free Energies= -1010.080402
____________________________________________________________________________________
Molecule = 7PRX. Final optimised geometry with frequency analysis.
----------------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------
E(RB+HF-LYP) = -1010.30719095 A.U.
--------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
Page 187
Annexure 1
40
1 6 0 -0.617862 -0.295722 -1.558667
2 1 0 -0.589542 0.470666 -2.353538
3 1 0 -0.041189 -1.159770 -1.902180
4 7 0 -0.089814 0.208897 -0.284479
5 6 0 1.183003 0.935391 -0.405100
6 1 0 1.286450 1.325408 -1.432422
7 6 0 1.132832 2.173505 0.498759
8 1 0 2.029522 2.781461 0.376295
9 1 0 1.046641 1.892149 1.555142
10 6 0 -1.178484 0.952845 0.387946
11 1 0 -1.048477 0.899275 1.476575
12 6 0 -1.185936 2.440223 0.012521
13 8 0 -2.148811 3.069754 -0.351027
14 8 0 0.032526 3.026435 0.116686
15 6 0 2.401560 0.077061 -0.093811
16 6 0 3.629739 0.376146 -0.697419
17 6 0 2.334252 -0.977667 0.822949
18 6 0 4.772705 -0.360321 -0.386401
19 1 0 3.690472 1.186267 -1.422107
20 6 0 3.476489 -1.717482 1.132700
21 1 0 1.378004 -1.227261 1.272032
22 6 0 4.698282 -1.409525 0.531940
23 1 0 5.717472 -0.120412 -0.866676
24 1 0 3.409604 -2.538736 1.841154
25 1 0 5.585994 -1.988484 0.771495
26 8 0 -2.787699 -2.063574 0.551056
27 6 0 -2.924924 -0.766077 1.025698
28 6 0 -2.236470 -2.081223 -0.723633
29 6 0 -2.467480 0.224037 -0.036852
30 8 0 -3.326478 -0.539824 2.129863
31 6 0 -2.076076 -0.654716 -1.236692
32 8 0 -1.957734 -3.105231 -1.275302
33 1 0 -3.258923 0.952852 -0.226856
34 1 0 -2.721544 -0.535032 -2.111405
---------------------------------------------------------------------
Rotational constants (GHZ): 0.4645499 0.2371098 0.1849717
------------------------------------------------------------------------------------
Zero-point correction= 0.264971 (Hartree/Particle)
Thermal correction to Energy= 0.281115
Thermal correction to Enthalpy= 0.282059
Thermal correction to Gibbs Free Energy= 0.218868
Sum of electronic and zero-point Energies= -1010.042219
Sum of electronic and thermal Energies= -1010.026076
Sum of electronic and thermal Enthalpies= -1010.025132
Sum of electronic and thermal Free Energies= -1010.088323
______________________________________________________________________________________
Molecule =7TRN. Final optimised geometry with frequency analysis.
-----------------------------------------------------------------
# opt=(calcfc,qst3) freq b3lyp/6-31g(d) geom=connectivity
---------------------------------------------------------
: E(RB+HF-LYP) = -1010.22984926 A.U
--------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -0.106449 0.413850 1.830441
2 1 0 -1.052456 0.917870 1.696132
3 1 0 0.331273 0.368214 2.818715
4 7 0 0.216872 -0.569181 0.978773
5 6 0 -0.516708 -0.706933 -0.332872
6 1 0 -0.041550 -0.006859 -1.024474
7 6 0 -0.270131 -2.127035 -0.841175
8 1 0 -0.710815 -2.234641 -1.833552
9 1 0 -0.732174 -2.864324 -0.172615
10 6 0 1.424545 -1.182780 1.065014
11 1 0 1.919015 -1.168887 2.025624
12 6 0 1.923600 -2.143417 0.084849
13 8 0 3.018452 -2.651393 0.173932
14 8 0 1.119235 -2.421543 -0.988348
15 6 0 -1.990489 -0.381832 -0.223089
16 6 0 -2.499523 0.729813 -0.906652
17 6 0 -2.866114 -1.184544 0.524473
18 6 0 -3.862463 1.027492 -0.855078
19 1 0 -1.825647 1.373991 -1.465285
20 6 0 -4.226415 -0.884966 0.576018
21 1 0 -2.487019 -2.039923 1.077839
Page 188
Annexure 1
41
22 6 0 -4.727824 0.219491 -0.117499
23 1 0 -4.242910 1.894348 -1.387392
24 1 0 -4.894783 -1.513320 1.158011
25 1 0 -5.788435 0.451333 -0.076701
26 8 0 1.509084 1.858568 -1.058346
27 6 0 2.609345 1.051993 -0.667631
28 6 0 0.953027 2.447567 0.076839
29 6 0 2.634590 1.036763 0.804485
30 8 0 3.324228 0.546429 -1.487300
31 6 0 1.638022 1.873809 1.259268
32 8 0 0.061076 3.252885 -0.002332
33 1 0 3.483197 0.637568 1.341296
34 1 0 1.565526 2.353711 2.225798
---------------------------------------------------------------------
Rotational constants (GHZ): 0.4887113 0.2677739 0.2066844
--------------------------------------------------------------------------
Zero-point correction= 0.259589 (Hartree/Particle)
Thermal correction to Energy= 0.276704
Thermal correction to Enthalpy= 0.277648
Thermal correction to Gibbs Free Energy= 0.212965
Sum of electronic and zero-point Energies= -1009.970261
Sum of electronic and thermal Energies= -1009.953145
Sum of electronic and thermal Enthalpies= -1009.951291
Sum of electronic and thermal Free Energies= -1010.016884
-----------------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
---------------------------------------
E(RB+HF-LYP) = -1010.49304343 A.U.
_____________________________________________________________________________________
Molecule = 7TRX. Final optimised geometry with frequency analysis.
--------------------------------------------------------------------
# opt=qst3 freq b3lyp/6-31g(d) geom=connectivity
------------------------------------------------
E(RB+HF-LYP) = -1010.22661867 A.U.
--------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.083977 -0.965526 -0.836755
2 1 0 -0.767854 -1.613471 -0.691781
3 1 0 0.819452 -1.229028 -1.585616
4 7 0 -0.044639 0.333040 -0.536335
5 6 0 -1.132496 0.755096 0.402866
6 1 0 -0.763755 0.535196 1.412428
7 6 0 -1.300700 2.269194 0.270255
8 1 0 -2.032055 2.617785 1.001614
9 1 0 -1.665962 2.521815 -0.733708
10 6 0 1.002353 1.189564 -0.678284
11 1 0 1.758052 0.940218 -1.409526
12 6 0 1.024718 2.545076 -0.141572
13 8 0 1.988836 3.271335 -0.220717
14 8 0 -0.092342 2.970908 0.542333
15 6 0 -2.444368 0.036053 0.172291
16 6 0 -3.067976 -0.623982 1.237567
17 6 0 -3.084676 0.072445 -1.075828
18 6 0 -4.310605 -1.235757 1.063735
19 1 0 -2.580221 -0.658683 2.208992
20 6 0 -4.322887 -0.543410 -1.250729
21 1 0 -2.608539 0.569618 -1.916968
22 6 0 -4.939500 -1.196699 -0.180721
23 1 0 -4.781660 -1.745729 1.899066
24 1 0 -4.806328 -0.513407 -2.222973
25 1 0 -5.904360 -1.676134 -0.318927
26 8 0 3.475780 -1.667341 -0.465464
27 6 0 2.384546 -2.349328 0.066805
28 6 0 3.545148 -0.385679 0.120478
29 6 0 1.629998 -1.394681 0.912518
30 8 0 2.164086 -3.503503 -0.189748
31 6 0 2.349213 -0.223316 0.973509
32 8 0 4.464155 0.351381 -0.104206
33 1 0 0.866291 -1.744263 1.594466
34 1 0 2.274813 0.588261 1.682878
---------------------------------------------------------------------
Rotational constants (GHZ): 0.4836976 0.2171404 0.1643902
------------------------------------------------------------------------------------
Page 189
Annexure 1
42
Zero-point correction= 0.259275 (Hartree/Particle)
Thermal correction to Energy= 0.276494
Thermal correction to Enthalpy= 0.277439
Thermal correction to Gibbs Free Energy= 0.212012
Sum of electronic and zero-point Energies= -1009.967344
Sum of electronic and thermal Energies= -1009.950124
Sum of electronic and thermal Enthalpies= -1009.949180
Sum of electronic and thermal Free Energies= -1010.014606
------------------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
---------------------------------------
E(RB+HF-LYP) = -1010.49088278 A.U.
_____________________________________________________________________________________
Molecule =7AY. Final optimised geometry with frequency analysis.
------------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------
E(RB+HF-LYP) = -630.935103556 A.U.
--------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.383258 2.243802 -0.381132
2 1 0 -0.671946 2.232835 -0.594781
3 1 0 0.938454 3.167486 -0.288636
4 7 0 1.030868 1.103746 -0.221813
5 6 0 0.296654 -0.190499 -0.474002
6 1 0 0.464431 -0.410877 -1.533084
7 6 0 0.973620 -1.286681 0.353234
8 1 0 0.492655 -2.243132 0.135612
9 1 0 0.853628 -1.072976 1.424359
10 6 0 2.358452 0.980030 0.064834
11 1 0 2.921796 1.898911 0.154202
12 6 0 3.085479 -0.253784 0.085060
13 8 0 4.298003 -0.338222 0.141324
14 8 0 2.342140 -1.429775 0.024778
15 6 0 -1.188525 -0.128923 -0.194414
16 6 0 -2.096852 -0.449149 -1.210233
17 6 0 -1.679952 0.172840 1.085320
18 6 0 -3.469566 -0.472319 -0.957047
19 1 0 -1.727395 -0.683603 -2.205770
20 6 0 -3.050754 0.155114 1.337287
21 1 0 -0.990720 0.436984 1.882819
22 6 0 -3.948831 -0.169768 0.317453
23 1 0 -4.161093 -0.722709 -1.756565
24 1 0 -3.418133 0.394795 2.331206
25 1 0 -5.016799 -0.183932 0.516347
---------------------------------------------------------------------
Rotational constants (GHZ): 1.8546708 0.3874175 0.3644421
--------------------------------------------------------------------------------
Zero-point correction= 0.201731 (Hartree/Particle)
Thermal correction to Energy= 0.213102
Thermal correction to Enthalpy= 0.214046
Thermal correction to Gibbs Free Energy= 0.163654
Sum of electronic and zero-point Energies= -630.733373
Sum of electronic and thermal Energies= -630.722002
Sum of electronic and thermal Enthalpies= -630.723958
Sum of electronic and thermal Free Energies= -630.771450
--------------------------------------------------------------------------------
# b3lyp/6-311+g(d) geom=connectivity sp
---------------------------------------
E(RB+HF-LYP) = -631.092231900 A.U.
Page 190
Annexure 1
43
IRC polt
1TS 1TS –IRC
2TRN 2TRN-IRC
2TRX 2TRX-IRC
2TSN 2TSN-IRC
2TSX 2TSX-IRC
3TRN 3TRN-IRC
Page 191
Annexure 1
44
3TRX 3TRX-IRC
3TSN 3TSN-IRC
3TSX 3TSX-IRC
4TRN 4TRN-IRC
4TRX 4TRX-IRC
4TSN 4TSN-IRC
Page 192
Annexure 1
45
4TSX 4TSX-IRC
5TRN 5TRN-IRC
5TRN-R 5TRN-R-IRC
5TRX 5TRX-IRC
5TRX-R 5TRX-R-IRC
5TSN 5TSN-IRC
Page 193
Annexure 1
46
5TSN-R 5TSN-R-IRC
5TSX 5TSX-IRC
5TSX-R 5TSX-R-IRC
6TRN 6TRN-IRC
6TRX 6TRX-IRC
7TRN 7TRN-IRC
7TRX 7TRX-IRC
Page 195
Annexure 2
47
4.3. Result Discussion
4.3.2. Experimental results for the cycloadditions of 1-pyrroline-1-oxide (N1) to methyl cinnamate (E1) and
benzylidene acetophenone (E2)
The cycloaddition between N1 and E1 was carried out in dry toluene at 82ºC under nitrogen atmosphere. It afforded two
diastereomeric cycloadducts (III/1prn) and (IV/1prx). The change in diastereomeric ratio of the cycloadducts for reaction
between N1 and E1 were noted after the intervals of 4 hours, 8 hours and 14 hours from the integration pattern of 300 MHz
1H NMR study of the crude reaction mixture as given in Table-4.5. The ratios of products were evaluated through integration
from 300 MHz 1H NMR spectra of the crude reaction mixtures and the products were characterized on the basis of IR,
500MHz 1H NMR, 125.5MHz 13C NMR, DQF-COSY, HMQC, HMBC, X-Ray crystallographic studies (Figs.4.4-4.6) and
theoretical NMR calculations43. The results have been given in Table 4.5. Ali et al34 carried out the cycloaddition between N1
and E1 in toluene at 55˚C for 2 hours under nitrogen atmosphere. They reported 87:13 ratio for the cycloadducts (III/1prn):
(IV/1prx) with the overall yield of 79%. When we carried out the reaction with N1 and E1 in toluene under nitrogen
atmosphere at 82ºC, we observed a remarkable decrease in diastereomeric excess from 4 to 14 hours as given in Table 4.5.
However, the overall yield remained almost the same within 4 to 14 hours (about 20%). It should be noted that the reaction
was continued for a period from 4 to 14 hours since the proportion of cycloadduct (IV/1prx) increased during that period.
Fig. 4.4. ORTEP of the asymmetric unit content (hydrogen's are drawn
as spheres with arbitrary radius). The ellipsoids encompass
50 % of the electron density of the atom (A and B of (I/2psx))
Fig. 4.5. One single copy of the asymmetric unit (molecule A of (I/2psx))
Page 196
Annexure 2
48
Fig. 4.6. One single molecule (A of (I/2psx)) viewed along the N-2 C-3 bond showing
the puckering of the two fused five-membered rings. The size of ellipsoids
is reduced (30 % of the electron density) and hydrogen's omitted for clarity.
Scheme: 4.1. IV/2psx : III/2psn=64:36 after 4hours
IV/2psx : III/2psn=64:36 after 14 hours III /1prn : IV/1prx = 89:11 after 4 hours III /1prn : IV/1prx = 87:13 after 8 hours III /1prn : IV/1prx = 65:35 after 14 hours
However, we failed to isolate the cycloadduct (IV/1prx) by column chromatography due to very reduced quantity of yields. It
was detected and identified from the chemical shift and coupling constant value of H2 in the 300 MHz 1H NMR spectrum of
the crude reaction mixture in which H2 appeared as a doublet in both (III/1prn) and (IV/1prx) resonating at δ 5.20 ppm (J2,3 =
9.2Hz ) and δ 5.09 ppm (J2,3 = 8.7Hz) respectively. These results were in complete agreement with that reported by Ali et al34.
The cycloadduct (III/1prn) was purified and heated at 82ºC in toluene under nitrogen atmosphere for 14 hours. The solution
turned into a gummy mass after removal of toluene under reduced pressure. 300MHz 1H NMR with the gummy mass
revealed that the cycloadduct (III/1prn) was no longer pure and had suffered decomposition due to heating. But, no signals of
the starting materials or of the cycloadduct (IV/1prx) appeared in the NMR spectrum. Hence, it could be concluded that the
lower amount of overall yield and the decrease in diastereomeric excess resulted from thermal decomposition of the
cycloadduct (III/1prn). The reaction was not reversible since the cycloadduct did not revert back to the starting materials after
heating but suffered decomposition. The thermal instability of the cycloadduct (III/1prn) resulted in reduced diastereomeric
excess at 82ºC after 4h as compared to that reported by Ali et al. at 55ºC after 2h.
The reaction between N1 and E2 was also carried out in dry toluene at 82ºC under nitrogen atmosphere for 14h. It resulted in
two diastereomeric cycloadducts (I/2psx) and (II/2psn) (Fig.-4.3) with the diastereomeric excess of 28%. In case of the
cycloaddition between N1 and E2, the cycloadducts were not thermally unstable and the diastereomeric ratio remained
unchanged from 4 to 14 hours.
4.3.3. General methods
Elementary analysis of compound (I/2psx) was done by using a Perkin Elmer 2400 Series II analyzer. Melting point was
recorded on an electrically heated Köfler Block apparatus and is uncorrected. The IR spectra were recorded in KBr pellets
using a Perkin Elmer RX-9 FT-IR Spectrophotometer. 1H NMR and 13C NMR spectra of crude reaction mixtures were
recorded using a Bruker AV-300 NMR spectrometer at 300 and 75.5 MHz respectively. 1H NMR and 13C NMR spectra of the
major cycloadducts in both the cycloadditions were recorded using a Bruker DRX 500 NMR spectrometer at 500 and 125.5
MHz respectively. DQF COSY, HMQC and HMBC spectra were also obtained by using a Bruker DRX 500 NMR
spectrometer. Chemical shifts for 1H NMR and 13C NMR were reported in parts per million downfield from tetramethylsilane
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(TMS). X-Ray crystallographic studies were carried out using a single crystal of approximate size 0.3x0.2x0.2 mm on the
NONIUS CCD diffractometer. The wavelength was the MoK radiation: =0.7107 Å. The cell dimensions were first
evaluated using a rapid rotation of 10°. The structure was solved using SHELXS and refined with SHELXL.
4.3.4. Materials
1-pyrroline-1-oxide was prepared by selenium dioxide catalyzed hydrogen peroxide oxidation of pyrrolidine according to the
procedure of Murahashi and Shiota61-63. Benzylidene acetophenone63 and methyl cinnamate64 were synthesized according to
literature. Neutral alumina (Activity I-II, Merck) was used for column chromatography. Analytical TLC was performed
using Merck silica gel G support. Organic extracts were dried over anhydrous sodium sulphate.
Cycloaddition of 1-pyrroline-1-oxide (N1) and methyl cinnamate (E1):
1-pyrroline-1-oxide (0.0019 moles, 0.1615 gm) and methyl cinnamate (0.00285 moles, 0.4617 gm) were heated in dry
thiophene free toluene (10 ml) at 82ºC under nitrogen atmosphere. The progress of the reaction was monitored by 300 MHz
1H NMR spectroscopy of the crude reaction mixture after 4 hours, 8 hours and 14 hours. The crude reaction mixture after 14
hours was subjected to column chromatography over neutral alumina. Petrol (60˚C -80 ˚C) - benzene (4:1) eluates were
collected and after removal of the solvent under reduced pressure, the cycloadduct (III/1prn) was obtained as a colourless oil.
The cycloadduct (III/1prn) was then heated in toluene at 82ºC under nitrogen atmosphere for 14 hours, toluene was removed
under reduced pressure and 300 MHz 1H NMR spectrum of the resulting orange gummy mass was recorded. The signals of
the starting materials or of the cycloadduct (IV/1prx) were not detected in the spectrum. It was also evident from the spectrum
that the compound (III/1prn) was no longer pure and had suffered decomposition due to heating. It was not possible to isolate
the decomposition products from the gummy mass. We failed to isolate the minor isomer (IV/1prx) and it was detected and
identified from the 300MHz 1H spectrum of the crude reaction mixture prior to column chromatography.
Cycloaddition of 1-pyrroline-1-oxide (N1) and benzylidene acetophenone (E2)
1-pyrroline-1-oxide (0.0019 moles, 0.1615 gm) and benzylidene acetophenone (0.00285 moles, 0.5928 gm) were heated in
dry thiophene free toluene (10 ml) at 82ºC under nitrogen atmosphere for 14 hours. Toluene was removed under reduced
pressure in a Büchi rotary evaporator and the crude post reaction mixture was chromatographed over neutral alumina to
isolate the cycloadducts. 1H NMR analysis of the crude thermolysate was used to determine the product ratio in the original
reaction mixture. The major cycloadduct (I/2psx) (yield 34 %) was isolated as shiny white crystals from 20% benzene in
petrol (60˚C -80 ˚C)- benzene (4:1) eluates. We failed to isolate the minor isomer due to very low diastereomeric excess. A
mixture of the major and minor isomer (yield 20 %) from 300MHz 1H NMR spectrum of the crude reaction mixture prior to
column chromatography) was also isolated as white solid from 10% benzene in petrol: benzene (4:1) eluates to identify the
minor isomer by spectroscopy.
Data for (2,3-trans-3,3a-cis)--3-carbomethoxy-2-phenyl--pyrrolo-[1,2-b]-isoxazolidine (III/1prn)
Yield (11%)
1H NMR (CDCl3, δ, 500MHz): 4.00 (1H multiplet, H3a), 3.55 (1H m, H3), 5.20 (1H d, J 9.2, H2), 1.79 (1H m, H4), 1.65
(1H m, H4), 1.55 (1H m, H5), 1.95 (1H m, H5), 3.22, 3.17 (2H m, H6a,6b)), 3.57 (1H, s, -OCH3), 7.36 (2H d, J 7.7, H2,6
(A)), 7.23 (2H, dist. t, H3,5 (A)), 7.17 (1H tt, J 7.3,1.2, H4 (A))
13C NMR (CDCl3, δ, 125.5 MHz): 68.0 (C3a), 60.3 (C3), 79.7 (C2), 27.8 (C4), 24.8 (C5), 57.8 (C6), 52.4 (-OCH3),
139.3(C1 (A)), 127.1(C2,6 (A)), 128.9 (C3,5 (A)), 128.5 (C4 (A)), 170.9 (C=O),[ phenyl ring = (A), numbering refer to Fig.
4.4.]
Data for(2,3-trans-3,3a-trans)-2-phenyl-3-oxophenyl-pyrrolo-[1,2-b]-isoxazolidine (I/2psx)
M.pt 114ºC (yield 34%)
IR: υ =1669 (s,-C=O), 763 (s), 698 (s),
(Found: C, 77.60; H, 6.41; N, 4.71. C19H19NO2 requires C, 77.79; H, 6.53; N, 4.77)
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1H NMR (CDCl3, δ, 500MHz): 4.07 (1H multiplet, H3a), 4.00 (1H dd, J 8.3,5.0, H3), 5.34(1H d, J 8.3, H2), 2.12 (1H m,
H4a), 1.97 (1H m, H4b), 1.87 (1H m, H5a), 2.30 (1H m, H5b), 3.04 (1H ddd, J 13.5Hz, 6.9 Hz, 9.8 Hz, H6b), 3.59 (1H ddd,
J 13.5 Hz, 7.1 Hz, 3.0 Hz, H6a), 7.72 (2H dd, J 7.5 Hz,1.2 Hz, H2,6 (B)), 7.35 (2H t, J 7.5 Hz, H3,5(B)), 7.51 (1H tt, J 7.5
Hz,1.2 Hz, H4 (B)),7.24-7.32 (5H m, H2,3,4,5,6 (A)) [oxophenyl ring = (B), phenyl ring (A),numbering refer to Fig. 4.5.]
13C NMR (CDCl3, δ, 125.5 MHz): 71.7 (C3a), 66.3 (C3), 83.7 (C2), 32.5 (C4), 24.8 (C5), 57.4 (C6), 137.1 (C1 (B)), 129.0
(C2,6 (B)), 129.0 (C3,5 (B)), 133.8 (C4 (B)), 138.3 (C1 (A)), 126.9 (C2,6 (A)), 128.9 (C3,5 (A)), 128.8 (C4 (A)), 198.2
(C=O) [ oxophenyl ring = (B), phenyl ring (A), numbering refer to Fig. 4.5.]
Data for (2,3-trans-3,3a-cis)-2-phenyl-3-oxophenyl-pyrrolo-[1,2-b]-isoxazolidine (II/2psn)
Yield (20%)
1H NMR (CDCl3, δ, 300MHz): 4.46 (1H dist. triplet, H3a), 4.28 (1H distorted dd, H3), 5.63 (1H d, J 9.0, H2), 1.48-1.82 (4H
m, H4,5), 3.30 (2H dist t, H6), 7.92 (2H d, J 8.0 Hz, H2,6 (B)), 7.41-7.57 (3H m, H3,4,5(B)), 7.19-7.33 (5H m, H2,3,4,5,6
(A)) [ oxophenyl ring = (B), phenyl ring (A), numbering refer to Fig. 4.6.]
13C NMR (CDCl3, δ, 75.5 MHz): 68.2 (C3a), 63.0 (C3), 78.9 (C2), 26.8 (C4), 24.4 (C5), 56.9 (C6), 136.0 (C1 (B)),
128.8(C2,6 (B)), 128.1(C3,5 (B)), 133.6 (C4 (B)), 139.1 (C1 (A)), 126.4 (C2,6 (A)), 128.5 (C3,5 (A)), 127.9 (C4 (A)), 196.0
(C=O), [ oxophenyl ring = (B), phenyl ring (A), numbering refer to Fig. 4.6.]
S. 1 500 MHz 1H NMR spectrum of (III/1prn) which was
separated as an oily liquid containing trace of E1.
S. 2 500 MHz 1H NMR spectrum of (III/1prn) which was
separated as an oily liquid containing trace of E1(expanded)
S. 3 125.5 13C NMR spectrum (fully decoupled) of (III/1prn) which was separated as an oily liquid containing trace of E1.
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S. 4 125.5 13C NMR spectrum (fully decoupled) of (III/1prn) which
was separated as an oily liquid containing trace of E1(expanded)
S. 5 125.5 13C NMR spectrum (DEPT 135º) of (III/1prn)
which was separated as an oily liquid containing trace of E1.
S. 6 DQF COSY spectrum of (III/1prn) which was
separated as an oily liquid containing trace of E1
S. 7 DQF COSY spectrum of (III/1prn) which was separated as an oily liquid containing trace of E1 (expanded).
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S. 8 DQF COSY spectrum of (III/1prn) which was separated as an oily
liquid containing trace of E1 (expanded).
S. 8 HMQC spectrum of of (III/1prn) which was separated as an oily liquid
containing trace of E1.
S. 9 HMQC spectrum of (III/1prn) which was separated as an oily
liquid containing trace of E1. (expanded)
S. 10 300 MHz 1H NMR spectrum of the crude reaction mixture of the reaction
between N1 and E1 after 4 hours
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S. 11 300 MHz 1H NMR spectrum of the crude reaction mixture of the reaction between
N1 and E1 after 8 hours
S. 13 300 MHz 1H NMR spectrum of the crude reaction mixture of the reaction between
N1 and E1 after 14 hours
S. 14 300MHz 1H NMR spectrum of the crude reaction mixture after 14 hours for
the reaction between N1 and E2
S. 15 75.5MHz 13CNMR spectrum of the two cycloadducts after purification by
column chromatography for the reaction between N1 and E
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S. 16 75.5MHz 13CNMR spectrum of the two cycloadducts after purification
by column chromatography for the reaction between N1 and E2
S. 17 500 MHz 1H NMR spectrum of (I/2psx )
S. 18 500 MHz 1H NMR spectrum of (I/2psx ) (expanded).
S. 19 500 MHz 1H NMR spectrum (I/2psx) (expanded)
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S. 20 500 MHz 1H NMR spectrum of (I/2psx) (expanded)
S. 21 125.5 MHz 13C NMR spectrum (fully decoupled)of (I/2psx)
S. 22 125.5 MHz 13C NMR spectrum (fully decoupled) of (I/2psx) (expanded)
S. 23 125.5 MHz 13C NMR (DEPT 135º) spectrum of (I/2psx) (expanded)
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S. 24 DQF COSY spectrum of (I/2psx) (using Bruker DRX 500 NMR spectrometer) (expanded)
S. 25 DQF COSY spectrum of (I/2psx ) (using Bruker DRX 500 NMR spectrometer) (expanded)
S. 26 HMQC spectrum of (I/2psx ) (using Bruker DRX 500 NMR spectrometer)
S. 27 HMQC spectrum of (I/2psx) (using Bruker DRX 500 NMR spectrometer) (expanded)
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S. 28 HMBC spectrum of (I/2psx) (using Bruker DRX 500 NMR spectrometer)
X-Ray data of (I/2psx)
Symmetry used
in scaling p222
a (Å) 19.5855 (7)
b (Å) 9.2809 (2)
c (Å) 17.1942 (6)
alpha (°) 90.0
beta (°) 90.0
gamma (°) 90.0
Volume (A3) 3125.5(6)
Z 8
Mosaicity (°) 0.46
Final Data Set:
Number of 'full' reflections 14 460
Number of 'partial' reflections 10 370
Total number of integrated reflections 23 567
Total number of unique reflections 4 401
Data completeness 99.6%
Resolution range 50.0-0.89 Å
Theta range 0.41°-23.53°
Average Intensity 43.1
Average Sigma(I) 1.1
Overall R-merge (linear) 0.050
Refinement statistics of (I)
Compound: (2psx)
Formula C19H19NO2
Mw 293,35
No of reflections used 4401
No of observed reflections* 3541
No of refined parameters 398
R-factor (observed Fs) 0.044
R-factor (all data) 0.062
Rw on F2 (observed) 0.111
Rw on F2 (all data) 0.124
Goodness of fit 1.006
Min – max in last F density map (e-) -0.20 / +0.19
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* Criterion: F ≥ 4 (F)
The stereochemistry is trans for ring hydrogen's (or substituents on oxazolidine ring) but H3 is cis with respect to the lone
pair of N2 (cis junction of the two five-membered rings)
Ring parameters:
The internal dihedral angles are as follows:
Compound: (2psx) (A) (2psx) (B)
Dihedral angles (°):
N2-C3-C4-C5
C3-C4-C5-O1
C4-C5-O1-N2
C5-O1-N2-C3
O1-N2-C3-C4
Puckering parameters (°):
m
P
Closest pucker Descriptor:
-19.6
39.6
-45.4
32.9
-6.9
45.4
63.8
C5/O1-T*
-17.5
39.5
-47.0
35.5
-9.7
46.6
67.2
C5/O1-T*
*(ideal twist has P = 72°, Envelope P = 54°
Positional parameters (x104) and mean recalculated isotropic
-------- factors (x103)for non-hydrogen atoms
Molecule A:
ATOM X Y Z <U>
O1A 1481(12) 5057(2) 3385(15) 66(6) N2A 1389(15) 5181(3) 4233( 2) 71(8)
C3A 1753(19) 6542(4) 4472( 2) 69(9)
C4A 2124(14) 7050(3) 3720(19) 50(8)
C5A 2142(15) 5677(3) 3236( 2) 53(8) C6A 666( 2) 5489(5) 4359( 4) 108(1)
C7A 559( 2) 6963(5) 4428( 4) 129(2)
C8A 1206( 3) 7554(4) 4766( 3) 96(1)
C4AA 2828(17) 7636(3) 3893( 2) 54(9) O4A 3275(12) 6799(2) 4105(17) 84(8)
C41A 2983(14) 9200(3) 3837(17) 46(7)
C42A 2495(16) 10219(3) 3628( 2) 56(8)
C43A 2663(18) 11664(3) 3601( 2) 67(1) C44A 3308(18) 12115(4) 3783( 3) 69(1)
C45A 3795(17) 11125(4) 3990( 2) 68(9)
C46A 3635(15) 9682(3) 4019(19) 58(8)
C51A 2236(15) 5845(3) 2378(19) 50(8) C52A 2781(16) 5200(3) 2011( 2) 57(8)
C53A 2877( 2) 5362(4) 1228( 3) 76(1)
C54A 2417( 2) 6149(4) 793( 2) 80(1)
C55A 1864( 2) 6778(4) 1150( 2) 74(1) C56A 1774(17) 6654(3) 1943( 2) 63(9)
Molecule B:
O1B 981(11) 143(2) 2475(12) 56(6)
N2B 1044(13) 292(3) 1622(15) 54(7) C3B 687(17) 1672(3) 1434(18) 56(8)
C4B 323(14) 2128(3) 2184(17) 44(7)
C5B 323(14) 722(3) 2644(17) 47(7)
C4AB -391(16) 2696(3) 2023( 2) 48(8) O4B -844(11) 1851(2) 1884(17) 75(7)
C41B -524(13) 4270(3) 2011(18) 46(7)
C42B -1184(16) 4750(3) 1852( 2) 61(9)
C43B -1332(17) 6205(4) 1829( 2) 71(1) C44B -834(19) 7196(4) 1963( 3) 76(1)
C45B -186(18) 6748(3) 2118( 3) 81(1)
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C46B -28(15) 5294(3) 2154( 2) 61(9)
C51B 237(14) 861(3) 3509(17) 46(7) C52B -321(16) 240(3) 3876(19) 54(8)
C53B -421(18) 386(4) 4658( 2) 66(9)
C54B 39( 2) 1149(4) 5097( 2) 74(1)
C55B 605( 2) 1772(4) 4749( 2) 70(1) C56B 696(16) 1640(3) 3956(19) 57(8)
C6B 1770(18) 539(4) 1474( 3) 78(1)
C7B 1881( 2) 2101(5) 1491( 3) 97(1)
C8B 1241( 3) 2688(4) 1130( 3) 87(1)
Positional parameters (x103) and mean recalculated isotropic
-------- factors (x103) for hydrogens atoms
Molecule A:
ATOM X Y Z U H3A 209 634 488 83
H4A 185 779 346 61
H5A 250 504 344 64
H61A 40 512 393 130 H62A 51 501 483 130
H71A 18 716 477 155
H72A 47 739 392 155
H81A 119 755 533 115 H82B 129 853 459 115
H42A 205 993 351 68
H43A 233 1234 346 81
H44A 342 1309 377 84 H45A 423 1143 411 82
H46A 397 902 416 70
H52A 309 465 230 69
H53A 325 494 99 91 H54A 248 625 26 97
H55A 155 729 86 89
H56A 141 711 219 76
Molecule B:
H3B 35 150 103 68
H4B 59 286 246 54
H5B -3 8 244 57 H42B -153 408 176 74
H43B -178 651 172 86
H44B -94 818 195 92
H45B 16 743 220 97
H46B 41 501 228 74
H52B -63 -29 358 66
H53B -80 -3 489 80
H54B -3 125 563 89 H55B 92 228 505 84
H56B 107 208 372 69
H61B 205 7 187 94 H62B 190 15 97 94
H71B 228 237 119 117
H72B 194 245 202 117
H81B 127 266 57 105 H82B 116 367 130 105
Table-7:
Anisotropic thermal parameters (x103)
-------- for non-hydrogen atoms
Molecule A:
ATOM U11 U22 U33 U23 U13 U12
O1A 58 (14) 54 (12) 85 (18) 0 (11) 5 (12) -18 (10)
N2A 72 ( 2) 53 (16) 89 ( 2) 3 (14) 23 (16) -3 (13)
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C3A 67 ( 2) 75 ( 2) 65 ( 2) 3 (17) -2 (18) -6 (17)
C4A 47 (18) 41 (15) 64 ( 2) -4 (15) -6 (15) 0 (13) C5A 44 (18) 39 (15) 76 ( 2) -1 (14) -1 (15) 0 (12)
C6A 64 ( 3) 99 ( 3) 162 ( 5) -44 ( 3) 30 ( 3) -10 ( 2)
C7A 73 ( 3) 90 ( 3) 223 ( 7) -49 ( 4) 26 ( 4) 2 ( 3)
C8A 110 ( 4) 79 ( 3) 99 ( 4) -28 ( 2) 34 ( 3) -18 ( 2) C4AA 49 ( 2) 53 (18) 62 ( 2) -4 (15) -6 (18) 4 (14)
O4A 60 (15) 56 (14) 136 ( 2) 1 (14) -35 (15) 7 (11)
C41A 42 (16) 49 (16) 48 (17) 0 (13) -1 (14) 0 (12)
C42A 45 (17) 53 (19) 70 ( 2) 5 (15) -11 (15) -3 (13) C43A 57 ( 2) 52 (19) 93 ( 3) 13 (17) -12 (18) -3 (14)
C44A 56 ( 2) 56 (18) 96 ( 3) 13 ( 2) -10 ( 2) -12 (17)
C45A 44 (18) 71 ( 2) 91 ( 3) 0 (18) -5 (18) -18 (16)
C46A 41 (19) 64 ( 2) 70 ( 2) 0 (15) -3 (16) -1 (14) C51A 47 (18) 35 (15) 68 ( 2) -7 (14) -2 (15) -4 (12)
C52A 52 (19) 44 (17) 76 ( 2) -12 (16) 3 (18) -2 (13)
C53A 78 ( 3) 65 ( 2) 85 ( 3) -20 ( 2) 9 ( 2) -3 ( 2)
C54A 103 ( 3) 80 ( 3) 58 ( 2) -13 ( 2) 2 ( 2) -22 ( 2)
C55A 78 ( 3) 76 ( 3) 69 ( 3) -3 (18) -15 ( 2) 0 (19)
C56A 55 ( 2) 58 (18) 76 ( 2) -8 (16) -4 (18) 2 (15)
O1B 57 (14) 48 (11) 63 (14) 2 (10) 0 (11) 12 ( 9)
Molecule B: N2B 55 (17) 48 (14) 60 (17) -6 (11) 7 (13) 2 (12)
C3B 64 ( 2) 53 (17) 53 ( 2) -1 (14) 2 (15) 8 (15)
C4B 46 (18) 36 (13) 51 (18) -2 (14) -5 (14) 0 (11)
C5B 45 (18) 38 (16) 58 ( 2) -1 (13) -1 (14) 0 (12) C4AB 44 (18) 44 (16) 56 ( 2) 1 (14) -5 (17) -3 (13)
O4B 51 (13) 54 (13) 120 ( 2) 1 (13) -20 (13) -11 (11)
C41B 38 (15) 50 (17) 52 (17) 4 (13) -2 (14) 2 (12)
C42B 41 (18) 62 ( 2) 82 ( 3) 5 (17) -6 (17) 0 (14) C43B 49 ( 2) 64 ( 2) 101 ( 3) 12 (19) -6 (19) 15 (17)
C44B 62 ( 2) 49 (18) 119 ( 3) 7 ( 2) -1 ( 2) 13 (18)
C45B 56 ( 2) 44 (18) 143 ( 4) 1 ( 2) -16 ( 2) 3 (15)
C46B 42 (18) 47 (18) 95 ( 3) -1 (16) -14 (18) 7 (13) C51B 47 (17) 38 (14) 55 (18) 6 (13) -2 (14) 5 (12)
C52B 51 (18) 48 (17) 64 ( 2) 13 (14) -5 (16) -1 (13)
C53B 58 ( 2) 70 ( 2) 72 ( 2) 18 (18) 7 (18) -2 (17)
C54B 88 ( 3) 78 ( 2) 56 ( 2) 10 (18) 8 ( 2) 3 ( 2)
C55B 77 ( 3) 73 ( 2) 60 ( 2) 2 (16) -13 (19) -5 (19)
C56B 52 (19) 57 (18) 63 ( 2) 0 (14) -3 (16) -5 (14)
C6B 58 ( 2) 86 ( 3) 92 ( 3) -3 ( 2) 14 ( 2) 2 (19)
C7B 85 ( 3) 89 ( 3) 118 ( 4) -19 ( 3) 24 ( 3) -31 ( 3) C8B 118 ( 4) 61 ( 2) 83 ( 3) 5 (18) 46 ( 3) 2 ( 2)
Table-8:
Distances (Å) for non-hydrogen atoms (e.s.d.'s given in parentheses)
Molecule A:
O1A - C5A 1.440(4) O1A - N2A 1.473(4) N2A - C6A
N2A - C3A 1.508(4) C3A - C8A 1.511(6) C3A - C4A 5)
C4A - C4AA 1.512(4) C4A - C5A 1.523(4) C5A - C51A 7A 1.390(6) C7A - C8A 1.499(6) C4AA - O4A 1.226(4) C4AA - C41A 1.485(4) C41A - C46A1.389(4) C41A - C42A 1.392(4)
C42A - C43A 1.382(4) C43A - C44A1.367(5) C44A - C45A 1.372(5)
C45A - C46A 1.376(5) C51A - C52A1.378(4) C51A - C56A 1.393(4) C52A - C53A 1.368(5) C53A - C54A1.380(6) C54A - C55A 1.376(6)
C55A - C56A 1.378(5)
Molecule B:
O1B - C5B 1.428(3) O1B - N2B 1.478(3) N2B - C6B 1.463(4) N2B - C3B 1.495(4) C3B - C8B (5)
C3B - C4B 1.533(4) C4B - C4AB 1.522(4) C4B - C5B )
C5B - C51B 1.501(4) C4AB - O4B 1.207(3) C4AB - C41B
C41B - C46B 1.381(4) C41B - C42B 1.395(4) C42B - C43B - C44B 1.360(5) C44B - C45B 1.362(5) C45B - C46B 1.386(4) C51B - C56B 1.385(4) C51B - C52B 1.389(4) C52B - C53B
C53B - C54B 1.374(5) C54B - C55B 1.385(5) C55B - C56B 5)
C6B - C7B 1.466(6) C7B - C8B 1.501(6)
Table-5: Bond angles (degr.) for non-hydrogen atoms
-------- with e.s.d.'s given in parentheses
Molecule A:
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C5A - O1A - N2A 104.8(2) C6A - N2A - O1A 106.3(3)
C6A - N2A - C3A 104.7(3) O1A - N2A - C3A 106.0(2) N2A - C3A - C8A 106.1(3) N2A - C3A - C4A 104.4(3)
C8A - C3A - C4A 114.9(3) C4AA - C4A - C5A 112.8(2)
C4AA - C4A - C3A 111.8(3) C5A - C4A - C3A 102.2(2)
O1A - C5A - C51A 109.1(3) O1A - C5A - C4A 102.4(2) C51A - C5A - C4A 117.1(2) C7A - C6A - N2A 110.7(4)
C6A - C7A - C8A 105.3(4) C7A - C8A - C3A 104.1(3)
O4A - C4AA - C41A 119.6(3) O4A - C4AA - C4A 118.8(3)
C41A - C4AA - C4A 121.6(3) C46A - C41A - C42A 118.1(3) C46A - C41A - C4AA 119.2(3) C42A - C41A - C4AA 122.7(3)
C43A - C42A - C41A 120.3(3) C44A - C43A - C42A 120.6(3)
C43A - C44A - C45A 119.8(3) C44A - C45A - C46A 120.2(3)
C45A - C46A - C41A 120.9(3) C52A - C51A - C56A 119.4(3) C52A - C51A - C5A 120.1(3) C56A - C51A - C5A 120.5(3)
C53A - C52A - C51A 120.6(3) C52A - C53A - C54A 120.1(4)
C55A - C54A - C53A 119.8(4) C54A - C55A - C56A 120.4(4)
C55A - C56A - C51A 119.6(3)
Molecule B:
C5B - O1B - N2B 104.0(2)
C6B - N2B - O1B 105.6(3) C6B - N2B - C3B 106.4(3) O1B - N2B - C3B 104.9(2) N2B - C3B - C8B 105.7(3)
N2B - C3B - C4B 105.8(2) C8B - C3B - C4B 116.5(3)
C4AB - C4B - C5B 112.9(2) C4AB - C4B - C3B 111.7(3)
C5B - C4B - C3B 101.6(2) O1B - C5B - C51B 109.6(2) O1B - C5B - C4B 102.5(2) C51B - C5B - C4B 116.1(2)
O4B - C4AB - C41B 120.5(3) O4B - C4AB - C4B 119.2(3)
C41B - C4AB - C4B 120.3(2) C46B - C41B - C42B 117.8(3)
C46B - C41B - C4AB 123.5(2) C42B - C41B - C4AB 118.6(3) C43B - C42B - C41B 120.8(3) C44B - C43B - C42B 120.4(3)
C43B - C44B - C45B 119.6(3) C44B - C45B - C46B 120.9(3)
C41B - C46B - C45B 120.4(3) C56B - C51B - C52B 118.4(3)
C56B - C51B - C5B 121.5(3) C52B - C51B - C5B 120.1(3) C53B - C52B - C51B 121.3(3) C52B - C53B - C54B 119.9(3)
C53B - C54B - C55B 120.2(3) C56B - C55B - C54B 119.6(3)
C55B - C56B - C51B 120.7(3) C7B - C6B - N2B 107.2(3)
C6B - C7B - C8B 103.2(3) C7B - C8B - C3B 103.1(3)
--------------------------0---------------------------------------0---------------------------------0-----------------------------------------
Theoretical calculation results
Molecule = N1. Final optimized geometry with frequency analysis. -------------------------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
------------------------------------------------------
E(RB+HF-LYP) = -286.540959367 A.U. ------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z
--------------------------------------------------------------------------
1 8 0 -2.097683 0.019562 -0.044123
2 7 0 -0.837127 0.090505 -0.007145 3 6 0 -0.060262 1.146455 -0.028700
4 1 0 -0.513713 2.127396 -0.080014
5 6 0 1.391813 0.806312 0.088280 6 1 0 2.012387 1.341674 -0.640441
7 1 0 1.787157 1.065803 1.082492
8 6 0 1.406219 -0.730996 -0.150146
9 1 0 1.672310 -0.941847 -1.190464 10 1 0 2.129292 -1.245936 0.487794
11 6 0 -0.035796 -1.171813 0.123080
12 1 0 -0.450219 -1.888644 -0.587937
13 1 0 -0.207705 -1.548221 1.136483 -------------------------------------------------------------------------------------
Page 210
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Rotational constants (GHZ): 7.4250128 3.4271899 2.4711136
Zero-point correction= 0.110805 (Hartree/Particle)
Thermal correction to Energy= 0.116065
Thermal correction to Enthalpy= 0.117009 Thermal correction to Gibbs Free Energy= 0.082092
Sum of electronic and zero-point Energies= -286.430154
Sum of electronic and thermal Energies= -286.424895
Sum of electronic and thermal Enthalpies= -286.423951
Sum of electronic and thermal Free Energies= -286.458867
-----------------------------------------------------------------------------------
Molecule = E1. Final optimized geometry with frequency analysis.
----------------------------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity ----------------------------------------------------
E(RB+HF-LYP) = -537.529586647 A.U.
----------------------------------------------------
Standard orientation: ---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
--------------------------------------------------------------------- 1 6 0 -0.164019 -0.257179 -0.000187
2 1 0 -0.540021 -1.278077 0.000540
3 6 0 -1.071801 0.737206 -0.000372
4 1 0 -0.790824 1.785621 -0.000780 5 6 0 1.295084 -0.127901 -0.000059
6 6 0 2.073297 -1.299729 -0.000230
7 6 0 1.961878 1.112750 0.000231
8 6 0 3.465449 -1.240446 -0.000138 9 1 0 1.573318 -2.265444 -0.000414
10 6 0 3.351247 1.172613 0.000296
11 1 0 1.389320 2.035381 0.000383
12 6 0 4.109707 -0.002838 0.000116 13 1 0 4.045857 -2.159004 -0.000265
14 1 0 3.847701 2.139225 0.000479
15 1 0 5.195033 0.048782 0.000156
16 6 0 -2.532093 0.532179 -0.000131 17 8 0 -3.340511 1.441918 -0.000173
18 8 0 -2.892018 -0.777287 0.000159
19 6 0 -4.305340 -1.018435 0.000303
20 1 0 -4.417401 -2.103422 -0.001311 21 1 0 -4.771288 -0.586128 0.890216
22 1 0 -4.771916 -0.583300 -0.887877
-------------------------------------------------------------------------------------
Rotational constants (GHZ): 3.0364831 0.3725689 0.3325473 ---------------------------------------------------------------------------------------
Zero-point correction= 0.177540 (Hartree/Particle)
Thermal correction to Energy= 0.188678 Thermal correction to Enthalpy= 0.189622
Thermal correction to Gibbs Free Energy= 0.138997
Sum of electronic and zero-point Energies= -537.352046
Sum of electronic and thermal Energies= -537.340909 Sum of electronic and thermal Enthalpies= -537.339965
Sum of electronic and thermal Free Energies= -537.390589
----------------------------------------------------------------------------------
Transition State = 1TRN. Final optimized geometry with frequency analysis.
------------------------------------------------------------------------------------
# opt=qst3 freq b3lyp/6-31g(d) geom=connectivity
------------------------------------------------ E(RB+HF-LYP) = -824.04991718 A.U.
-----------------------------------------------
Transition State = 1TRX. Final optimized geometry with frequency analysis.
-------------------------------------------------------------------------------------
# opt=qst3 freq b3lyp/6-31g(d) geom=connectivity
Page 211
Annexure 2
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---------------------------------------------------------------
E(RB+HF-LYP) = -824.04696094 A.U.
Transition State = 1TSN. Final optimized geometry with frequency analysis. ------------------------------------------------------------------------------------
# opt=qst3 freq b3lyp/6-31g(d) geom=connectivity
------------------------------------------------------------
E(RB+HF-LYP) = -824.049917096 A.U. -------------------------------------------------
Transition State = 1TSX. Final optimized geometry with frequency analysis.
-----------------------------------------------------------------------------------
# opt=qst3 freq b3lyp/6-31g(d) geom=connectivity --------------------------------------------------------------
E(RB+HF-LYP) = -824.047345240 A.U.
-------------------------------------------------------
Zero-point correction= 0.290296 (Hartree/Particle)
Thermal correction to Energy= 0.306851
Thermal correction to Enthalpy= 0.307795
Thermal correction to Gibbs Free Energy= 0.244312
Sum of electronic and zero-point Energies= -823.757049 Sum of electronic and thermal Energies= -823.740494
Sum of electronic and thermal Enthalpies= -823.739550
Sum of electronic and thermal Free Energies= -823.803033
----------------------------------------------------------------------------------
Molecule = E2. Final optimized geometry with frequency analysis -------------------------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
-------------------------------------------------
E(RB+HF-LYP) = -654.034372622 A.U. -----------------------------------------------------
Standard orientation:
--------------------------------------------------------------------- Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.796394 0.165916 -0.117002 2 1 0 0.215090 -0.686094 -0.464325
3 6 0 0.137133 1.296318 0.210419
4 1 0 0.673895 2.197295 0.497801
5 6 0 2.245618 -0.054522 -0.090369 6 6 0 2.745169 -1.297519 -0.520172
7 6 0 3.167248 0.915232 0.350032
8 6 0 4.112383 -1.566126 -0.514103
9 1 0 2.047182 -2.057673 -0.863460 10 6 0 4.531907 0.647514 0.356782
11 1 0 2.813075 1.883697 0.689913
12 6 0 5.011419 -0.593584 -0.075115
13 1 0 4.474839 -2.533214 -0.851743 14 1 0 5.227122 1.408830 0.700056
15 1 0 6.078473 -0.798248 -0.068452
16 6 0 -1.319250 1.526578 0.057343
17 8 0 -1.721767 2.677957 -0.092338
18 6 0 -2.298138 0.387092 0.062528
19 6 0 -3.488916 0.546393 -0.663876
20 6 0 -2.110341 -0.782025 0.815532 21 6 0 -4.453980 -0.456253 -0.667730
22 1 0 -3.636600 1.468006 -1.217661
23 6 0 -3.086967 -1.779108 0.825344
24 1 0 -1.216115 -0.898349 1.419341 25 6 0 -4.254369 -1.622893 0.076945
26 1 0 -5.365989 -0.328325 -1.244628
27 1 0 -2.937655 -2.674601 1.422635
28 1 0 -5.011054 -2.403054 0.079882 ---------------------------------------------------------------------------------------
Rotational constants (GHZ): 1.2553419 0.2346604 0.2053201
----------------------------------------------------------------------------------------
Page 212
Annexure 2
64
Zero-point correction= 0.225546 (Hartree/Particle)
Thermal correction to Energy= 0.238563 Thermal correction to Enthalpy= 0.239507
Thermal correction to Gibbs Free Energy= 0.183949
Sum of electronic and zero-point Energies= -653.808826
Sum of electronic and thermal Energies= -653.795810 Sum of electronic and thermal Enthalpies= -653.794865
Sum of electronic and thermal Free Energies= -653.850424
---------------------------------------------------------------------------------------
Transition State = 2TRN. Final optimized geometry with frequency analysis
-------------------------------------------------------------------------------------- # opt=qst3 freq b3lyp/6-31g(d) geom=connectivity
------------------------------------------------------------
E(RB+HF-LYP) = -940.550927935 A.U.
----------------------------------------------------
Zero-point correction= 0.338351 (Hartree/Particle)
Thermal correction to Energy= 0.356606
Thermal correction to Enthalpy= 0.357550 Thermal correction to Gibbs Free Energy= 0.290201
Sum of electronic and zero-point Energies= -940.212577
Sum of electronic and thermal Energies= -940.194322
Sum of electronic and thermal Enthalpies= -940.193378 Sum of electronic and thermal Free Energies= -940.260727
--------------------------------------------------------------------------------
Transition State = 2TRX. Final optimized geometry with frequency analysis
------------------------------------------------------------------------------------
# opt=qst3 freq b3lyp/6-31g(d) geom=connectivity -----------------------------------------------------------
E(RB+HF-LYP) = -940.553142446 A.U.
--------------------------------------------------------------------------
Zero-point correction= 0.338719 (Hartree/Particle) Thermal correction to Energy= 0.357034
Thermal correction to Enthalpy= 0.357978
Thermal correction to Gibbs Free Energy= 0.290737
Sum of electronic and zero-point Energies= -940.214424 Sum of electronic and thermal Energies= -940.196109
Sum of electronic and thermal Enthalpies= -940.195165
Sum of electronic and thermal Free Energies= -940.262405
------------------------------------------------------------------------------------------------------------
Suplimentary of IRC
The TS of different facial attack and their corresponding IRC of the reaction of scheme 1
The TS and IRC of 1TRN
Page 213
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The TS and IRC of 1TRX
The TS and IRC of 1TSN
The TS and IRC of 1TSX
The TS of different facial attack and their corresponding IRC of the reaction of scheme 2
The TS and IRC of 2TRN
The TS and IRC of 2TRX
Page 215
Annexure 3
66
1trn nbo wiberg analysis:
Wiberg bond index matrix in the NAO basis:
Atom 1 2 3 4 5 6 7 8 9
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0000 0.9147 0.9107 0.9270 1.0337 0.0032 0.0122 0.0084 0.0119
2. H 0.9147 0.0000 0.0006 0.0007 0.0023 0.0096 0.0017 0.0048 0.0003
3. H 0.9107 0.0006 0.0000 0.0006 0.0024 0.0001 0.0063 0.0061 0.0002
4. H 0.9270 0.0007 0.0006 0.0000 0.0034 0.0006 0.0091 0.0011 0.0004
5. C 1.0337 0.0023 0.0024 0.0034 0.0000 0.9040 1.2890 0.2031 0.0126
6. H 0.0032 0.0096 0.0001 0.0006 0.9040 0.0000 0.0027 0.0166 0.0005
7. N 0.0122 0.0017 0.0063 0.0091 1.2890 0.0027 0.0000 1.2453 0.8954
8. O 0.0084 0.0048 0.0061 0.0011 0.2031 0.0166 1.2453 0.0000 0.0551
9. C 0.0119 0.0003 0.0002 0.0004 0.0126 0.0005 0.8954 0.0551 0.0000
10. H 0.0001 0.0000 0.0002 0.0002 0.0074 0.0000 0.0039 0.0032 0.8864
11. C 0.0006 0.0000 0.0000 0.0001 0.0068 0.0006 0.0096 0.0078 1.0052
12. H 0.0004 0.0000 0.0000 0.0001 0.0001 0.0001 0.0097 0.0023 0.0035
13. H 0.0000 0.0000 0.0000 0.0000 0.0002 0.0000 0.0012 0.0037 0.0018
14. H 0.0000 0.0000 0.0000 0.0000 0.0004 0.0000 0.0009 0.0003 0.0024
15. C 0.0003 0.0001 0.0000 0.0001 0.0025 0.0029 0.0075 0.0101 0.9985
16. C 0.0001 0.0002 0.0000 0.0000 0.0019 0.0002 0.0087 0.0023 0.0107
17. C 0.0001 0.0001 0.0001 0.0000 0.0020 0.0001 0.0051 0.0027 0.0104
18. C 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0005 0.0006 0.0071
19. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0001 0.0018
20. C 0.0000 0.0000 0.0000 0.0000 0.0003 0.0001 0.0008 0.0004 0.0078
21. H 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0006 0.0001 0.0020
22. C 0.0000 0.0001 0.0000 0.0000 0.0008 0.0000 0.0028 0.0014 0.0011
23. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0001 0.0003
24. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0004
25. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0004
26. H 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0001 0.0000
27. C 0.0004 0.0000 0.0001 0.0000 0.0004 0.0000 0.0100 0.0233 0.0006
28. C 0.0002 0.0000 0.0002 0.0000 0.0059 0.0000 0.0011 0.0043 0.0006
29. C 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0002 0.0003 0.0006
30. C 0.0051 0.0002 0.0010 0.0002 0.0049 0.0004 0.1059 0.2594 0.0006
31. C 0.0004 0.0000 0.0001 0.0000 0.0003 0.0000 0.0105 0.0177 0.0002
32. C 0.0004 0.0000 0.0000 0.0000 0.0002 0.0000 0.0101 0.0170 0.0003
33. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
34. C 0.0040 0.0013 0.0135 0.0008 0.4222 0.0005 0.0204 0.0245 0.0006
35. H 0.0000 0.0001 0.0000 0.0000 0.0003 0.0000 0.0001 0.0004 0.0000
36. C 0.0000 0.0000 0.0000 0.0000 0.0006 0.0000 0.0001 0.0006 0.0003
37. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000
38. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
39. H 0.0002 0.0002 0.0002 0.0000 0.0006 0.0000 0.0015 0.0024 0.0000
40. H 0.0011 0.0000 0.0003 0.0004 0.0010 0.0000 0.0038 0.0071 0.0002
41. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Atom 10 11 12 13 14 15 16 17 18
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0001 0.0006 0.0004 0.0000 0.0000 0.0003 0.0001 0.0001 0.0000
2. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0002 0.0001 0.0000
3. H 0.0002 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000
4. H 0.0002 0.0001 0.0001 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000
5. C 0.0074 0.0068 0.0001 0.0002 0.0004 0.0025 0.0019 0.0020 0.0001
6. H 0.0000 0.0006 0.0001 0.0000 0.0000 0.0029 0.0002 0.0001 0.0000
7. N 0.0039 0.0096 0.0097 0.0012 0.0009 0.0075 0.0087 0.0051 0.0005
8. O 0.0032 0.0078 0.0023 0.0037 0.0003 0.0101 0.0023 0.0027 0.0006
9. C 0.8864 1.0052 0.0035 0.0018 0.0024 0.9985 0.0107 0.0104 0.0071
10. H 0.0000 0.0037 0.0005 0.0010 0.0111 0.0021 0.0015 0.0066 0.0003
11. C 0.0037 0.0000 0.9256 0.9098 0.9288 0.0106 0.0100 0.0070 0.0004
12. H 0.0005 0.9256 0.0000 0.0007 0.0006 0.0006 0.0001 0.0002 0.0000
13. H 0.0010 0.9098 0.0007 0.0000 0.0006 0.0083 0.0011 0.0012 0.0002
14. H 0.0111 0.9288 0.0006 0.0006 0.0000 0.0009 0.0001 0.0005 0.0000
15. C 0.0021 0.0106 0.0006 0.0083 0.0009 0.0000 1.4125 1.3882 0.0120
16. C 0.0015 0.0100 0.0001 0.0011 0.0001 1.4125 0.0000 0.0117 1.4297
17. C 0.0066 0.0070 0.0002 0.0012 0.0005 1.3882 0.0117 0.0000 0.1119
18. C 0.0003 0.0004 0.0000 0.0002 0.0000 0.0120 1.4297 0.1119 0.0000
19. H 0.0008 0.0001 0.0000 0.0001 0.0000 0.0036 0.9148 0.0092 0.0036
20. C 0.0001 0.0005 0.0000 0.0001 0.0001 0.0120 0.1084 1.4507 0.0110
21. H 0.0004 0.0001 0.0000 0.0001 0.0004 0.0035 0.0087 0.9114 0.0003
22. C 0.0002 0.0040 0.0000 0.0009 0.0000 0.1084 0.0110 0.0110 1.4426
23. H 0.0000 0.0001 0.0000 0.0000 0.0000 0.0079 0.0032 0.0002 0.9157
24. H 0.0003 0.0000 0.0000 0.0000 0.0000 0.0080 0.0002 0.0033 0.0083
25. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0085 0.0083 0.0034
26. H 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
27. C 0.0004 0.0001 0.0000 0.0000 0.0000 0.0001 0.0001 0.0001 0.0000
28. C 0.0007 0.0001 0.0000 0.0002 0.0000 0.0001 0.0000 0.0000 0.0000
29. C 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
30. C 0.0063 0.0009 0.0000 0.0000 0.0002 0.0005 0.0003 0.0004 0.0002
31. C 0.0011 0.0002 0.0000 0.0003 0.0000 0.0001 0.0000 0.0001 0.0000
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Annexure 3
67
32. C 0.0004 0.0001 0.0000 0.0000 0.0000 0.0001 0.0000 0.0001 0.0000
33. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
34. C 0.0016 0.0002 0.0002 0.0000 0.0000 0.0002 0.0001 0.0005 0.0000
35. H 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
36. C 0.0002 0.0001 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
37. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
38. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
39. H 0.0003 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000
40. H 0.0002 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
41. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Atom 19 20 21 22 23 24 25 26 27
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0004
2. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
3. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001
4. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
5. C 0.0000 0.0003 0.0001 0.0008 0.0000 0.0000 0.0000 0.0001 0.0004
6. H 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
7. N 0.0002 0.0008 0.0006 0.0028 0.0001 0.0000 0.0000 0.0000 0.0100
8. O 0.0001 0.0004 0.0001 0.0014 0.0001 0.0000 0.0000 0.0001 0.0233
9. C 0.0018 0.0078 0.0020 0.0011 0.0003 0.0004 0.0004 0.0000 0.0006
10. H 0.0008 0.0001 0.0004 0.0002 0.0000 0.0003 0.0000 0.0001 0.0004
11. C 0.0001 0.0005 0.0001 0.0040 0.0001 0.0000 0.0000 0.0000 0.0001
12. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
13. H 0.0001 0.0001 0.0001 0.0009 0.0000 0.0000 0.0000 0.0000 0.0000
14. H 0.0000 0.0001 0.0004 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
15. C 0.0036 0.0120 0.0035 0.1084 0.0079 0.0080 0.0002 0.0000 0.0001
16. C 0.9148 0.1084 0.0087 0.0110 0.0032 0.0002 0.0085 0.0000 0.0001
17. C 0.0092 1.4507 0.9114 0.0110 0.0002 0.0033 0.0083 0.0000 0.0001
18. C 0.0036 0.0110 0.0003 1.4426 0.9157 0.0083 0.0034 0.0000 0.0000
19. H 0.0000 0.0003 0.0004 0.0084 0.0021 0.0004 0.0004 0.0000 0.0000
20. C 0.0003 0.0000 0.0036 1.4239 0.0085 0.9155 0.0033 0.0000 0.0001
21. H 0.0004 0.0036 0.0000 0.0084 0.0004 0.0021 0.0004 0.0000 0.0000
22. C 0.0084 1.4239 0.0084 0.0000 0.0034 0.0033 0.9159 0.0000 0.0000
23. H 0.0021 0.0085 0.0004 0.0034 0.0000 0.0004 0.0020 0.0000 0.0000
24. H 0.0004 0.9155 0.0021 0.0033 0.0004 0.0000 0.0020 0.0000 0.0000
25. H 0.0004 0.0033 0.0004 0.9159 0.0020 0.0020 0.0000 0.0000 0.0000
26. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.9177
27. C 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.9177 0.0000
28. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0035 1.3559
29. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0036 1.4564
30. C 0.0000 0.0003 0.0002 0.0001 0.0000 0.0000 0.0000 0.0018 0.0103
31. C 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0089 0.0107
32. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0085 0.0116
33. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0021 0.0033
34. C 0.0000 0.0000 0.0002 0.0001 0.0000 0.0000 0.0000 0.0006 0.0191
35. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0079
36. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0003 0.1023
37. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0005 0.0088
38. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0004 0.0083
39. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0017 0.0004
40. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0003
41. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0004 0.0002
Atom 28 29 30 31 32 33 34 35 36
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0002 0.0000 0.0051 0.0004 0.0004 0.0000 0.0040 0.0000 0.0000
2. H 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000 0.0013 0.0001 0.0000
3. H 0.0002 0.0000 0.0010 0.0001 0.0000 0.0000 0.0135 0.0000 0.0000
4. H 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000 0.0008 0.0000 0.0000
5. C 0.0059 0.0001 0.0049 0.0003 0.0002 0.0000 0.4222 0.0003 0.0006
6. H 0.0000 0.0000 0.0004 0.0000 0.0000 0.0000 0.0005 0.0000 0.0000
7. N 0.0011 0.0002 0.1059 0.0105 0.0101 0.0000 0.0204 0.0001 0.0001
8. O 0.0043 0.0003 0.2594 0.0177 0.0170 0.0000 0.0245 0.0004 0.0006
9. C 0.0006 0.0006 0.0006 0.0002 0.0003 0.0000 0.0006 0.0000 0.0003
10. H 0.0007 0.0001 0.0063 0.0011 0.0004 0.0000 0.0016 0.0001 0.0002
11. C 0.0001 0.0001 0.0009 0.0002 0.0001 0.0000 0.0002 0.0000 0.0001
12. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0000 0.0000
13. H 0.0002 0.0000 0.0000 0.0003 0.0000 0.0000 0.0000 0.0000 0.0001
14. H 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
15. C 0.0001 0.0000 0.0005 0.0001 0.0001 0.0000 0.0002 0.0000 0.0000
16. C 0.0000 0.0000 0.0003 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000
17. C 0.0000 0.0000 0.0004 0.0001 0.0001 0.0000 0.0005 0.0000 0.0000
18. C 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
19. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
20. C 0.0000 0.0000 0.0003 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
21. H 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000 0.0002 0.0000 0.0000
22. C 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000
23. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
24. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
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25. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
26. H 0.0035 0.0036 0.0018 0.0089 0.0085 0.0021 0.0006 0.0002 0.0003
27. C 1.3559 1.4564 0.0103 0.0107 0.0116 0.0033 0.0191 0.0079 0.1023
28. C 0.0000 0.0117 1.1082 1.3546 0.0974 0.0082 0.0106 0.0023 0.0111
29. C 0.0117 0.0000 0.0105 0.1024 1.4225 0.9177 0.0005 0.0001 0.0110
30. C 1.1082 0.0105 0.0000 0.0103 0.0007 0.0003 1.4998 0.9081 0.0088
31. C 1.3546 0.1024 0.0103 0.0000 0.0113 0.0003 0.0277 0.0017 1.4611
32. C 0.0974 1.4225 0.0007 0.0113 0.0000 0.0034 0.0152 0.0007 1.4194
33. H 0.0082 0.9177 0.0003 0.0003 0.0034 0.0000 0.0001 0.0003 0.0085
34. C 0.0106 0.0005 1.4998 0.0277 0.0152 0.0001 0.0000 0.0048 0.0002
35. H 0.0023 0.0001 0.9081 0.0017 0.0007 0.0003 0.0048 0.0000 0.0002
36. C 0.0111 0.0110 0.0088 1.4611 1.4194 0.0085 0.0002 0.0002 0.0000
37. H 0.0033 0.0003 0.0016 0.9151 0.0085 0.0004 0.0003 0.0006 0.0035
38. H 0.0002 0.0033 0.0003 0.0084 0.9181 0.0020 0.0000 0.0000 0.0034
39. H 0.0017 0.0001 0.0049 0.0003 0.0001 0.0000 0.9230 0.0125 0.0000
40. H 0.0085 0.0001 0.0046 0.0001 0.0001 0.0000 0.9121 0.0022 0.0003
41. H 0.0084 0.0084 0.0002 0.0034 0.0033 0.0004 0.0002 0.0000 0.9168
Atom 37 38 39 40 41
---- ------ ------ ------ ------ ------
1. C 0.0000 0.0000 0.0002 0.0011 0.0000
2. H 0.0000 0.0000 0.0002 0.0000 0.0000
3. H 0.0000 0.0000 0.0002 0.0003 0.0000
4. H 0.0000 0.0000 0.0000 0.0004 0.0000
5. C 0.0000 0.0000 0.0006 0.0010 0.0000
6. H 0.0000 0.0000 0.0000 0.0000 0.0000
7. N 0.0000 0.0000 0.0015 0.0038 0.0000
8. O 0.0001 0.0000 0.0024 0.0071 0.0000
9. C 0.0000 0.0000 0.0000 0.0002 0.0000
10. H 0.0000 0.0000 0.0003 0.0002 0.0000
11. C 0.0000 0.0000 0.0000 0.0000 0.0000
12. H 0.0000 0.0000 0.0000 0.0000 0.0000
13. H 0.0000 0.0000 0.0000 0.0000 0.0000
14. H 0.0000 0.0000 0.0000 0.0000 0.0000
15. C 0.0000 0.0000 0.0001 0.0000 0.0000
16. C 0.0000 0.0000 0.0000 0.0000 0.0000
17. C 0.0000 0.0000 0.0000 0.0000 0.0000
18. C 0.0000 0.0000 0.0000 0.0000 0.0000
19. H 0.0000 0.0000 0.0000 0.0000 0.0000
20. C 0.0000 0.0000 0.0000 0.0000 0.0000
21. H 0.0000 0.0000 0.0000 0.0000 0.0000
22. C 0.0000 0.0000 0.0000 0.0000 0.0000
23. H 0.0000 0.0000 0.0000 0.0000 0.0000
24. H 0.0000 0.0000 0.0000 0.0000 0.0000
25. H 0.0000 0.0000 0.0000 0.0000 0.0000
26. H 0.0005 0.0004 0.0017 0.0000 0.0004
27. C 0.0088 0.0083 0.0004 0.0003 0.0002
28. C 0.0033 0.0002 0.0017 0.0085 0.0084
29. C 0.0003 0.0033 0.0001 0.0001 0.0084
30. C 0.0016 0.0003 0.0049 0.0046 0.0002
31. C 0.9151 0.0084 0.0003 0.0001 0.0034
32. C 0.0085 0.9181 0.0001 0.0001 0.0033
33. H 0.0004 0.0020 0.0000 0.0000 0.0004
34. C 0.0003 0.0000 0.9230 0.9121 0.0002
35. H 0.0006 0.0000 0.0125 0.0022 0.0000
36. C 0.0035 0.0034 0.0000 0.0003 0.9168
37. H 0.0000 0.0004 0.0000 0.0000 0.0022
38. H 0.0004 0.0000 0.0000 0.0000 0.0020
39. H 0.0000 0.0000 0.0000 0.0003 0.0000
40. H 0.0000 0.0000 0.0003 0.0000 0.0000
41. H 0.0022 0.0020 0.0000 0.0000 0.0000
Wiberg bond index, Totals by atom:
Atom 1
---- ------
1. C 3.8354
2. H 0.9370
3. H 0.9427
4. H 0.9449
5. C 3.9098
6. H 0.9424
7. N 3.6772
8. O 1.9328
9. C 3.9203
10. H 0.9414
11. C 3.8335
12. H 0.9447
13. H 0.9318
14. H 0.9475
15. C 4.0022
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16. C 3.9464
17. C 3.9434
18. C 3.9481
19. H 0.9464
20. C 3.9481
21. H 0.9434
22. C 3.9478
23. H 0.9446
24. H 0.9445
25. H 0.9448
26. H 0.9506
27. C 3.9492
28. C 3.9992
29. C 3.9501
30. C 3.9576
31. C 3.9475
32. C 3.9496
33. H 0.9470
34. C 3.9050
35. H 0.9427
36. C 3.9490
37. H 0.9459
38. H 0.9468
39. H 0.9506
40. H 0.9432
41. H 0.9461
1trx nbo wiberg analysis:
Wiberg bond index matrix in the NAO basis:
Atom 1 2 3 4 5 6 7 8 9
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0000 0.9082 0.9101 0.9279 1.0358 0.0034 0.0126 0.0082 0.0120
2. H 0.9082 0.0000 0.0007 0.0007 0.0023 0.0094 0.0015 0.0042 0.0003
3. H 0.9101 0.0007 0.0000 0.0006 0.0025 0.0001 0.0067 0.0069 0.0002
4. H 0.9279 0.0007 0.0006 0.0000 0.0034 0.0006 0.0090 0.0012 0.0004
5. C 1.0358 0.0023 0.0025 0.0034 0.0000 0.9031 1.2829 0.2036 0.0124
6. H 0.0034 0.0094 0.0001 0.0006 0.9031 0.0000 0.0026 0.0170 0.0005
7. N 0.0126 0.0015 0.0067 0.0090 1.2829 0.0026 0.0000 1.2391 0.9015
8. O 0.0082 0.0042 0.0069 0.0012 0.2036 0.0170 1.2391 0.0000 0.0570
9. C 0.0120 0.0003 0.0002 0.0004 0.0124 0.0005 0.9015 0.0570 0.0000
10. H 0.0002 0.0000 0.0003 0.0002 0.0095 0.0000 0.0052 0.0021 0.8873
11. C 0.0006 0.0000 0.0001 0.0001 0.0075 0.0005 0.0099 0.0077 1.0045
12. H 0.0004 0.0000 0.0000 0.0001 0.0001 0.0001 0.0097 0.0018 0.0032
13. H 0.0000 0.0000 0.0000 0.0000 0.0004 0.0000 0.0014 0.0058 0.0018
14. H 0.0000 0.0000 0.0000 0.0000 0.0004 0.0000 0.0009 0.0003 0.0024
15. C 0.0004 0.0000 0.0000 0.0001 0.0021 0.0033 0.0070 0.0113 0.9992
16. C 0.0001 0.0002 0.0000 0.0000 0.0020 0.0001 0.0086 0.0026 0.0108
17. C 0.0001 0.0001 0.0000 0.0001 0.0024 0.0003 0.0054 0.0030 0.0103
18. C 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0005 0.0006 0.0071
19. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0001 0.0018
20. C 0.0000 0.0000 0.0000 0.0000 0.0003 0.0001 0.0007 0.0004 0.0078
21. H 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0005 0.0001 0.0019
22. C 0.0000 0.0001 0.0000 0.0000 0.0009 0.0000 0.0029 0.0016 0.0011
23. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0001 0.0003
24. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0003
25. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0004
26. H 0.0001 0.0000 0.0000 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000
27. C 0.0006 0.0013 0.0001 0.0000 0.0003 0.0000 0.0118 0.0212 0.0001
28. C 0.0004 0.0009 0.0001 0.0000 0.0049 0.0000 0.0007 0.0019 0.0001
29. C 0.0005 0.0000 0.0001 0.0000 0.0001 0.0000 0.0001 0.0002 0.0000
30. C 0.0047 0.0001 0.0013 0.0001 0.0055 0.0004 0.1055 0.2513 0.0009
31. C 0.0007 0.0001 0.0001 0.0000 0.0003 0.0000 0.0119 0.0171 0.0000
32. C 0.0005 0.0000 0.0000 0.0000 0.0001 0.0000 0.0111 0.0160 0.0000
33. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
34. C 0.0037 0.0016 0.0127 0.0008 0.4229 0.0006 0.0186 0.0233 0.0009
35. H 0.0001 0.0000 0.0001 0.0000 0.0006 0.0000 0.0006 0.0012 0.0001
36. C 0.0003 0.0001 0.0000 0.0000 0.0007 0.0000 0.0001 0.0002 0.0000
37. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0000
38. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
39. H 0.0007 0.0000 0.0002 0.0003 0.0010 0.0000 0.0023 0.0049 0.0002
40. H 0.0002 0.0001 0.0001 0.0000 0.0007 0.0000 0.0032 0.0038 0.0001
41. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Atom 10 11 12 13 14 15 16 17 18
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0002 0.0006 0.0004 0.0000 0.0000 0.0004 0.0001 0.0001 0.0000
2. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0001 0.0000
3. H 0.0003 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
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4. H 0.0002 0.0001 0.0001 0.0000 0.0000 0.0001 0.0000 0.0001 0.0000
5. C 0.0095 0.0075 0.0001 0.0004 0.0004 0.0021 0.0020 0.0024 0.0001
6. H 0.0000 0.0005 0.0001 0.0000 0.0000 0.0033 0.0001 0.0003 0.0000
7. N 0.0052 0.0099 0.0097 0.0014 0.0009 0.0070 0.0086 0.0054 0.0005
8. O 0.0021 0.0077 0.0018 0.0058 0.0003 0.0113 0.0026 0.0030 0.0006
9. C 0.8873 1.0045 0.0032 0.0018 0.0024 0.9992 0.0108 0.0103 0.0071
10. H 0.0000 0.0035 0.0005 0.0008 0.0114 0.0022 0.0015 0.0066 0.0003
11. C 0.0035 0.0000 0.9266 0.9110 0.9283 0.0104 0.0100 0.0068 0.0004
12. H 0.0005 0.9266 0.0000 0.0007 0.0006 0.0005 0.0001 0.0002 0.0000
13. H 0.0008 0.9110 0.0007 0.0000 0.0006 0.0084 0.0011 0.0012 0.0002
14. H 0.0114 0.9283 0.0006 0.0006 0.0000 0.0009 0.0002 0.0005 0.0000
15. C 0.0022 0.0104 0.0005 0.0084 0.0009 0.0000 1.4123 1.3875 0.0120
16. C 0.0015 0.0100 0.0001 0.0011 0.0002 1.4123 0.0000 0.0118 1.4298
17. C 0.0066 0.0068 0.0002 0.0012 0.0005 1.3875 0.0118 0.0000 0.1118
18. C 0.0003 0.0004 0.0000 0.0002 0.0000 0.0120 1.4298 0.1118 0.0000
19. H 0.0008 0.0001 0.0000 0.0001 0.0000 0.0036 0.9147 0.0092 0.0036
20. C 0.0001 0.0005 0.0000 0.0001 0.0001 0.0120 0.1084 1.4508 0.0110
21. H 0.0004 0.0002 0.0000 0.0001 0.0004 0.0035 0.0087 0.9115 0.0003
22. C 0.0001 0.0038 0.0000 0.0009 0.0000 0.1083 0.0110 0.0110 1.4426
23. H 0.0001 0.0001 0.0000 0.0000 0.0000 0.0079 0.0032 0.0002 0.9154
24. H 0.0003 0.0000 0.0000 0.0000 0.0000 0.0080 0.0002 0.0033 0.0083
25. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0085 0.0083 0.0034
26. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
27. C 0.0008 0.0002 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000
28. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
29. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
30. C 0.0079 0.0015 0.0000 0.0001 0.0002 0.0003 0.0002 0.0005 0.0001
31. C 0.0008 0.0002 0.0000 0.0000 0.0000 0.0001 0.0000 0.0001 0.0000
32. C 0.0008 0.0002 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000
33. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
34. C 0.0020 0.0002 0.0002 0.0000 0.0001 0.0002 0.0002 0.0004 0.0000
35. H 0.0002 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
36. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
37. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
38. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
39. H 0.0002 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
40. H 0.0008 0.0000 0.0000 0.0000 0.0000 0.0002 0.0001 0.0000 0.0000
41. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Atom 19 20 21 22 23 24 25 26 27
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0006
2. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0013
3. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001
4. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000
5. C 0.0000 0.0003 0.0001 0.0009 0.0000 0.0000 0.0000 0.0001 0.0003
6. H 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
7. N 0.0002 0.0007 0.0005 0.0029 0.0001 0.0000 0.0000 0.0000 0.0118
8. O 0.0001 0.0004 0.0001 0.0016 0.0001 0.0000 0.0000 0.0000 0.0212
9. C 0.0018 0.0078 0.0019 0.0011 0.0003 0.0003 0.0004 0.0000 0.0001
10. H 0.0008 0.0001 0.0004 0.0001 0.0001 0.0003 0.0000 0.0000 0.0008
11. C 0.0001 0.0005 0.0002 0.0038 0.0001 0.0000 0.0000 0.0000 0.0002
12. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
13. H 0.0001 0.0001 0.0001 0.0009 0.0000 0.0000 0.0000 0.0000 0.0000
14. H 0.0000 0.0001 0.0004 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
15. C 0.0036 0.0120 0.0035 0.1083 0.0079 0.0080 0.0002 0.0000 0.0001
16. C 0.9147 0.1084 0.0087 0.0110 0.0032 0.0002 0.0085 0.0000 0.0000
17. C 0.0092 1.4508 0.9115 0.0110 0.0002 0.0033 0.0083 0.0000 0.0000
18. C 0.0036 0.0110 0.0003 1.4426 0.9154 0.0083 0.0034 0.0000 0.0000
19. H 0.0000 0.0003 0.0004 0.0084 0.0021 0.0004 0.0004 0.0000 0.0000
20. C 0.0003 0.0000 0.0037 1.4239 0.0085 0.9152 0.0033 0.0000 0.0000
21. H 0.0004 0.0037 0.0000 0.0084 0.0004 0.0021 0.0004 0.0000 0.0000
22. C 0.0084 1.4239 0.0084 0.0000 0.0034 0.0033 0.9156 0.0000 0.0000
23. H 0.0021 0.0085 0.0004 0.0034 0.0000 0.0004 0.0020 0.0000 0.0000
24. H 0.0004 0.9152 0.0021 0.0033 0.0004 0.0000 0.0020 0.0000 0.0000
25. H 0.0004 0.0033 0.0004 0.9156 0.0020 0.0020 0.0000 0.0000 0.0000
26. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.9176
27. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.9176 0.0000
28. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0034 1.3536
29. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0036 1.4573
30. C 0.0000 0.0003 0.0002 0.0000 0.0000 0.0000 0.0000 0.0018 0.0103
31. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0089 0.0106
32. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0085 0.0114
33. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0021 0.0033
34. C 0.0000 0.0001 0.0001 0.0001 0.0000 0.0000 0.0000 0.0005 0.0200
35. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0076
36. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0003 0.1026
37. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0005 0.0089
38. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0004 0.0083
39. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0015 0.0004
40. H 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0003
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41. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0004 0.0002
Atom 28 29 30 31 32 33 34 35 36
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0004 0.0005 0.0047 0.0007 0.0005 0.0000 0.0037 0.0001 0.0003
2. H 0.0009 0.0000 0.0001 0.0001 0.0000 0.0000 0.0016 0.0000 0.0001
3. H 0.0001 0.0001 0.0013 0.0001 0.0000 0.0000 0.0127 0.0001 0.0000
4. H 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0008 0.0000 0.0000
5. C 0.0049 0.0001 0.0055 0.0003 0.0001 0.0000 0.4229 0.0006 0.0007
6. H 0.0000 0.0000 0.0004 0.0000 0.0000 0.0000 0.0006 0.0000 0.0000
7. N 0.0007 0.0001 0.1055 0.0119 0.0111 0.0000 0.0186 0.0006 0.0001
8. O 0.0019 0.0002 0.2513 0.0171 0.0160 0.0000 0.0233 0.0012 0.0002
9. C 0.0001 0.0000 0.0009 0.0000 0.0000 0.0000 0.0009 0.0001 0.0000
10. H 0.0000 0.0000 0.0079 0.0008 0.0008 0.0000 0.0020 0.0002 0.0000
11. C 0.0000 0.0000 0.0015 0.0002 0.0002 0.0000 0.0002 0.0000 0.0000
12. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0000 0.0000
13. H 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
14. H 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000
15. C 0.0000 0.0000 0.0003 0.0001 0.0001 0.0000 0.0002 0.0000 0.0000
16. C 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000 0.0002 0.0000 0.0000
17. C 0.0000 0.0000 0.0005 0.0001 0.0000 0.0000 0.0004 0.0000 0.0000
18. C 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
19. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
20. C 0.0000 0.0000 0.0003 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000
21. H 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000
22. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000
23. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
24. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
25. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
26. H 0.0034 0.0036 0.0018 0.0089 0.0085 0.0021 0.0005 0.0002 0.0003
27. C 1.3536 1.4573 0.0103 0.0106 0.0114 0.0033 0.0200 0.0076 0.1026
28. C 0.0000 0.0115 1.1146 1.3539 0.0968 0.0082 0.0110 0.0024 0.0111
29. C 0.0115 0.0000 0.0102 0.1026 1.4224 0.9176 0.0004 0.0001 0.0110
30. C 1.1146 0.0102 0.0000 0.0104 0.0007 0.0003 1.4991 0.9102 0.0090
31. C 1.3539 0.1026 0.0104 0.0000 0.0112 0.0003 0.0287 0.0015 1.4605
32. C 0.0968 1.4224 0.0007 0.0112 0.0000 0.0034 0.0157 0.0003 1.4202
33. H 0.0082 0.9176 0.0003 0.0003 0.0034 0.0000 0.0000 0.0004 0.0085
34. C 0.0110 0.0004 1.4991 0.0287 0.0157 0.0000 0.0000 0.0046 0.0002
35. H 0.0024 0.0001 0.9102 0.0015 0.0003 0.0004 0.0046 0.0000 0.0002
36. C 0.0111 0.0110 0.0090 1.4605 1.4202 0.0085 0.0002 0.0002 0.0000
37. H 0.0033 0.0003 0.0017 0.9159 0.0086 0.0004 0.0003 0.0006 0.0036
38. H 0.0002 0.0033 0.0003 0.0084 0.9182 0.0020 0.0000 0.0000 0.0033
39. H 0.0016 0.0001 0.0054 0.0004 0.0001 0.0000 0.9161 0.0115 0.0000
40. H 0.0091 0.0001 0.0040 0.0001 0.0001 0.0000 0.9195 0.0024 0.0003
41. H 0.0084 0.0084 0.0002 0.0034 0.0033 0.0004 0.0002 0.0000 0.9169
Atom 37 38 39 40 41
---- ------ ------ ------ ------ ------
1. C 0.0000 0.0000 0.0007 0.0002 0.0000
2. H 0.0000 0.0000 0.0000 0.0001 0.0000
3. H 0.0000 0.0000 0.0002 0.0001 0.0000
4. H 0.0000 0.0000 0.0003 0.0000 0.0000
5. C 0.0000 0.0000 0.0010 0.0007 0.0000
6. H 0.0000 0.0000 0.0000 0.0000 0.0000
7. N 0.0000 0.0000 0.0023 0.0032 0.0000
8. O 0.0002 0.0000 0.0049 0.0038 0.0000
9. C 0.0000 0.0000 0.0002 0.0001 0.0000
10. H 0.0000 0.0000 0.0002 0.0008 0.0000
11. C 0.0000 0.0000 0.0001 0.0000 0.0000
12. H 0.0000 0.0000 0.0000 0.0000 0.0000
13. H 0.0000 0.0000 0.0000 0.0000 0.0000
14. H 0.0000 0.0000 0.0000 0.0000 0.0000
15. C 0.0000 0.0000 0.0000 0.0002 0.0000
16. C 0.0000 0.0000 0.0000 0.0001 0.0000
17. C 0.0000 0.0000 0.0000 0.0000 0.0000
18. C 0.0000 0.0000 0.0000 0.0000 0.0000
19. H 0.0000 0.0000 0.0000 0.0001 0.0000
20. C 0.0000 0.0000 0.0000 0.0001 0.0000
21. H 0.0000 0.0000 0.0000 0.0000 0.0000
22. C 0.0000 0.0000 0.0000 0.0000 0.0000
23. H 0.0000 0.0000 0.0000 0.0000 0.0000
24. H 0.0000 0.0000 0.0000 0.0000 0.0000
25. H 0.0000 0.0000 0.0000 0.0000 0.0000
26. H 0.0005 0.0004 0.0015 0.0000 0.0004
27. C 0.0089 0.0083 0.0004 0.0003 0.0002
28. C 0.0033 0.0002 0.0016 0.0091 0.0084
29. C 0.0003 0.0033 0.0001 0.0001 0.0084
30. C 0.0017 0.0003 0.0054 0.0040 0.0002
31. C 0.9159 0.0084 0.0004 0.0001 0.0034
32. C 0.0086 0.9182 0.0001 0.0001 0.0033
33. H 0.0004 0.0020 0.0000 0.0000 0.0004
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34. C 0.0003 0.0000 0.9161 0.9195 0.0002
35. H 0.0006 0.0000 0.0115 0.0024 0.0000
36. C 0.0036 0.0033 0.0000 0.0003 0.9169
37. H 0.0000 0.0004 0.0000 0.0001 0.0022
38. H 0.0004 0.0000 0.0000 0.0000 0.0020
39. H 0.0000 0.0000 0.0000 0.0003 0.0000
40. H 0.0001 0.0000 0.0003 0.0000 0.0000
41. H 0.0022 0.0020 0.0000 0.0000 0.0000
Wiberg bond index, Totals by atom:
Atom 1
---- ------
1. C 3.8324
2. H 0.9322
3. H 0.9428
4. H 0.9457
5. C 3.9089
6. H 0.9421
7. N 3.6752
8. O 1.9160
9. C 3.9271
10. H 0.9470
11. C 3.8349
12. H 0.9449
13. H 0.9347
14. H 0.9473
15. C 4.0020
16. C 3.9464
17. C 3.9435
18. C 3.9479
19. H 0.9464
20. C 3.9479
21. H 0.9435
22. C 3.9476
23. H 0.9443
24. H 0.9442
25. H 0.9445
26. H 0.9500
27. C 3.9491
28. C 3.9982
29. C 3.9500
30. C 3.9592
31. C 3.9482
32. C 3.9499
33. H 0.9468
34. C 3.9047
35. H 0.9451
36. C 3.9492
37. H 0.9468
38. H 0.9469
39. H 0.9475
40. H 0.9458
41. H 0.9463
1tsn nbo wiberg index:
Wiberg bond index matrix in the NAO basis:
Atom 1 2 3 4 5 6 7 8 9
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0000 0.9149 0.9168 0.9288 1.0228 0.0031 0.0129 0.0089 0.0109
2. H 0.9149 0.0000 0.0006 0.0005 0.0021 0.0001 0.0053 0.0049 0.0001
3. H 0.9168 0.0006 0.0000 0.0007 0.0023 0.0095 0.0013 0.0041 0.0003
4. H 0.9288 0.0005 0.0007 0.0000 0.0034 0.0005 0.0089 0.0008 0.0003
5. C 1.0228 0.0021 0.0023 0.0034 0.0000 0.9017 1.2579 0.1834 0.0114
6. H 0.0031 0.0001 0.0095 0.0005 0.9017 0.0000 0.0032 0.0164 0.0004
7. N 0.0129 0.0053 0.0013 0.0089 1.2579 0.0032 0.0000 1.2626 0.8926
8. O 0.0089 0.0049 0.0041 0.0008 0.1834 0.0164 1.2626 0.0000 0.0588
9. C 0.0109 0.0001 0.0003 0.0003 0.0114 0.0004 0.8926 0.0588 0.0000
10. H 0.0002 0.0002 0.0001 0.0000 0.0082 0.0000 0.0038 0.0030 0.8860
11. C 0.0004 0.0001 0.0000 0.0003 0.0076 0.0005 0.0101 0.0080 1.0094
12. H 0.0005 0.0000 0.0000 0.0001 0.0002 0.0001 0.0102 0.0020 0.0038
13. H 0.0000 0.0000 0.0000 0.0000 0.0003 0.0000 0.0013 0.0043 0.0019
14. H 0.0000 0.0000 0.0000 0.0000 0.0002 0.0000 0.0008 0.0002 0.0025
15. C 0.0005 0.0000 0.0000 0.0000 0.0024 0.0036 0.0079 0.0109 1.0000
16. C 0.0002 0.0000 0.0001 0.0001 0.0029 0.0008 0.0097 0.0040 0.0106
17. C 0.0001 0.0000 0.0002 0.0001 0.0019 0.0001 0.0073 0.0033 0.0107
18. C 0.0000 0.0000 0.0000 0.0000 0.0005 0.0000 0.0003 0.0004 0.0073
19. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0001 0.0018
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20. C 0.0000 0.0000 0.0000 0.0000 0.0003 0.0000 0.0008 0.0006 0.0080
21. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0002 0.0019
22. C 0.0000 0.0000 0.0001 0.0000 0.0011 0.0000 0.0042 0.0025 0.0012
23. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0003
24. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0003
25. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0004
26. H 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000
27. C 0.0009 0.0001 0.0000 0.0000 0.0005 0.0000 0.0163 0.0287 0.0002
28. C 0.0002 0.0002 0.0000 0.0001 0.0081 0.0000 0.0013 0.0043 0.0004
29. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0003 0.0000
30. C 0.0084 0.0010 0.0002 0.0004 0.0056 0.0006 0.1248 0.2542 0.0013
31. C 0.0008 0.0001 0.0000 0.0000 0.0003 0.0000 0.0126 0.0194 0.0001
32. C 0.0008 0.0001 0.0000 0.0000 0.0002 0.0000 0.0137 0.0205 0.0001
33. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000
34. C 0.0046 0.0132 0.0014 0.0007 0.4807 0.0007 0.0188 0.0227 0.0009
35. H 0.0000 0.0000 0.0002 0.0000 0.0002 0.0000 0.0001 0.0004 0.0000
36. C 0.0000 0.0000 0.0000 0.0000 0.0011 0.0000 0.0002 0.0007 0.0000
37. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000
38. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
39. H 0.0003 0.0002 0.0002 0.0000 0.0007 0.0001 0.0015 0.0023 0.0000
40. H 0.0015 0.0004 0.0000 0.0005 0.0012 0.0000 0.0043 0.0085 0.0001
41. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Atom 10 11 12 13 14 15 16 17 18
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0002 0.0004 0.0005 0.0000 0.0000 0.0005 0.0002 0.0001 0.0000
2. H 0.0002 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
3. H 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0002 0.0000
4. H 0.0000 0.0003 0.0001 0.0000 0.0000 0.0000 0.0001 0.0001 0.0000
5. C 0.0082 0.0076 0.0002 0.0003 0.0002 0.0024 0.0029 0.0019 0.0005
6. H 0.0000 0.0005 0.0001 0.0000 0.0000 0.0036 0.0008 0.0001 0.0000
7. N 0.0038 0.0101 0.0102 0.0013 0.0008 0.0079 0.0097 0.0073 0.0003
8. O 0.0030 0.0080 0.0020 0.0043 0.0002 0.0109 0.0040 0.0033 0.0004
9. C 0.8860 1.0094 0.0038 0.0019 0.0025 1.0000 0.0106 0.0107 0.0073
10. H 0.0000 0.0033 0.0006 0.0011 0.0111 0.0022 0.0017 0.0071 0.0003
11. C 0.0033 0.0000 0.9256 0.9119 0.9196 0.0092 0.0088 0.0048 0.0003
12. H 0.0006 0.9256 0.0000 0.0007 0.0007 0.0005 0.0001 0.0001 0.0000
13. H 0.0011 0.9119 0.0007 0.0000 0.0007 0.0084 0.0007 0.0010 0.0003
14. H 0.0111 0.9196 0.0007 0.0007 0.0000 0.0009 0.0002 0.0002 0.0000
15. C 0.0022 0.0092 0.0005 0.0084 0.0009 0.0000 1.4061 1.3909 0.0119
16. C 0.0017 0.0088 0.0001 0.0007 0.0002 1.4061 0.0000 0.0115 1.4338
17. C 0.0071 0.0048 0.0001 0.0010 0.0002 1.3909 0.0115 0.0000 0.1112
18. C 0.0003 0.0003 0.0000 0.0003 0.0000 0.0119 1.4338 0.1112 0.0000
19. H 0.0008 0.0002 0.0000 0.0001 0.0000 0.0035 0.9145 0.0091 0.0036
20. C 0.0001 0.0003 0.0000 0.0001 0.0000 0.0119 0.1082 1.4473 0.0110
21. H 0.0003 0.0004 0.0000 0.0000 0.0009 0.0037 0.0085 0.9083 0.0003
22. C 0.0003 0.0022 0.0000 0.0006 0.0000 0.1080 0.0110 0.0111 1.4387
23. H 0.0001 0.0002 0.0000 0.0000 0.0000 0.0080 0.0033 0.0002 0.9153
24. H 0.0003 0.0000 0.0000 0.0000 0.0000 0.0080 0.0002 0.0034 0.0084
25. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0085 0.0083 0.0034
26. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0000
27. C 0.0009 0.0010 0.0000 0.0000 0.0032 0.0002 0.0002 0.0009 0.0001
28. C 0.0001 0.0008 0.0001 0.0001 0.0007 0.0001 0.0000 0.0005 0.0000
29. C 0.0000 0.0009 0.0000 0.0000 0.0005 0.0000 0.0000 0.0005 0.0000
30. C 0.0063 0.0023 0.0000 0.0000 0.0006 0.0009 0.0006 0.0002 0.0002
31. C 0.0007 0.0004 0.0001 0.0001 0.0000 0.0001 0.0001 0.0001 0.0000
32. C 0.0009 0.0003 0.0001 0.0000 0.0001 0.0001 0.0001 0.0001 0.0000
33. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
34. C 0.0005 0.0004 0.0000 0.0000 0.0001 0.0008 0.0002 0.0005 0.0002
35. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
36. C 0.0000 0.0004 0.0000 0.0000 0.0001 0.0000 0.0000 0.0003 0.0000
37. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
38. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
39. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0011 0.0001
40. H 0.0002 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001
41. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Atom 19 20 21 22 23 24 25 26 27
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0009
2. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001
3. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
4. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
5. C 0.0000 0.0003 0.0000 0.0011 0.0000 0.0000 0.0000 0.0001 0.0005
6. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
7. N 0.0001 0.0008 0.0002 0.0042 0.0000 0.0000 0.0000 0.0000 0.0163
8. O 0.0001 0.0006 0.0002 0.0025 0.0001 0.0000 0.0000 0.0000 0.0287
9. C 0.0018 0.0080 0.0019 0.0012 0.0003 0.0003 0.0004 0.0000 0.0002
10. H 0.0008 0.0001 0.0003 0.0003 0.0001 0.0003 0.0000 0.0000 0.0009
11. C 0.0002 0.0003 0.0004 0.0022 0.0002 0.0000 0.0000 0.0000 0.0010
12. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
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13. H 0.0001 0.0001 0.0000 0.0006 0.0000 0.0000 0.0000 0.0000 0.0000
14. H 0.0000 0.0000 0.0009 0.0000 0.0000 0.0000 0.0000 0.0000 0.0032
15. C 0.0035 0.0119 0.0037 0.1080 0.0080 0.0080 0.0002 0.0000 0.0002
16. C 0.9145 0.1082 0.0085 0.0110 0.0033 0.0002 0.0085 0.0000 0.0002
17. C 0.0091 1.4473 0.9083 0.0111 0.0002 0.0034 0.0083 0.0002 0.0009
18. C 0.0036 0.0110 0.0003 1.4387 0.9153 0.0084 0.0034 0.0000 0.0001
19. H 0.0000 0.0003 0.0004 0.0084 0.0021 0.0004 0.0004 0.0000 0.0000
20. C 0.0003 0.0000 0.0037 1.4269 0.0085 0.9154 0.0033 0.0000 0.0002
21. H 0.0004 0.0037 0.0000 0.0082 0.0004 0.0020 0.0003 0.0006 0.0024
22. C 0.0084 1.4269 0.0082 0.0000 0.0034 0.0033 0.9156 0.0000 0.0000
23. H 0.0021 0.0085 0.0004 0.0034 0.0000 0.0004 0.0020 0.0000 0.0000
24. H 0.0004 0.9154 0.0020 0.0033 0.0004 0.0000 0.0020 0.0000 0.0000
25. H 0.0004 0.0033 0.0003 0.9156 0.0020 0.0020 0.0000 0.0000 0.0000
26. H 0.0000 0.0000 0.0006 0.0000 0.0000 0.0000 0.0000 0.0000 0.9170
27. C 0.0000 0.0002 0.0024 0.0000 0.0000 0.0000 0.0000 0.9170 0.0000
28. C 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000 0.0000 0.0036 1.3463
29. C 0.0000 0.0000 0.0003 0.0000 0.0000 0.0000 0.0000 0.0036 1.4488
30. C 0.0000 0.0003 0.0002 0.0001 0.0000 0.0000 0.0000 0.0017 0.0110
31. C 0.0000 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000 0.0089 0.0105
32. C 0.0000 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000 0.0084 0.0120
33. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0020 0.0033
34. C 0.0000 0.0003 0.0001 0.0001 0.0000 0.0000 0.0000 0.0006 0.0196
35. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0083
36. C 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000 0.0000 0.0003 0.0985
37. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0004 0.0088
38. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0004 0.0084
39. H 0.0000 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000 0.0017 0.0004
40. H 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0003
41. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0004 0.0002
Atom 28 29 30 31 32 33 34 35 36
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0002 0.0000 0.0084 0.0008 0.0008 0.0000 0.0046 0.0000 0.0000
2. H 0.0002 0.0000 0.0010 0.0001 0.0001 0.0000 0.0132 0.0000 0.0000
3. H 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000 0.0014 0.0002 0.0000
4. H 0.0001 0.0000 0.0004 0.0000 0.0000 0.0000 0.0007 0.0000 0.0000
5. C 0.0081 0.0000 0.0056 0.0003 0.0002 0.0000 0.4807 0.0002 0.0011
6. H 0.0000 0.0000 0.0006 0.0000 0.0000 0.0000 0.0007 0.0000 0.0000
7. N 0.0013 0.0001 0.1248 0.0126 0.0137 0.0000 0.0188 0.0001 0.0002
8. O 0.0043 0.0003 0.2542 0.0194 0.0205 0.0001 0.0227 0.0004 0.0007
9. C 0.0004 0.0000 0.0013 0.0001 0.0001 0.0000 0.0009 0.0000 0.0000
10. H 0.0001 0.0000 0.0063 0.0007 0.0009 0.0000 0.0005 0.0000 0.0000
11. C 0.0008 0.0009 0.0023 0.0004 0.0003 0.0000 0.0004 0.0000 0.0004
12. H 0.0001 0.0000 0.0000 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000
13. H 0.0001 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
14. H 0.0007 0.0005 0.0006 0.0000 0.0001 0.0000 0.0001 0.0000 0.0001
15. C 0.0001 0.0000 0.0009 0.0001 0.0001 0.0000 0.0008 0.0000 0.0000
16. C 0.0000 0.0000 0.0006 0.0001 0.0001 0.0000 0.0002 0.0000 0.0000
17. C 0.0005 0.0005 0.0002 0.0001 0.0001 0.0000 0.0005 0.0000 0.0003
18. C 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000 0.0002 0.0000 0.0000
19. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
20. C 0.0000 0.0000 0.0003 0.0001 0.0001 0.0000 0.0003 0.0000 0.0000
21. H 0.0002 0.0003 0.0002 0.0001 0.0001 0.0000 0.0001 0.0000 0.0002
22. C 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000
23. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
24. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
25. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
26. H 0.0036 0.0036 0.0017 0.0089 0.0084 0.0020 0.0006 0.0002 0.0003
27. C 1.3463 1.4488 0.0110 0.0105 0.0120 0.0033 0.0196 0.0083 0.0985
28. C 0.0000 0.0116 1.1326 1.3398 0.0933 0.0082 0.0109 0.0024 0.0111
29. C 0.0116 0.0000 0.0096 0.1028 1.4295 0.9175 0.0005 0.0001 0.0110
30. C 1.1326 0.0096 0.0000 0.0105 0.0008 0.0003 1.4526 0.9098 0.0105
31. C 1.3398 0.1028 0.0105 0.0000 0.0113 0.0003 0.0260 0.0018 1.4734
32. C 0.0933 1.4295 0.0008 0.0113 0.0000 0.0034 0.0148 0.0007 1.4080
33. H 0.0082 0.9175 0.0003 0.0003 0.0034 0.0000 0.0001 0.0004 0.0086
34. C 0.0109 0.0005 1.4526 0.0260 0.0148 0.0001 0.0000 0.0047 0.0003
35. H 0.0024 0.0001 0.9098 0.0018 0.0007 0.0004 0.0047 0.0000 0.0002
36. C 0.0111 0.0110 0.0105 1.4734 1.4080 0.0086 0.0003 0.0002 0.0000
37. H 0.0033 0.0003 0.0016 0.9153 0.0086 0.0004 0.0003 0.0005 0.0036
38. H 0.0002 0.0034 0.0003 0.0083 0.9182 0.0020 0.0000 0.0000 0.0033
39. H 0.0017 0.0001 0.0047 0.0003 0.0001 0.0000 0.9199 0.0124 0.0000
40. H 0.0084 0.0001 0.0046 0.0002 0.0001 0.0000 0.9088 0.0020 0.0004
41. H 0.0085 0.0084 0.0002 0.0035 0.0033 0.0004 0.0002 0.0000 0.9168
Atom 37 38 39 40 41
---- ------ ------ ------ ------ ------
1. C 0.0000 0.0000 0.0003 0.0015 0.0000
2. H 0.0000 0.0000 0.0002 0.0004 0.0000
3. H 0.0000 0.0000 0.0002 0.0000 0.0000
4. H 0.0000 0.0000 0.0000 0.0005 0.0000
5. C 0.0000 0.0000 0.0007 0.0012 0.0000
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6. H 0.0000 0.0000 0.0001 0.0000 0.0000
7. N 0.0000 0.0000 0.0015 0.0043 0.0000
8. O 0.0001 0.0000 0.0023 0.0085 0.0000
9. C 0.0000 0.0000 0.0000 0.0001 0.0000
10. H 0.0000 0.0000 0.0000 0.0002 0.0000
11. C 0.0000 0.0000 0.0000 0.0001 0.0000
12. H 0.0000 0.0000 0.0000 0.0000 0.0000
13. H 0.0000 0.0000 0.0000 0.0000 0.0000
14. H 0.0000 0.0000 0.0000 0.0000 0.0000
15. C 0.0000 0.0000 0.0001 0.0000 0.0000
16. C 0.0000 0.0000 0.0000 0.0000 0.0000
17. C 0.0000 0.0000 0.0011 0.0000 0.0000
18. C 0.0000 0.0000 0.0001 0.0001 0.0000
19. H 0.0000 0.0000 0.0000 0.0000 0.0000
20. C 0.0000 0.0000 0.0001 0.0001 0.0000
21. H 0.0000 0.0000 0.0001 0.0000 0.0000
22. C 0.0000 0.0000 0.0000 0.0000 0.0000
23. H 0.0000 0.0000 0.0000 0.0000 0.0000
24. H 0.0000 0.0000 0.0000 0.0000 0.0000
25. H 0.0000 0.0000 0.0000 0.0000 0.0000
26. H 0.0004 0.0004 0.0017 0.0000 0.0004
27. C 0.0088 0.0084 0.0004 0.0003 0.0002
28. C 0.0033 0.0002 0.0017 0.0084 0.0085
29. C 0.0003 0.0034 0.0001 0.0001 0.0084
30. C 0.0016 0.0003 0.0047 0.0046 0.0002
31. C 0.9153 0.0083 0.0003 0.0002 0.0035
32. C 0.0086 0.9182 0.0001 0.0001 0.0033
33. H 0.0004 0.0020 0.0000 0.0000 0.0004
34. C 0.0003 0.0000 0.9199 0.9088 0.0002
35. H 0.0005 0.0000 0.0124 0.0020 0.0000
36. C 0.0036 0.0033 0.0000 0.0004 0.9168
37. H 0.0000 0.0004 0.0000 0.0000 0.0022
38. H 0.0004 0.0000 0.0000 0.0000 0.0020
39. H 0.0000 0.0000 0.0000 0.0004 0.0000
40. H 0.0000 0.0000 0.0004 0.0000 0.0000
41. H 0.0022 0.0020 0.0000 0.0000 0.0000
Wiberg bond index, Totals by atom:
Atom 1
---- ------
1. C 3.8384
2. H 0.9443
3. H 0.9380
4. H 0.9462
5. C 3.9096
6. H 0.9416
7. N 3.6953
8. O 1.9417
9. C 3.9239
10. H 0.9404
11. C 3.8302
12. H 0.9454
13. H 0.9337
14. H 0.9434
15. C 4.0013
16. C 3.9468
17. C 3.9425
18. C 3.9477
19. H 0.9459
20. C 3.9481
21. H 0.9442
22. C 3.9475
23. H 0.9442
24. H 0.9444
25. H 0.9445
26. H 0.9504
27. C 3.9493
28. C 3.9989
29. C 3.9499
30. C 3.9590
31. C 3.9477
32. C 3.9497
33. H 0.9469
34. C 3.9063
35. H 0.9444
36. C 3.9492
37. H 0.9460
38. H 0.9468
39. H 0.9489
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40. H 0.9422
41. H 0.9462
1tsx nbo wiberg bond order index:
Wiberg bond index matrix in the NAO basis:
Atom 1 2 3 4 5 6 7 8 9
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0000 0.9293 0.9126 0.9100 1.0290 0.0033 0.0130 0.0081 0.0117
2. H 0.9293 0.0000 0.0005 0.0007 0.0033 0.0006 0.0091 0.0008 0.0004
3. H 0.9126 0.0005 0.0000 0.0006 0.0023 0.0001 0.0060 0.0061 0.0001
4. H 0.9100 0.0007 0.0006 0.0000 0.0023 0.0095 0.0013 0.0038 0.0003
5. C 1.0290 0.0033 0.0023 0.0023 0.0000 0.9032 1.2656 0.1931 0.0127
6. H 0.0033 0.0006 0.0001 0.0095 0.9032 0.0000 0.0027 0.0168 0.0006
7. N 0.0130 0.0091 0.0060 0.0013 1.2656 0.0027 0.0000 1.2440 0.8995
8. O 0.0081 0.0008 0.0061 0.0038 0.1931 0.0168 1.2440 0.0000 0.0586
9. C 0.0117 0.0004 0.0001 0.0003 0.0127 0.0006 0.8995 0.0586 0.0000
10. H 0.0003 0.0000 0.0001 0.0000 0.0084 0.0002 0.0032 0.0028 0.8786
11. C 0.0003 0.0003 0.0002 0.0000 0.0091 0.0002 0.0102 0.0043 1.0085
12. H 0.0003 0.0001 0.0000 0.0000 0.0008 0.0001 0.0097 0.0009 0.0030
13. H 0.0001 0.0000 0.0000 0.0000 0.0005 0.0000 0.0016 0.0053 0.0021
14. H 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0008 0.0003 0.0029
15. C 0.0003 0.0001 0.0000 0.0000 0.0018 0.0031 0.0069 0.0114 0.9995
16. C 0.0001 0.0000 0.0001 0.0001 0.0018 0.0001 0.0074 0.0035 0.0100
17. C 0.0001 0.0000 0.0000 0.0002 0.0019 0.0005 0.0100 0.0025 0.0107
18. C 0.0000 0.0000 0.0000 0.0000 0.0003 0.0001 0.0007 0.0003 0.0078
19. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0001 0.0018
20. C 0.0000 0.0000 0.0000 0.0000 0.0002 0.0000 0.0005 0.0006 0.0076
21. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0020
22. C 0.0000 0.0000 0.0000 0.0001 0.0008 0.0000 0.0042 0.0018 0.0014
23. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0003
24. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0003
25. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0004
26. H 0.0001 0.0001 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000
27. C 0.0008 0.0000 0.0001 0.0013 0.0003 0.0000 0.0133 0.0223 0.0001
28. C 0.0004 0.0000 0.0001 0.0010 0.0054 0.0000 0.0008 0.0017 0.0001
29. C 0.0005 0.0000 0.0001 0.0000 0.0001 0.0000 0.0002 0.0002 0.0000
30. C 0.0068 0.0002 0.0013 0.0001 0.0057 0.0005 0.1168 0.2604 0.0005
31. C 0.0010 0.0000 0.0001 0.0000 0.0003 0.0000 0.0136 0.0183 0.0000
32. C 0.0007 0.0000 0.0000 0.0000 0.0001 0.0000 0.0127 0.0173 0.0000
33. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
34. C 0.0041 0.0007 0.0126 0.0016 0.4578 0.0006 0.0198 0.0230 0.0006
35. H 0.0001 0.0000 0.0001 0.0000 0.0007 0.0000 0.0004 0.0008 0.0001
36. C 0.0003 0.0000 0.0000 0.0001 0.0007 0.0000 0.0001 0.0002 0.0000
37. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0003 0.0000
38. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
39. H 0.0009 0.0003 0.0003 0.0000 0.0011 0.0000 0.0023 0.0055 0.0001
40. H 0.0003 0.0000 0.0002 0.0001 0.0007 0.0000 0.0027 0.0041 0.0001
41. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Atom 10 11 12 13 14 15 16 17 18
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0003 0.0003 0.0003 0.0001 0.0000 0.0003 0.0001 0.0001 0.0000
2. H 0.0000 0.0003 0.0001 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000
3. H 0.0001 0.0002 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000
4. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0002 0.0000
5. C 0.0084 0.0091 0.0008 0.0005 0.0001 0.0018 0.0018 0.0019 0.0003
6. H 0.0002 0.0002 0.0001 0.0000 0.0000 0.0031 0.0001 0.0005 0.0001
7. N 0.0032 0.0102 0.0097 0.0016 0.0008 0.0069 0.0074 0.0100 0.0007
8. O 0.0028 0.0043 0.0009 0.0053 0.0003 0.0114 0.0035 0.0025 0.0003
9. C 0.8786 1.0085 0.0030 0.0021 0.0029 0.9995 0.0100 0.0107 0.0078
10. H 0.0000 0.0028 0.0008 0.0011 0.0111 0.0027 0.0028 0.0098 0.0002
11. C 0.0028 0.0000 0.9232 0.9139 0.9311 0.0070 0.0068 0.0028 0.0004
12. H 0.0008 0.9232 0.0000 0.0008 0.0005 0.0004 0.0001 0.0002 0.0000
13. H 0.0011 0.9139 0.0008 0.0000 0.0006 0.0084 0.0003 0.0008 0.0002
14. H 0.0111 0.9311 0.0005 0.0006 0.0000 0.0007 0.0001 0.0004 0.0000
15. C 0.0027 0.0070 0.0004 0.0084 0.0007 0.0000 1.3918 1.4094 0.0116
16. C 0.0028 0.0068 0.0001 0.0003 0.0001 1.3918 0.0000 0.0117 1.4512
17. C 0.0098 0.0028 0.0002 0.0008 0.0004 1.4094 0.0117 0.0000 0.1081
18. C 0.0002 0.0004 0.0000 0.0002 0.0000 0.0116 1.4512 0.1081 0.0000
19. H 0.0003 0.0004 0.0000 0.0001 0.0000 0.0034 0.9130 0.0088 0.0036
20. C 0.0001 0.0004 0.0000 0.0001 0.0000 0.0121 0.1115 1.4294 0.0110
21. H 0.0002 0.0009 0.0000 0.0000 0.0009 0.0037 0.0088 0.9131 0.0003
22. C 0.0021 0.0005 0.0000 0.0002 0.0001 0.1087 0.0111 0.0110 1.4236
23. H 0.0000 0.0002 0.0000 0.0000 0.0000 0.0081 0.0034 0.0002 0.9151
24. H 0.0002 0.0001 0.0000 0.0000 0.0000 0.0078 0.0002 0.0032 0.0085
25. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0083 0.0085 0.0033
26. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
27. C 0.0004 0.0008 0.0000 0.0000 0.0000 0.0001 0.0000 0.0001 0.0001
28. C 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
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29. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
30. C 0.0033 0.0071 0.0004 0.0006 0.0002 0.0003 0.0003 0.0003 0.0005
31. C 0.0004 0.0008 0.0000 0.0000 0.0000 0.0001 0.0000 0.0001 0.0001
32. C 0.0004 0.0007 0.0000 0.0000 0.0000 0.0001 0.0000 0.0001 0.0001
33. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
34. C 0.0004 0.0023 0.0001 0.0002 0.0003 0.0001 0.0004 0.0001 0.0000
35. H 0.0000 0.0005 0.0000 0.0008 0.0000 0.0000 0.0000 0.0000 0.0000
36. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
37. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
38. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
39. H 0.0000 0.0003 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
40. H 0.0000 0.0003 0.0000 0.0000 0.0009 0.0001 0.0000 0.0001 0.0000
41. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Atom 19 20 21 22 23 24 25 26 27
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0008
2. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000
3. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001
4. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0013
5. C 0.0000 0.0002 0.0000 0.0008 0.0000 0.0000 0.0000 0.0001 0.0003
6. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
7. N 0.0002 0.0005 0.0000 0.0042 0.0000 0.0000 0.0000 0.0000 0.0133
8. O 0.0001 0.0006 0.0002 0.0018 0.0000 0.0001 0.0000 0.0000 0.0223
9. C 0.0018 0.0076 0.0020 0.0014 0.0003 0.0003 0.0004 0.0000 0.0001
10. H 0.0003 0.0001 0.0002 0.0021 0.0000 0.0002 0.0000 0.0000 0.0004
11. C 0.0004 0.0004 0.0009 0.0005 0.0002 0.0001 0.0000 0.0000 0.0008
12. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
13. H 0.0001 0.0001 0.0000 0.0002 0.0000 0.0000 0.0000 0.0000 0.0000
14. H 0.0000 0.0000 0.0009 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
15. C 0.0034 0.0121 0.0037 0.1087 0.0081 0.0078 0.0002 0.0000 0.0001
16. C 0.9130 0.1115 0.0088 0.0111 0.0034 0.0002 0.0083 0.0000 0.0000
17. C 0.0088 1.4294 0.9131 0.0110 0.0002 0.0032 0.0085 0.0000 0.0001
18. C 0.0036 0.0110 0.0003 1.4236 0.9151 0.0085 0.0033 0.0000 0.0001
19. H 0.0000 0.0003 0.0004 0.0085 0.0021 0.0004 0.0004 0.0000 0.0000
20. C 0.0003 0.0000 0.0036 1.4426 0.0083 0.9156 0.0034 0.0000 0.0000
21. H 0.0004 0.0036 0.0000 0.0082 0.0004 0.0020 0.0004 0.0000 0.0000
22. C 0.0085 1.4426 0.0082 0.0000 0.0033 0.0034 0.9156 0.0000 0.0000
23. H 0.0021 0.0083 0.0004 0.0033 0.0000 0.0004 0.0020 0.0000 0.0000
24. H 0.0004 0.9156 0.0020 0.0034 0.0004 0.0000 0.0020 0.0000 0.0000
25. H 0.0004 0.0034 0.0004 0.9156 0.0020 0.0020 0.0000 0.0000 0.0000
26. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.9176
27. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.9176 0.0000
28. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0034 1.3514
29. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0036 1.4579
30. C 0.0001 0.0003 0.0000 0.0001 0.0000 0.0000 0.0000 0.0018 0.0104
31. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0089 0.0106
32. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0085 0.0114
33. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0021 0.0033
34. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0005 0.0190
35. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0078
36. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0003 0.1020
37. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0005 0.0088
38. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0004 0.0083
39. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0016 0.0004
40. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0003
41. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0004 0.0002
Atom 28 29 30 31 32 33 34 35 36
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0004 0.0005 0.0068 0.0010 0.0007 0.0000 0.0041 0.0001 0.0003
2. H 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000 0.0007 0.0000 0.0000
3. H 0.0001 0.0001 0.0013 0.0001 0.0000 0.0000 0.0126 0.0001 0.0000
4. H 0.0010 0.0000 0.0001 0.0000 0.0000 0.0000 0.0016 0.0000 0.0001
5. C 0.0054 0.0001 0.0057 0.0003 0.0001 0.0000 0.4578 0.0007 0.0007
6. H 0.0000 0.0000 0.0005 0.0000 0.0000 0.0000 0.0006 0.0000 0.0000
7. N 0.0008 0.0002 0.1168 0.0136 0.0127 0.0000 0.0198 0.0004 0.0001
8. O 0.0017 0.0002 0.2604 0.0183 0.0173 0.0000 0.0230 0.0008 0.0002
9. C 0.0001 0.0000 0.0005 0.0000 0.0000 0.0000 0.0006 0.0001 0.0000
10. H 0.0000 0.0000 0.0033 0.0004 0.0004 0.0000 0.0004 0.0000 0.0000
11. C 0.0001 0.0000 0.0071 0.0008 0.0007 0.0000 0.0023 0.0005 0.0000
12. H 0.0000 0.0000 0.0004 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000
13. H 0.0000 0.0000 0.0006 0.0000 0.0000 0.0000 0.0002 0.0008 0.0000
14. H 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000 0.0003 0.0000 0.0000
15. C 0.0000 0.0000 0.0003 0.0001 0.0001 0.0000 0.0001 0.0000 0.0000
16. C 0.0000 0.0000 0.0003 0.0000 0.0000 0.0000 0.0004 0.0000 0.0000
17. C 0.0000 0.0000 0.0003 0.0001 0.0001 0.0000 0.0001 0.0000 0.0000
18. C 0.0000 0.0000 0.0005 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000
19. H 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
20. C 0.0000 0.0000 0.0003 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
21. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
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22. C 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
23. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
24. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
25. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
26. H 0.0034 0.0036 0.0018 0.0089 0.0085 0.0021 0.0005 0.0002 0.0003
27. C 1.3514 1.4579 0.0104 0.0106 0.0114 0.0033 0.0190 0.0078 0.1020
28. C 0.0000 0.0115 1.1206 1.3505 0.0960 0.0082 0.0108 0.0024 0.0110
29. C 0.0115 0.0000 0.0104 0.1022 1.4219 0.9176 0.0004 0.0001 0.0110
30. C 1.1206 0.0104 0.0000 0.0104 0.0007 0.0003 1.4684 0.9103 0.0092
31. C 1.3505 0.1022 0.0104 0.0000 0.0112 0.0003 0.0273 0.0016 1.4623
32. C 0.0960 1.4219 0.0007 0.0112 0.0000 0.0033 0.0148 0.0005 1.4189
33. H 0.0082 0.9176 0.0003 0.0003 0.0033 0.0000 0.0000 0.0004 0.0085
34. C 0.0108 0.0004 1.4684 0.0273 0.0148 0.0000 0.0000 0.0045 0.0002
35. H 0.0024 0.0001 0.9103 0.0016 0.0005 0.0004 0.0045 0.0000 0.0002
36. C 0.0110 0.0110 0.0092 1.4623 1.4189 0.0085 0.0002 0.0002 0.0000
37. H 0.0033 0.0003 0.0016 0.9157 0.0086 0.0004 0.0003 0.0006 0.0035
38. H 0.0002 0.0033 0.0003 0.0084 0.9183 0.0020 0.0000 0.0000 0.0033
39. H 0.0017 0.0001 0.0053 0.0004 0.0001 0.0000 0.9151 0.0111 0.0000
40. H 0.0089 0.0001 0.0040 0.0001 0.0001 0.0000 0.9193 0.0024 0.0003
41. H 0.0084 0.0084 0.0002 0.0034 0.0033 0.0004 0.0002 0.0000 0.9169
Atom 37 38 39 40 41
---- ------ ------ ------ ------ ------
1. C 0.0000 0.0000 0.0009 0.0003 0.0000
2. H 0.0000 0.0000 0.0003 0.0000 0.0000
3. H 0.0000 0.0000 0.0003 0.0002 0.0000
4. H 0.0000 0.0000 0.0000 0.0001 0.0000
5. C 0.0000 0.0000 0.0011 0.0007 0.0000
6. H 0.0000 0.0000 0.0000 0.0000 0.0000
7. N 0.0000 0.0000 0.0023 0.0027 0.0000
8. O 0.0003 0.0000 0.0055 0.0041 0.0000
9. C 0.0000 0.0000 0.0001 0.0001 0.0000
10. H 0.0000 0.0000 0.0000 0.0000 0.0000
11. C 0.0000 0.0000 0.0003 0.0003 0.0000
12. H 0.0000 0.0000 0.0000 0.0000 0.0000
13. H 0.0000 0.0000 0.0000 0.0000 0.0000
14. H 0.0000 0.0000 0.0000 0.0009 0.0000
15. C 0.0000 0.0000 0.0000 0.0001 0.0000
16. C 0.0000 0.0000 0.0000 0.0000 0.0000
17. C 0.0000 0.0000 0.0000 0.0001 0.0000
18. C 0.0000 0.0000 0.0000 0.0000 0.0000
19. H 0.0000 0.0000 0.0000 0.0000 0.0000
20. C 0.0000 0.0000 0.0000 0.0000 0.0000
21. H 0.0000 0.0000 0.0000 0.0000 0.0000
22. C 0.0000 0.0000 0.0000 0.0000 0.0000
23. H 0.0000 0.0000 0.0000 0.0000 0.0000
24. H 0.0000 0.0000 0.0000 0.0000 0.0000
25. H 0.0000 0.0000 0.0000 0.0000 0.0000
26. H 0.0005 0.0004 0.0016 0.0000 0.0004
27. C 0.0088 0.0083 0.0004 0.0003 0.0002
28. C 0.0033 0.0002 0.0017 0.0089 0.0084
29. C 0.0003 0.0033 0.0001 0.0001 0.0084
30. C 0.0016 0.0003 0.0053 0.0040 0.0002
31. C 0.9157 0.0084 0.0004 0.0001 0.0034
32. C 0.0086 0.9183 0.0001 0.0001 0.0033
33. H 0.0004 0.0020 0.0000 0.0000 0.0004
34. C 0.0003 0.0000 0.9151 0.9193 0.0002
35. H 0.0006 0.0000 0.0111 0.0024 0.0000
36. C 0.0035 0.0033 0.0000 0.0003 0.9169
37. H 0.0000 0.0004 0.0000 0.0000 0.0022
38. H 0.0004 0.0000 0.0000 0.0000 0.0020
39. H 0.0000 0.0000 0.0000 0.0003 0.0000
40. H 0.0000 0.0000 0.0003 0.0000 0.0000
41. H 0.0022 0.0020 0.0000 0.0000 0.0000
Wiberg bond index, Totals by atom:
Atom 1
---- ------
1. C 3.8344
2. H 0.9466
3. H 0.9438
4. H 0.9333
5. C 3.9106
6. H 0.9425
7. N 3.6795
8. O 1.9199
9. C 3.9223
10. H 0.9329
11. C 3.8364
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79
12. H 0.9419
13. H 0.9377
14. H 0.9513
15. C 4.0000
16. C 3.9451
17. C 3.9441
18. C 3.9475
19. H 0.9439
20. C 3.9483
21. H 0.9451
22. C 3.9475
23. H 0.9440
24. H 0.9445
25. H 0.9445
26. H 0.9500
27. C 3.9492
28. C 3.9981
29. C 3.9500
30. C 3.9598
31. C 3.9482
32. C 3.9500
33. H 0.9469
34. C 3.9057
35. H 0.9456
36. C 3.9492
37. H 0.9467
38. H 0.9469
39. H 0.9472
40. H 0.9456
41. H 0.9463
2trx nbo wiberg bond order index:
Wiberg bond index matrix in the NAO basis:
Atom 1 2 3 4 5 6 7 8 9
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0000 0.9116 0.9233 1.5503 0.0050 0.0115 0.0111 0.0158 0.0075
2. H 0.9116 0.0000 0.0003 0.0056 0.0110 0.0025 0.0002 0.0004 0.0051
3. H 0.9233 0.0003 0.0000 0.0042 0.0021 0.0107 0.0001 0.0001 0.0008
4. C 1.5503 0.0056 0.0042 0.0000 0.9090 1.0280 0.0025 0.0028 0.0283
5. H 0.0050 0.0110 0.0021 0.9090 0.0000 0.0024 0.0003 0.0000 0.0101
6. C 0.0115 0.0025 0.0107 1.0280 0.0024 0.0000 0.9136 0.8892 0.9376
7. H 0.0111 0.0002 0.0001 0.0025 0.0003 0.9136 0.0000 0.0006 0.0241
8. H 0.0158 0.0004 0.0001 0.0028 0.0000 0.8892 0.0006 0.0000 0.0078
9. O 0.0075 0.0051 0.0008 0.0283 0.0101 0.9376 0.0241 0.0078 0.0000
10. H 0.0019 0.0007 0.0000 0.0005 0.0000 0.0040 0.0006 0.0120 0.7648
11. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
12. C 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
13. C 0.0000 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000 0.0000 0.0000
14. C 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
15. C 0.0003 0.0000 0.0000 0.0005 0.0000 0.0000 0.0000 0.0000 0.0000
16. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
17. C 0.0001 0.0000 0.0001 0.0002 0.0000 0.0000 0.0000 0.0000 0.0000
18. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
19. C 0.0001 0.0000 0.0001 0.0002 0.0000 0.0000 0.0000 0.0000 0.0000
20. H 0.0001 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000 0.0000 0.0000
21. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
22. C 0.0010 0.0001 0.0001 0.0006 0.0001 0.0002 0.0001 0.0001 0.0001
23. H 0.0028 0.0002 0.0004 0.0078 0.0001 0.0001 0.0002 0.0003 0.0001
24. C 0.0003 0.0001 0.0000 0.0016 0.0000 0.0000 0.0000 0.0001 0.0000
25. N 0.0282 0.0027 0.0014 0.1071 0.0006 0.0009 0.0026 0.0046 0.0004
26. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
27. H 0.0003 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
28. H 0.0001 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
29. C 0.4023 0.0016 0.0006 0.0061 0.0021 0.0011 0.0002 0.0001 0.0013
30. O 0.0244 0.0057 0.0021 0.2955 0.0012 0.0056 0.0076 0.0092 0.0004
31. H 0.0010 0.0003 0.0002 0.0056 0.0000 0.0002 0.0001 0.0002 0.0032
32. H 0.0004 0.0000 0.0000 0.0004 0.0000 0.0000 0.0000 0.0000 0.0001
Atom 10 11 12 13 14 15 16 17 18
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0019 0.0000 0.0001 0.0000 0.0000 0.0003 0.0000 0.0001 0.0000
2. H 0.0007 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
3. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000
4. C 0.0005 0.0000 0.0000 0.0002 0.0001 0.0005 0.0000 0.0002 0.0000
5. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
6. C 0.0040 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
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7. H 0.0006 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
8. H 0.0120 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
9. O 0.7648 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
10. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
11. H 0.0000 0.0000 0.9157 0.0033 0.0034 0.0083 0.0020 0.0085 0.0020
12. C 0.0000 0.9157 0.0000 1.4243 1.4422 0.0110 0.0033 0.0110 0.0034
13. C 0.0000 0.0033 1.4243 0.0000 0.0110 1.4504 0.9152 0.1085 0.0085
14. C 0.0000 0.0034 1.4422 0.0110 0.0000 0.1118 0.0083 1.4302 0.9155
15. C 0.0000 0.0083 0.0110 1.4504 0.1118 0.0000 0.0033 0.0118 0.0002
16. H 0.0000 0.0020 0.0033 0.9152 0.0083 0.0033 0.0000 0.0002 0.0004
17. C 0.0000 0.0085 0.0110 0.1085 1.4302 0.0118 0.0002 0.0000 0.0032
18. H 0.0000 0.0020 0.0034 0.0085 0.9155 0.0002 0.0004 0.0032 0.0000
19. C 0.0000 0.0002 0.1084 0.0119 0.0119 1.3881 0.0080 1.4125 0.0079
20. H 0.0000 0.0004 0.0084 0.0037 0.0003 0.9113 0.0021 0.0087 0.0004
21. H 0.0000 0.0004 0.0084 0.0003 0.0036 0.0092 0.0004 0.9148 0.0021
22. C 0.0000 0.0004 0.0011 0.0079 0.0071 0.0103 0.0004 0.0107 0.0003
23. H 0.0000 0.0000 0.0001 0.0001 0.0003 0.0066 0.0003 0.0015 0.0001
24. C 0.0000 0.0000 0.0037 0.0005 0.0004 0.0066 0.0000 0.0099 0.0001
25. N 0.0004 0.0000 0.0031 0.0007 0.0006 0.0057 0.0000 0.0087 0.0001
26. H 0.0000 0.0000 0.0008 0.0001 0.0002 0.0012 0.0000 0.0010 0.0000
27. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0000 0.0001 0.0000
28. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0005 0.0000 0.0002 0.0000
29. C 0.0001 0.0000 0.0008 0.0004 0.0001 0.0024 0.0000 0.0017 0.0000
30. O 0.0001 0.0000 0.0018 0.0005 0.0007 0.0032 0.0000 0.0027 0.0001
31. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
32. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0003 0.0000 0.0001 0.0000
Atom 19 20 21 22 23 24 25 26 27
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0001 0.0001 0.0000 0.0010 0.0028 0.0003 0.0282 0.0000 0.0003
2. H 0.0000 0.0000 0.0000 0.0001 0.0002 0.0001 0.0027 0.0000 0.0000
3. H 0.0001 0.0000 0.0000 0.0001 0.0004 0.0000 0.0014 0.0000 0.0000
4. C 0.0002 0.0002 0.0000 0.0006 0.0078 0.0016 0.1071 0.0001 0.0001
5. H 0.0000 0.0000 0.0000 0.0001 0.0001 0.0000 0.0006 0.0000 0.0000
6. C 0.0000 0.0000 0.0000 0.0002 0.0001 0.0000 0.0009 0.0000 0.0000
7. H 0.0000 0.0000 0.0000 0.0001 0.0002 0.0000 0.0026 0.0000 0.0000
8. H 0.0000 0.0000 0.0000 0.0001 0.0003 0.0001 0.0046 0.0000 0.0000
9. O 0.0000 0.0000 0.0000 0.0001 0.0001 0.0000 0.0004 0.0000 0.0000
10. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0004 0.0000 0.0000
11. H 0.0002 0.0004 0.0004 0.0004 0.0000 0.0000 0.0000 0.0000 0.0000
12. C 0.1084 0.0084 0.0084 0.0011 0.0001 0.0037 0.0031 0.0008 0.0000
13. C 0.0119 0.0037 0.0003 0.0079 0.0001 0.0005 0.0007 0.0001 0.0000
14. C 0.0119 0.0003 0.0036 0.0071 0.0003 0.0004 0.0006 0.0002 0.0000
15. C 1.3881 0.9113 0.0092 0.0103 0.0066 0.0066 0.0057 0.0012 0.0002
16. H 0.0080 0.0021 0.0004 0.0004 0.0003 0.0000 0.0000 0.0000 0.0000
17. C 1.4125 0.0087 0.9148 0.0107 0.0015 0.0099 0.0087 0.0010 0.0001
18. H 0.0079 0.0004 0.0021 0.0003 0.0001 0.0001 0.0001 0.0000 0.0000
19. C 0.0000 0.0035 0.0036 0.9997 0.0022 0.0103 0.0071 0.0084 0.0005
20. H 0.0035 0.0000 0.0004 0.0019 0.0004 0.0002 0.0005 0.0001 0.0000
21. H 0.0036 0.0004 0.0000 0.0018 0.0008 0.0001 0.0002 0.0001 0.0000
22. C 0.9997 0.0019 0.0018 0.0000 0.8880 1.0049 0.9000 0.0018 0.0031
23. H 0.0022 0.0004 0.0008 0.8880 0.0000 0.0034 0.0053 0.0008 0.0005
24. C 0.0103 0.0002 0.0001 1.0049 0.0034 0.0000 0.0100 0.9110 0.9269
25. N 0.0071 0.0005 0.0002 0.9000 0.0053 0.0100 0.0000 0.0015 0.0098
26. H 0.0084 0.0001 0.0001 0.0018 0.0008 0.9110 0.0015 0.0000 0.0007
27. H 0.0005 0.0000 0.0000 0.0031 0.0005 0.9269 0.0098 0.0007 0.0000
28. H 0.0009 0.0005 0.0000 0.0024 0.0114 0.9287 0.0008 0.0006 0.0006
29. C 0.0019 0.0001 0.0000 0.0152 0.0102 0.0084 1.3356 0.0004 0.0002
30. O 0.0115 0.0001 0.0001 0.0546 0.0020 0.0072 1.2223 0.0061 0.0015
31. H 0.0002 0.0000 0.0000 0.0122 0.0001 0.0005 0.0027 0.0000 0.0004
32. H 0.0026 0.0000 0.0000 0.0003 0.0000 0.0004 0.0025 0.0000 0.0001
Atom 28 29 30 31 32
---- ------ ------ ------ ------ ------
1. C 0.0001 0.4023 0.0244 0.0010 0.0004
2. H 0.0000 0.0016 0.0057 0.0003 0.0000
3. H 0.0000 0.0006 0.0021 0.0002 0.0000
4. C 0.0001 0.0061 0.2955 0.0056 0.0004
5. H 0.0000 0.0021 0.0012 0.0000 0.0000
6. C 0.0000 0.0011 0.0056 0.0002 0.0000
7. H 0.0000 0.0002 0.0076 0.0001 0.0000
8. H 0.0000 0.0001 0.0092 0.0002 0.0000
9. O 0.0000 0.0013 0.0004 0.0032 0.0001
10. H 0.0000 0.0001 0.0001 0.0000 0.0000
11. H 0.0000 0.0000 0.0000 0.0000 0.0000
12. C 0.0000 0.0008 0.0018 0.0000 0.0000
13. C 0.0001 0.0004 0.0005 0.0000 0.0001
14. C 0.0000 0.0001 0.0007 0.0000 0.0000
15. C 0.0005 0.0024 0.0032 0.0000 0.0003
16. H 0.0000 0.0000 0.0000 0.0000 0.0000
17. C 0.0002 0.0017 0.0027 0.0000 0.0001
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18. H 0.0000 0.0000 0.0001 0.0000 0.0000
19. C 0.0009 0.0019 0.0115 0.0002 0.0026
20. H 0.0005 0.0001 0.0001 0.0000 0.0000
21. H 0.0000 0.0000 0.0001 0.0000 0.0000
22. C 0.0024 0.0152 0.0546 0.0122 0.0003
23. H 0.0114 0.0102 0.0020 0.0001 0.0000
24. C 0.9287 0.0084 0.0072 0.0005 0.0004
25. N 0.0008 1.3356 1.2223 0.0027 0.0025
26. H 0.0006 0.0004 0.0061 0.0000 0.0000
27. H 0.0006 0.0002 0.0015 0.0004 0.0001
28. H 0.0000 0.0004 0.0003 0.0000 0.0000
29. C 0.0004 0.0000 0.2224 0.9093 0.9198
30. O 0.0003 0.2224 0.0000 0.0040 0.0187
31. H 0.0000 0.9093 0.0040 0.0000 0.0004
32. H 0.0000 0.9198 0.0187 0.0004 0.0000
Wiberg bond index, Totals by atom:
Atom 1
---- ------
1. C 3.8995
2. H 0.9482
3. H 0.9468
4. C 3.9576
5. H 0.9442
6. C 3.8077
7. H 0.9641
8. H 0.9434
9. O 1.7918
10. H 0.7851
11. H 0.9446
12. C 3.9476
13. C 3.9478
14. C 3.9479
15. C 3.9433
16. H 0.9441
17. C 3.9466
18. H 0.9444
19. C 4.0021
20. H 0.9431
21. H 0.9464
22. C 3.9265
23. H 0.9461
24. C 3.8354
25. N 3.6658
26. H 0.9349
27. H 0.9449
28. H 0.9477
29. C 3.8448
30. O 1.9116
31. H 0.9407
32. H 0.9462
2trn nbo wiberg bond order index:
Wiberg bond index matrix in the NAO basis:
Atom 1 2 3 4 5 6 7 8 9
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0000 0.9208 0.9142 1.4964 0.0052 0.0109 0.0108 0.0137 0.0064
2. H 0.9208 0.0000 0.0003 0.0051 0.0122 0.0024 0.0002 0.0003 0.0035
3. H 0.9142 0.0003 0.0000 0.0048 0.0023 0.0084 0.0001 0.0001 0.0005
4. C 1.4964 0.0051 0.0048 0.0000 0.9085 1.0300 0.0027 0.0024 0.0269
5. H 0.0052 0.0122 0.0023 0.9085 0.0000 0.0030 0.0004 0.0000 0.0104
6. C 0.0109 0.0024 0.0084 1.0300 0.0030 0.0000 0.9075 0.8977 0.9282
7. H 0.0108 0.0002 0.0001 0.0027 0.0004 0.9075 0.0000 0.0006 0.0232
8. H 0.0137 0.0003 0.0001 0.0024 0.0000 0.8977 0.0006 0.0000 0.0073
9. O 0.0064 0.0035 0.0005 0.0269 0.0104 0.9282 0.0232 0.0073 0.0000
10. H 0.0029 0.0011 0.0000 0.0009 0.0000 0.0040 0.0005 0.0122 0.7557
11. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
12. C 0.0002 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000 0.0000 0.0001
13. C 0.0004 0.0001 0.0001 0.0002 0.0000 0.0000 0.0000 0.0000 0.0002
14. C 0.0003 0.0001 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
15. C 0.0008 0.0013 0.0000 0.0002 0.0000 0.0004 0.0003 0.0000 0.0067
16. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001
17. C 0.0003 0.0000 0.0000 0.0005 0.0000 0.0000 0.0000 0.0000 0.0001
18. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
19. C 0.0015 0.0001 0.0000 0.0013 0.0000 0.0001 0.0000 0.0000 0.0001
20. H 0.0001 0.0002 0.0000 0.0001 0.0000 0.0003 0.0005 0.0000 0.0125
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21. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
22. C 0.0006 0.0000 0.0000 0.0014 0.0000 0.0002 0.0001 0.0001 0.0003
23. H 0.0009 0.0000 0.0001 0.0054 0.0000 0.0001 0.0001 0.0003 0.0001
24. C 0.0004 0.0000 0.0001 0.0015 0.0000 0.0010 0.0001 0.0004 0.0028
25. N 0.0337 0.0011 0.0026 0.1184 0.0002 0.0010 0.0031 0.0040 0.0006
26. H 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
27. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0001
28. H 0.0000 0.0000 0.0000 0.0005 0.0000 0.0007 0.0003 0.0003 0.0055
29. C 0.4493 0.0008 0.0013 0.0056 0.0008 0.0035 0.0006 0.0002 0.0005
30. O 0.0279 0.0023 0.0074 0.3365 0.0010 0.0045 0.0116 0.0058 0.0003
31. H 0.0018 0.0002 0.0004 0.0084 0.0000 0.0001 0.0002 0.0003 0.0001
32. H 0.0004 0.0000 0.0000 0.0005 0.0000 0.0000 0.0000 0.0000 0.0000
Atom 10 11 12 13 14 15 16 17 18
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0029 0.0000 0.0002 0.0004 0.0003 0.0008 0.0000 0.0003 0.0000
2. H 0.0011 0.0000 0.0000 0.0001 0.0001 0.0013 0.0000 0.0000 0.0000
3. H 0.0000 0.0000 0.0000 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000
4. C 0.0009 0.0000 0.0002 0.0002 0.0001 0.0002 0.0000 0.0005 0.0000
5. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
6. C 0.0040 0.0000 0.0000 0.0000 0.0000 0.0004 0.0000 0.0000 0.0000
7. H 0.0005 0.0000 0.0000 0.0000 0.0000 0.0003 0.0000 0.0000 0.0000
8. H 0.0122 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
9. O 0.7557 0.0000 0.0001 0.0002 0.0000 0.0067 0.0001 0.0001 0.0000
10. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000
11. H 0.0000 0.0000 0.9164 0.0033 0.0033 0.0084 0.0020 0.0085 0.0020
12. C 0.0000 0.9164 0.0000 1.4249 1.4410 0.0112 0.0032 0.0111 0.0035
13. C 0.0000 0.0033 1.4249 0.0000 0.0110 1.4500 0.9163 0.1079 0.0085
14. C 0.0000 0.0033 1.4410 0.0110 0.0000 0.1119 0.0084 1.4308 0.9160
15. C 0.0001 0.0084 0.0112 1.4500 0.1119 0.0000 0.0035 0.0116 0.0002
16. H 0.0000 0.0020 0.0032 0.9163 0.0084 0.0035 0.0000 0.0002 0.0004
17. C 0.0000 0.0085 0.0111 0.1079 1.4308 0.0116 0.0002 0.0000 0.0033
18. H 0.0000 0.0020 0.0035 0.0085 0.9160 0.0002 0.0004 0.0033 0.0000
19. C 0.0000 0.0002 0.1078 0.0117 0.0120 1.3873 0.0082 1.4101 0.0080
20. H 0.0003 0.0003 0.0078 0.0038 0.0003 0.8940 0.0019 0.0081 0.0004
21. H 0.0000 0.0004 0.0084 0.0003 0.0036 0.0092 0.0004 0.9151 0.0021
22. C 0.0000 0.0004 0.0012 0.0080 0.0073 0.0107 0.0003 0.0105 0.0003
23. H 0.0000 0.0000 0.0001 0.0001 0.0003 0.0067 0.0003 0.0016 0.0001
24. C 0.0002 0.0000 0.0026 0.0003 0.0003 0.0051 0.0000 0.0091 0.0001
25. N 0.0005 0.0000 0.0042 0.0007 0.0003 0.0066 0.0000 0.0100 0.0001
26. H 0.0000 0.0000 0.0006 0.0001 0.0003 0.0010 0.0000 0.0008 0.0000
27. H 0.0000 0.0000 0.0001 0.0000 0.0000 0.0001 0.0000 0.0001 0.0000
28. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0004 0.0000 0.0001 0.0000
29. C 0.0001 0.0000 0.0011 0.0003 0.0004 0.0016 0.0000 0.0030 0.0000
30. O 0.0001 0.0000 0.0024 0.0005 0.0004 0.0032 0.0000 0.0038 0.0001
31. H 0.0001 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0001 0.0000
32. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0001 0.0000 0.0006 0.0000
Atom 19 20 21 22 23 24 25 26 27
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0015 0.0001 0.0000 0.0006 0.0009 0.0004 0.0337 0.0001 0.0000
2. H 0.0001 0.0002 0.0000 0.0000 0.0000 0.0000 0.0011 0.0000 0.0000
3. H 0.0000 0.0000 0.0000 0.0000 0.0001 0.0001 0.0026 0.0000 0.0000
4. C 0.0013 0.0001 0.0000 0.0014 0.0054 0.0015 0.1184 0.0000 0.0000
5. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0000 0.0000
6. C 0.0001 0.0003 0.0000 0.0002 0.0001 0.0010 0.0010 0.0000 0.0001
7. H 0.0000 0.0005 0.0000 0.0001 0.0001 0.0001 0.0031 0.0000 0.0000
8. H 0.0000 0.0000 0.0000 0.0001 0.0003 0.0004 0.0040 0.0000 0.0000
9. O 0.0001 0.0125 0.0000 0.0003 0.0001 0.0028 0.0006 0.0000 0.0001
10. H 0.0000 0.0003 0.0000 0.0000 0.0000 0.0002 0.0005 0.0000 0.0000
11. H 0.0002 0.0003 0.0004 0.0004 0.0000 0.0000 0.0000 0.0000 0.0000
12. C 0.1078 0.0078 0.0084 0.0012 0.0001 0.0026 0.0042 0.0006 0.0001
13. C 0.0117 0.0038 0.0003 0.0080 0.0001 0.0003 0.0007 0.0001 0.0000
14. C 0.0120 0.0003 0.0036 0.0073 0.0003 0.0003 0.0003 0.0003 0.0000
15. C 1.3873 0.8940 0.0092 0.0107 0.0067 0.0051 0.0066 0.0010 0.0001
16. H 0.0082 0.0019 0.0004 0.0003 0.0003 0.0000 0.0000 0.0000 0.0000
17. C 1.4101 0.0081 0.9151 0.0105 0.0016 0.0091 0.0100 0.0008 0.0001
18. H 0.0080 0.0004 0.0021 0.0003 0.0001 0.0001 0.0001 0.0000 0.0000
19. C 0.0000 0.0038 0.0036 0.9996 0.0021 0.0095 0.0091 0.0085 0.0005
20. H 0.0038 0.0000 0.0004 0.0017 0.0002 0.0003 0.0001 0.0000 0.0000
21. H 0.0036 0.0004 0.0000 0.0018 0.0009 0.0002 0.0002 0.0001 0.0000
22. C 0.9996 0.0017 0.0018 0.0000 0.8903 1.0097 0.8924 0.0018 0.0039
23. H 0.0021 0.0002 0.0009 0.8903 0.0000 0.0034 0.0041 0.0011 0.0006
24. C 0.0095 0.0003 0.0002 1.0097 0.0034 0.0000 0.0094 0.9160 0.9245
25. N 0.0091 0.0001 0.0002 0.8924 0.0041 0.0094 0.0000 0.0013 0.0101
26. H 0.0085 0.0000 0.0001 0.0018 0.0011 0.9160 0.0013 0.0000 0.0007
27. H 0.0005 0.0000 0.0000 0.0039 0.0006 0.9245 0.0101 0.0007 0.0000
28. H 0.0009 0.0007 0.0000 0.0025 0.0108 0.9170 0.0007 0.0006 0.0007
29. C 0.0030 0.0000 0.0000 0.0133 0.0081 0.0077 1.3187 0.0003 0.0002
30. O 0.0099 0.0001 0.0001 0.0537 0.0032 0.0082 1.2274 0.0037 0.0023
31. H 0.0005 0.0000 0.0000 0.0115 0.0000 0.0005 0.0042 0.0000 0.0005
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32. H 0.0028 0.0000 0.0000 0.0002 0.0000 0.0005 0.0030 0.0000 0.0001
Atom 28 29 30 31 32
---- ------ ------ ------ ------ ------
1. C 0.0000 0.4493 0.0279 0.0018 0.0004
2. H 0.0000 0.0008 0.0023 0.0002 0.0000
3. H 0.0000 0.0013 0.0074 0.0004 0.0000
4. C 0.0005 0.0056 0.3365 0.0084 0.0005
5. H 0.0000 0.0008 0.0010 0.0000 0.0000
6. C 0.0007 0.0035 0.0045 0.0001 0.0000
7. H 0.0003 0.0006 0.0116 0.0002 0.0000
8. H 0.0003 0.0002 0.0058 0.0003 0.0000
9. O 0.0055 0.0005 0.0003 0.0001 0.0000
10. H 0.0000 0.0001 0.0001 0.0001 0.0000
11. H 0.0000 0.0000 0.0000 0.0000 0.0000
12. C 0.0000 0.0011 0.0024 0.0000 0.0000
13. C 0.0001 0.0003 0.0005 0.0000 0.0001
14. C 0.0000 0.0004 0.0004 0.0000 0.0000
15. C 0.0004 0.0016 0.0032 0.0001 0.0001
16. H 0.0000 0.0000 0.0000 0.0000 0.0000
17. C 0.0001 0.0030 0.0038 0.0001 0.0006
18. H 0.0000 0.0000 0.0001 0.0000 0.0000
19. C 0.0009 0.0030 0.0099 0.0005 0.0028
20. H 0.0007 0.0000 0.0001 0.0000 0.0000
21. H 0.0000 0.0000 0.0001 0.0000 0.0000
22. C 0.0025 0.0133 0.0537 0.0115 0.0002
23. H 0.0108 0.0081 0.0032 0.0000 0.0000
24. C 0.9170 0.0077 0.0082 0.0005 0.0005
25. N 0.0007 1.3187 1.2274 0.0042 0.0030
26. H 0.0006 0.0003 0.0037 0.0000 0.0000
27. H 0.0007 0.0002 0.0023 0.0005 0.0001
28. H 0.0000 0.0002 0.0003 0.0000 0.0000
29. C 0.0002 0.0000 0.2003 0.9126 0.9190
30. O 0.0003 0.2003 0.0000 0.0044 0.0182
31. H 0.0000 0.9126 0.0044 0.0000 0.0003
32. H 0.0000 0.9190 0.0182 0.0003 0.0000
Wiberg bond index, Totals by atom:
Atom 1
---- ------
1. C 3.8999
2. H 0.9525
3. H 0.9428
4. C 3.9587
5. H 0.9441
6. C 3.8041
7. H 0.9628
8. H 0.9460
9. O 1.7923
10. H 0.7792
11. H 0.9453
12. C 3.9482
13. C 3.9490
14. C 3.9483
15. C 3.9329
16. H 0.9456
17. C 3.9473
18. H 0.9450
19. C 4.0022
20. H 0.9384
21. H 0.9467
22. C 3.9242
23. H 0.9411
24. C 3.8310
25. N 3.6677
26. H 0.9374
27. H 0.9448
28. H 0.9425
29. C 3.8526
30. O 1.9399
31. H 0.9463
32. H 0.9460
-----------------------------------------------------------------------------------------------------------------------------------
2tsx nbo wiberg bond order index: Wiberg bond index matrix in the NAO basis:
Atom 1 2 3 4 5 6 7 8 9
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0000 0.9045 0.9197 1.5335 0.0056 0.0113 0.0149 0.0119 0.0049
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2. H 0.9045 0.0000 0.0003 0.0056 0.0099 0.0024 0.0006 0.0000 0.0030
3. H 0.9197 0.0003 0.0000 0.0043 0.0023 0.0106 0.0001 0.0001 0.0006
4. C 1.5335 0.0056 0.0043 0.0000 0.9069 1.0347 0.0030 0.0029 0.0153
5. H 0.0056 0.0099 0.0023 0.9069 0.0000 0.0024 0.0002 0.0001 0.0078
6. C 0.0113 0.0024 0.0106 1.0347 0.0024 0.0000 0.9035 0.9058 0.9264
7. H 0.0149 0.0006 0.0001 0.0030 0.0002 0.9035 0.0000 0.0005 0.0195
8. H 0.0119 0.0000 0.0001 0.0029 0.0001 0.9058 0.0005 0.0000 0.0266
9. O 0.0049 0.0030 0.0006 0.0153 0.0078 0.9264 0.0195 0.0266 0.0000
10. H 0.0004 0.0000 0.0000 0.0094 0.0006 0.0012 0.0006 0.0001 0.7622
11. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
12. C 0.0002 0.0001 0.0000 0.0004 0.0000 0.0000 0.0000 0.0000 0.0000
13. C 0.0001 0.0000 0.0000 0.0008 0.0003 0.0001 0.0000 0.0000 0.0000
14. C 0.0004 0.0000 0.0001 0.0005 0.0000 0.0001 0.0000 0.0000 0.0000
15. C 0.0005 0.0002 0.0000 0.0023 0.0019 0.0001 0.0000 0.0000 0.0000
16. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
17. C 0.0004 0.0001 0.0007 0.0002 0.0001 0.0000 0.0000 0.0000 0.0000
18. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
19. C 0.0018 0.0001 0.0007 0.0056 0.0001 0.0001 0.0002 0.0002 0.0000
20. H 0.0000 0.0000 0.0000 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000
21. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
22. C 0.0007 0.0000 0.0000 0.0007 0.0000 0.0002 0.0001 0.0001 0.0001
23. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
24. C 0.0008 0.0001 0.0000 0.0035 0.0000 0.0000 0.0001 0.0001 0.0000
25. N 0.0303 0.0030 0.0011 0.1179 0.0006 0.0008 0.0044 0.0041 0.0002
26. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
27. H 0.0005 0.0000 0.0000 0.0004 0.0000 0.0000 0.0000 0.0000 0.0000
28. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
29. C 0.4275 0.0017 0.0006 0.0078 0.0024 0.0013 0.0002 0.0004 0.0029
30. O 0.0230 0.0067 0.0019 0.2929 0.0007 0.0056 0.0072 0.0110 0.0008
31. H 0.0012 0.0004 0.0002 0.0076 0.0000 0.0003 0.0002 0.0002 0.0057
32. H 0.0004 0.0000 0.0000 0.0005 0.0000 0.0000 0.0000 0.0000 0.0002
Atom 10 11 12 13 14 15 16 17 18
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0004 0.0000 0.0002 0.0001 0.0004 0.0005 0.0000 0.0004 0.0000
2. H 0.0000 0.0000 0.0001 0.0000 0.0000 0.0002 0.0000 0.0001 0.0000
3. H 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0007 0.0000
4. C 0.0094 0.0000 0.0004 0.0008 0.0005 0.0023 0.0000 0.0002 0.0000
5. H 0.0006 0.0000 0.0000 0.0003 0.0000 0.0019 0.0000 0.0001 0.0000
6. C 0.0012 0.0000 0.0000 0.0001 0.0001 0.0001 0.0000 0.0000 0.0000
7. H 0.0006 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
8. H 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
9. O 0.7622 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
10. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
11. H 0.0000 0.0000 0.9165 0.0034 0.0033 0.0084 0.0020 0.0085 0.0020
12. C 0.0000 0.9165 0.0000 1.4281 1.4383 0.0113 0.0033 0.0111 0.0035
13. C 0.0000 0.0034 1.4281 0.0000 0.0110 1.4446 0.9161 0.1091 0.0085
14. C 0.0000 0.0033 1.4383 0.0110 0.0000 0.1106 0.0084 1.4331 0.9163
15. C 0.0000 0.0084 0.0113 1.4446 0.1106 0.0000 0.0034 0.0114 0.0002
16. H 0.0000 0.0020 0.0033 0.9161 0.0084 0.0034 0.0000 0.0002 0.0004
17. C 0.0000 0.0085 0.0111 0.1091 1.4331 0.0114 0.0002 0.0000 0.0033
18. H 0.0000 0.0020 0.0035 0.0085 0.9163 0.0002 0.0004 0.0033 0.0000
19. C 0.0000 0.0002 0.1082 0.0117 0.0120 1.3887 0.0081 1.4115 0.0080
20. H 0.0000 0.0003 0.0081 0.0036 0.0003 0.9040 0.0020 0.0083 0.0004
21. H 0.0000 0.0004 0.0084 0.0003 0.0036 0.0092 0.0004 0.9167 0.0020
22. C 0.0000 0.0004 0.0011 0.0078 0.0072 0.0100 0.0003 0.0103 0.0003
23. H 0.0000 0.0000 0.0001 0.0001 0.0003 0.0065 0.0003 0.0016 0.0001
24. C 0.0000 0.0000 0.0027 0.0003 0.0003 0.0055 0.0000 0.0088 0.0001
25. N 0.0000 0.0000 0.0040 0.0002 0.0005 0.0072 0.0000 0.0091 0.0001
26. H 0.0000 0.0000 0.0007 0.0002 0.0003 0.0010 0.0000 0.0008 0.0000
27. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0001 0.0000
28. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0003 0.0000 0.0001 0.0000
29. C 0.0001 0.0000 0.0011 0.0004 0.0002 0.0028 0.0000 0.0012 0.0001
30. O 0.0000 0.0000 0.0011 0.0017 0.0016 0.0084 0.0000 0.0013 0.0000
31. H 0.0000 0.0000 0.0001 0.0000 0.0000 0.0003 0.0000 0.0002 0.0000
32. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0001 0.0000
Atom 19 20 21 22 23 24 25 26 27
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0018 0.0000 0.0000 0.0007 0.0000 0.0008 0.0303 0.0000 0.0005
2. H 0.0001 0.0000 0.0000 0.0000 0.0000 0.0001 0.0030 0.0000 0.0000
3. H 0.0007 0.0000 0.0000 0.0000 0.0000 0.0000 0.0011 0.0000 0.0000
4. C 0.0056 0.0001 0.0001 0.0007 0.0000 0.0035 0.1179 0.0001 0.0004
5. H 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000 0.0006 0.0000 0.0000
6. C 0.0001 0.0000 0.0000 0.0002 0.0000 0.0000 0.0008 0.0000 0.0000
7. H 0.0002 0.0000 0.0000 0.0001 0.0000 0.0001 0.0044 0.0000 0.0000
8. H 0.0002 0.0000 0.0000 0.0001 0.0000 0.0001 0.0041 0.0000 0.0000
9. O 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0002 0.0000 0.0000
10. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
11. H 0.0002 0.0003 0.0004 0.0004 0.0000 0.0000 0.0000 0.0000 0.0000
12. C 0.1082 0.0081 0.0084 0.0011 0.0001 0.0027 0.0040 0.0007 0.0000
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13. C 0.0117 0.0036 0.0003 0.0078 0.0001 0.0003 0.0002 0.0002 0.0000
14. C 0.0120 0.0003 0.0036 0.0072 0.0003 0.0003 0.0005 0.0003 0.0000
15. C 1.3887 0.9040 0.0092 0.0100 0.0065 0.0055 0.0072 0.0010 0.0001
16. H 0.0081 0.0020 0.0004 0.0003 0.0003 0.0000 0.0000 0.0000 0.0000
17. C 1.4115 0.0083 0.9167 0.0103 0.0016 0.0088 0.0091 0.0008 0.0001
18. H 0.0080 0.0004 0.0020 0.0003 0.0001 0.0001 0.0001 0.0000 0.0000
19. C 0.0000 0.0036 0.0036 0.9921 0.0024 0.0088 0.0133 0.0090 0.0005
20. H 0.0036 0.0000 0.0004 0.0018 0.0003 0.0003 0.0001 0.0000 0.0000
21. H 0.0036 0.0004 0.0000 0.0018 0.0008 0.0002 0.0001 0.0001 0.0000
22. C 0.9921 0.0018 0.0018 0.0000 0.9013 1.0042 0.9023 0.0017 0.0026
23. H 0.0024 0.0003 0.0008 0.9013 0.0000 0.0038 0.0022 0.0011 0.0005
24. C 0.0088 0.0003 0.0002 1.0042 0.0038 0.0000 0.0113 0.9274 0.9271
25. N 0.0133 0.0001 0.0001 0.9023 0.0022 0.0113 0.0000 0.0008 0.0097
26. H 0.0090 0.0000 0.0001 0.0017 0.0011 0.9274 0.0008 0.0000 0.0006
27. H 0.0005 0.0000 0.0000 0.0026 0.0005 0.9271 0.0097 0.0006 0.0000
28. H 0.0007 0.0006 0.0000 0.0023 0.0109 0.9189 0.0016 0.0005 0.0006
29. C 0.0087 0.0002 0.0001 0.0130 0.0003 0.0097 1.3199 0.0001 0.0003
30. O 0.0040 0.0039 0.0000 0.0540 0.0113 0.0045 1.2165 0.0004 0.0011
31. H 0.0003 0.0000 0.0000 0.0111 0.0002 0.0003 0.0034 0.0000 0.0002
32. H 0.0002 0.0000 0.0000 0.0003 0.0004 0.0003 0.0027 0.0000 0.0001
Atom 28 29 30 31 32
---- ------ ------ ------ ------ ------
1. C 0.0000 0.4275 0.0230 0.0012 0.0004
2. H 0.0000 0.0017 0.0067 0.0004 0.0000
3. H 0.0000 0.0006 0.0019 0.0002 0.0000
4. C 0.0000 0.0078 0.2929 0.0076 0.0005
5. H 0.0000 0.0024 0.0007 0.0000 0.0000
6. C 0.0000 0.0013 0.0056 0.0003 0.0000
7. H 0.0000 0.0002 0.0072 0.0002 0.0000
8. H 0.0000 0.0004 0.0110 0.0002 0.0000
9. O 0.0000 0.0029 0.0008 0.0057 0.0002
10. H 0.0000 0.0001 0.0000 0.0000 0.0000
11. H 0.0000 0.0000 0.0000 0.0000 0.0000
12. C 0.0000 0.0011 0.0011 0.0001 0.0000
13. C 0.0001 0.0004 0.0017 0.0000 0.0000
14. C 0.0000 0.0002 0.0016 0.0000 0.0000
15. C 0.0003 0.0028 0.0084 0.0003 0.0001
16. H 0.0000 0.0000 0.0000 0.0000 0.0000
17. C 0.0001 0.0012 0.0013 0.0002 0.0001
18. H 0.0000 0.0001 0.0000 0.0000 0.0000
19. C 0.0007 0.0087 0.0040 0.0003 0.0002
20. H 0.0006 0.0002 0.0039 0.0000 0.0000
21. H 0.0000 0.0001 0.0000 0.0000 0.0000
22. C 0.0023 0.0130 0.0540 0.0111 0.0003
23. H 0.0109 0.0003 0.0113 0.0002 0.0004
24. C 0.9189 0.0097 0.0045 0.0003 0.0003
25. N 0.0016 1.3199 1.2165 0.0034 0.0027
26. H 0.0005 0.0001 0.0004 0.0000 0.0000
27. H 0.0006 0.0003 0.0011 0.0002 0.0001
28. H 0.0000 0.0005 0.0045 0.0000 0.0000
29. C 0.0005 0.0000 0.2152 0.9029 0.9271
30. O 0.0045 0.2152 0.0000 0.0036 0.0196
31. H 0.0000 0.9029 0.0036 0.0000 0.0004
32. H 0.0000 0.9271 0.0196 0.0004 0.0000
Wiberg bond index, Totals by atom:
Atom 1
---- ------
1. C 3.8946
2. H 0.9388
3. H 0.9435
4. C 3.9570
5. H 0.9420
6. C 3.8070
7. H 0.9555
8. H 0.9642
9. O 1.7763
10. H 0.7747
11. H 0.9455
12. C 3.9484
13. C 3.9487
14. C 3.9486
15. C 3.9391
16. H 0.9452
17. C 3.9484
18. H 0.9454
19. C 4.0048
20. H 0.9384
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21. H 0.9483
22. C 3.9276
23. H 0.9445
24. C 3.8391
25. N 3.6674
26. H 0.9450
27. H 0.9444
28. H 0.9417
29. C 3.8487
30. O 1.9024
31. H 0.9390
32. H 0.9526
2tsn –nbo wiberg bond index by Tapas: Wiberg bond index matrix in the NAO basis:
Atom 1 2 3 4 5 6 7 8 9
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0000 0.8655 0.9999 0.0107 0.0109 0.0079 0.0020 0.0071 0.0018
2. H 0.8655 0.0000 0.0024 0.0060 0.0015 0.0001 0.0003 0.0003 0.0007
3. C 0.9999 0.0024 0.0000 1.3889 1.4115 0.0120 0.0035 0.0118 0.0036
4. C 0.0107 0.0060 1.3889 0.0000 0.0115 1.4498 0.9121 0.1116 0.0090
5. C 0.0109 0.0015 1.4115 0.0115 0.0000 0.1086 0.0088 1.4312 0.9134
6. C 0.0079 0.0001 0.0120 1.4498 0.1086 0.0000 0.0036 0.0110 0.0003
7. H 0.0020 0.0003 0.0035 0.9121 0.0088 0.0036 0.0000 0.0003 0.0004
8. C 0.0071 0.0003 0.0118 0.1116 1.4312 0.0110 0.0003 0.0000 0.0035
9. H 0.0018 0.0007 0.0036 0.0090 0.9134 0.0003 0.0004 0.0035 0.0000
10. C 0.0011 0.0001 0.1085 0.0110 0.0110 1.4247 0.0084 1.4416 0.0083
11. H 0.0004 0.0003 0.0080 0.0033 0.0002 0.9158 0.0021 0.0084 0.0004
12. H 0.0003 0.0001 0.0080 0.0002 0.0033 0.0085 0.0004 0.9160 0.0021
13. H 0.0004 0.0000 0.0002 0.0083 0.0085 0.0033 0.0004 0.0034 0.0004
14. C 1.0042 0.0034 0.0101 0.0065 0.0099 0.0005 0.0002 0.0004 0.0001
15. H 0.0019 0.0007 0.0085 0.0011 0.0010 0.0001 0.0001 0.0002 0.0001
16. H 0.0031 0.0005 0.0005 0.0002 0.0001 0.0000 0.0000 0.0000 0.0000
17. H 0.0027 0.0104 0.0010 0.0005 0.0002 0.0001 0.0005 0.0000 0.0000
18. N 0.8952 0.0037 0.0067 0.0059 0.0087 0.0007 0.0004 0.0006 0.0002
19. C 0.0154 0.0097 0.0019 0.0026 0.0017 0.0005 0.0002 0.0001 0.0000
20. H 0.0126 0.0001 0.0003 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
21. H 0.0003 0.0001 0.0028 0.0004 0.0001 0.0001 0.0000 0.0000 0.0000
22. O 0.0542 0.0019 0.0115 0.0032 0.0027 0.0005 0.0001 0.0007 0.0001
23. H 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
24. O 0.0069 0.0135 0.0001 0.0001 0.0002 0.0000 0.0000 0.0000 0.0005
25. C 0.0009 0.0012 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
26. C 0.0008 0.0060 0.0002 0.0004 0.0002 0.0002 0.0002 0.0001 0.0000
27. H 0.0001 0.0005 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
28. H 0.0003 0.0020 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
29. C 0.0008 0.0023 0.0001 0.0003 0.0001 0.0000 0.0001 0.0000 0.0000
30. H 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
31. H 0.0000 0.0002 0.0001 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000
32. H 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Atom 10 11 12 13 14 15 16 17 18
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0011 0.0004 0.0003 0.0004 1.0042 0.0019 0.0031 0.0027 0.8952
2. H 0.0001 0.0003 0.0001 0.0000 0.0034 0.0007 0.0005 0.0104 0.0037
3. C 0.1085 0.0080 0.0080 0.0002 0.0101 0.0085 0.0005 0.0010 0.0067
4. C 0.0110 0.0033 0.0002 0.0083 0.0065 0.0011 0.0002 0.0005 0.0059
5. C 0.0110 0.0002 0.0033 0.0085 0.0099 0.0010 0.0001 0.0002 0.0087
6. C 1.4247 0.9158 0.0085 0.0033 0.0005 0.0001 0.0000 0.0001 0.0007
7. H 0.0084 0.0021 0.0004 0.0004 0.0002 0.0001 0.0000 0.0005 0.0004
8. C 1.4416 0.0084 0.9160 0.0034 0.0004 0.0002 0.0000 0.0000 0.0006
9. H 0.0083 0.0004 0.0021 0.0004 0.0001 0.0001 0.0000 0.0000 0.0002
10. C 0.0000 0.0033 0.0034 0.9162 0.0036 0.0008 0.0000 0.0000 0.0031
11. H 0.0033 0.0000 0.0004 0.0020 0.0000 0.0000 0.0000 0.0000 0.0000
12. H 0.0034 0.0004 0.0000 0.0020 0.0001 0.0000 0.0000 0.0000 0.0001
13. H 0.9162 0.0020 0.0020 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
14. C 0.0036 0.0000 0.0001 0.0000 0.0000 0.9126 0.9264 0.9313 0.0100
15. H 0.0008 0.0000 0.0000 0.0000 0.9126 0.0000 0.0007 0.0005 0.0015
16. H 0.0000 0.0000 0.0000 0.0000 0.9264 0.0007 0.0000 0.0006 0.0098
17. H 0.0000 0.0000 0.0000 0.0000 0.9313 0.0005 0.0006 0.0000 0.0008
18. N 0.0031 0.0000 0.0001 0.0000 0.0100 0.0015 0.0098 0.0008 0.0000
19. C 0.0008 0.0000 0.0000 0.0000 0.0087 0.0004 0.0002 0.0004 1.3446
20. H 0.0000 0.0000 0.0000 0.0000 0.0005 0.0000 0.0004 0.0000 0.0027
21. H 0.0000 0.0000 0.0000 0.0000 0.0004 0.0000 0.0001 0.0000 0.0025
22. O 0.0018 0.0000 0.0001 0.0000 0.0064 0.0058 0.0013 0.0003 1.2247
23. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001
24. O 0.0000 0.0000 0.0000 0.0000 0.0002 0.0001 0.0000 0.0001 0.0003
25. C 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0007
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26. C 0.0000 0.0000 0.0000 0.0000 0.0019 0.0000 0.0001 0.0001 0.1035
27. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0029
28. H 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0032
29. C 0.0001 0.0000 0.0000 0.0000 0.0003 0.0000 0.0003 0.0000 0.0319
30. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001
31. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0012
32. H 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0024
Atom 19 20 21 22 23 24 25 26 27
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0154 0.0126 0.0003 0.0542 0.0001 0.0069 0.0009 0.0008 0.0001
2. H 0.0097 0.0001 0.0001 0.0019 0.0001 0.0135 0.0012 0.0060 0.0005
3. C 0.0019 0.0003 0.0028 0.0115 0.0000 0.0001 0.0001 0.0002 0.0000
4. C 0.0026 0.0000 0.0004 0.0032 0.0000 0.0001 0.0000 0.0004 0.0000
5. C 0.0017 0.0000 0.0001 0.0027 0.0000 0.0002 0.0000 0.0002 0.0000
6. C 0.0005 0.0000 0.0001 0.0005 0.0000 0.0000 0.0000 0.0002 0.0000
7. H 0.0002 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0002 0.0000
8. C 0.0001 0.0000 0.0000 0.0007 0.0000 0.0000 0.0000 0.0001 0.0000
9. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0005 0.0000 0.0000 0.0000
10. C 0.0008 0.0000 0.0000 0.0018 0.0000 0.0000 0.0000 0.0000 0.0000
11. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
12. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
13. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
14. C 0.0087 0.0005 0.0004 0.0064 0.0000 0.0002 0.0001 0.0019 0.0000
15. H 0.0004 0.0000 0.0000 0.0058 0.0000 0.0001 0.0000 0.0000 0.0001
16. H 0.0002 0.0004 0.0001 0.0013 0.0000 0.0000 0.0000 0.0001 0.0000
17. H 0.0004 0.0000 0.0000 0.0003 0.0000 0.0001 0.0000 0.0001 0.0000
18. N 1.3446 0.0027 0.0025 1.2247 0.0001 0.0003 0.0007 0.1035 0.0029
19. C 0.0000 0.9161 0.9195 0.2151 0.0002 0.0004 0.0034 0.0051 0.0003
20. H 0.9161 0.0000 0.0003 0.0044 0.0000 0.0000 0.0000 0.0054 0.0002
21. H 0.9195 0.0003 0.0000 0.0184 0.0000 0.0000 0.0000 0.0003 0.0000
22. O 0.2151 0.0044 0.0184 0.0000 0.0000 0.0004 0.0048 0.3093 0.0050
23. H 0.0002 0.0000 0.0000 0.0000 0.0000 0.7596 0.0040 0.0005 0.0117
24. O 0.0004 0.0000 0.0000 0.0004 0.7596 0.0000 0.9323 0.0288 0.0074
25. C 0.0034 0.0000 0.0000 0.0048 0.0040 0.9323 0.0000 1.0285 0.9000
26. C 0.0051 0.0054 0.0003 0.3093 0.0005 0.0288 1.0285 0.0000 0.0023
27. H 0.0003 0.0002 0.0000 0.0050 0.0117 0.0074 0.9000 0.0023 0.0000
28. H 0.0005 0.0002 0.0000 0.0131 0.0004 0.0220 0.9054 0.0027 0.0005
29. C 0.4005 0.0012 0.0004 0.0271 0.0020 0.0059 0.0107 1.5443 0.0138
30. H 0.0008 0.0000 0.0000 0.0009 0.0000 0.0108 0.0029 0.9067 0.0001
31. H 0.0007 0.0001 0.0000 0.0023 0.0013 0.0039 0.0024 0.0052 0.0004
32. H 0.0011 0.0002 0.0000 0.0058 0.0000 0.0005 0.0091 0.0048 0.0001
Atom 28 29 30 31 32
---- ------ ------ ------ ------ ------
1. C 0.0003 0.0008 0.0001 0.0000 0.0001
2. H 0.0020 0.0023 0.0000 0.0002 0.0001
3. C 0.0000 0.0001 0.0000 0.0001 0.0000
4. C 0.0000 0.0003 0.0000 0.0000 0.0000
5. C 0.0000 0.0001 0.0000 0.0001 0.0000
6. C 0.0000 0.0000 0.0000 0.0000 0.0000
7. H 0.0000 0.0001 0.0000 0.0000 0.0000
8. C 0.0000 0.0000 0.0000 0.0000 0.0000
9. H 0.0000 0.0000 0.0000 0.0000 0.0000
10. C 0.0000 0.0001 0.0000 0.0000 0.0000
11. H 0.0000 0.0000 0.0000 0.0000 0.0000
12. H 0.0000 0.0000 0.0000 0.0000 0.0000
13. H 0.0000 0.0000 0.0000 0.0000 0.0000
14. C 0.0001 0.0003 0.0000 0.0000 0.0001
15. H 0.0000 0.0000 0.0000 0.0000 0.0000
16. H 0.0000 0.0003 0.0000 0.0000 0.0000
17. H 0.0000 0.0000 0.0000 0.0000 0.0000
18. N 0.0032 0.0319 0.0001 0.0012 0.0024
19. C 0.0005 0.4005 0.0008 0.0007 0.0011
20. H 0.0002 0.0012 0.0000 0.0001 0.0002
21. H 0.0000 0.0004 0.0000 0.0000 0.0000
22. O 0.0131 0.0271 0.0009 0.0023 0.0058
23. H 0.0004 0.0020 0.0000 0.0013 0.0000
24. O 0.0220 0.0059 0.0108 0.0039 0.0005
25. C 0.9054 0.0107 0.0029 0.0024 0.0091
26. C 0.0027 1.5443 0.9067 0.0052 0.0048
27. H 0.0005 0.0138 0.0001 0.0004 0.0001
28. H 0.0000 0.0122 0.0002 0.0001 0.0001
29. C 0.0122 0.0000 0.0052 0.9240 0.9161
30. H 0.0002 0.0052 0.0000 0.0126 0.0023
31. H 0.0001 0.9240 0.0126 0.0000 0.0003
32. H 0.0001 0.9161 0.0023 0.0003 0.0000
Wiberg bond index, Totals by atom:
Page 237
Annexure 3
88
Atom 1
---- ------
1. C 3.9076
2. H 0.9337
3. C 4.0022
4. C 3.9440
5. C 3.9453
6. C 3.9483
7. H 0.9440
8. C 3.9483
9. H 0.9450
10. C 3.9480
11. H 0.9447
12. H 0.9449
13. H 0.9451
14. C 3.8380
15. H 0.9364
16. H 0.9442
17. H 0.9497
18. N 3.6684
19. C 3.8510
20. H 0.9448
21. H 0.9458
22. O 1.9218
23. H 0.7803
24. O 1.7941
25. C 3.8067
26. C 3.9578
27. H 0.9455
28. H 0.9631
29. C 3.8999
30. H 0.9429
31. H 0.9549
32. H 0.9432
Molecule = 1 E1, Final optimized geometry with frequency calculation.
---------------------------------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------------------------
E(RB+HF-LYP) = -309.648271707 A.U.
--------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -1.476632 2.607700 0.000000
2 1 0 -2.414618 2.059053 0.000000
3 1 0 -1.555059 3.690568 0.000000
4 6 0 -0.280612 2.005550 0.000000
5 1 0 0.608807 2.636172 0.000000
6 6 0 0.000000 0.560111 0.000000
7 6 0 -1.008602 -0.421264 0.000000
8 6 0 1.337691 0.129380 0.000000
9 6 0 -0.687896 -1.775345 0.000000
10 1 0 -2.052973 -0.122549 0.000000
11 6 0 1.661449 -1.226931 0.000000
12 1 0 2.131855 0.872780 0.000000
13 6 0 0.648870 -2.186283 0.000000
14 1 0 -1.483672 -2.515830 0.000000
15 1 0 2.704322 -1.533175 0.000000
16 1 0 0.895734 -3.244542 0.000000
------------------------------------------------------------------------------------------
Rotational constants (GHZ): 5.1809692 1.5346142 1.1839312
-----------------------------------------------------------------------------------------
Zero-point correction= 0.133720 (Hartree/Particle)
Thermal correction to Energy= 0.140497
Thermal correction to Enthalpy= 0.141441
Thermal correction to Gibbs Free Energy= 0.102157
Sum of electronic and zero-point Energies= -309.514552
Sum of electronic and thermal Energies= -309.507775
Sum of electronic and thermal Enthalpies= -309.506831
Sum of electronic and thermal Free Energies= -309.546115
-------------------------------------------------------------------------------
________________________________________________________________________
Page 238
Annexure 3
89
Molecule = 1 N1, Final optimised geometry with frequency calculation.
-------------------------------------------------------------------------------------
# opt=calcfc b3lyp/6-31g(d) geom=connectivity
---------------------------------------------------------
E(RB+HF-LYP) = -518.801980805 A.U.
--------------------------------------------------------
Standard orientation:
----------------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
----------------------------------------------------------------------------
1 6 0 2.791968 -2.031656 -0.495928
2 1 0 2.499925 -2.992077 -0.928256
3 1 0 3.277253 -2.201260 0.473969
4 1 0 3.552925 -1.564615 -1.135369
5 6 0 1.610762 -1.138428 -0.339098
6 1 0 0.612836 -1.412042 -0.648431
7 7 0 1.777509 0.035328 0.211341
8 8 0 2.910039 0.463816 0.622261
9 6 0 0.640173 1.026102 0.409984
10 1 0 0.750155 1.278277 1.468770
11 6 0 0.964096 2.274276 -0.415421
12 1 0 0.240506 3.065345 -0.196263
13 1 0 1.967467 2.616366 -0.156336
14 1 0 0.937266 2.067154 -1.490246
15 6 0 -0.741846 0.441739 0.194285
16 6 0 -1.426446 -0.111554 1.286001
17 6 0 -1.369589 0.433243 -1.059841
18 6 0 -2.699760 -0.659710 1.133729
19 1 0 -0.953819 -0.109104 2.265651
20 6 0 -2.642558 -0.116863 -1.216732
21 1 0 -0.865789 0.859383 -1.922257
22 6 0 -3.311700 -0.664699 -0.120918
23 1 0 -3.214106 -1.078589 1.994434
24 1 0 -3.113314 -0.112911 -2.196218
25 1 0 -4.304784 -1.088456 -0.243293
---------------------------------------------------------------------------------------
Rotational constants (GHZ): 1.6307890 0.5873298 0.5288821
---------------------------------------------------------------------------------------
Zero-point correction= 0.212032 (Hartree/Particle)
Thermal correction to Energy= 0.223712
Thermal correction to Enthalpy= 0.224656
Thermal correction to Gibbs Free Energy= 0.173434
Sum of electronic and zero-point Energies= -518.589949
Sum of electronic and thermal Energies= -518.578269
Sum of electronic and thermal Enthalpies= -518.577325
Sum of electronic and thermal Free Energies= -518.628547
________________________________________________________________________
Molecule = 1 PRN. Final optimized geometry with frequency calculation.
-----------------------------------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
------------------------------------------------------
E(RB+HF-LYP) = -828.475033401 A.U.
--------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.963647 -2.538012 -1.090959
2 1 0 0.820380 -2.992145 -2.078868
3 1 0 0.435866 -3.151929 -0.354264
4 1 0 2.034220 -2.570220 -0.869786
5 6 0 0.436296 -1.094863 -1.108385
6 1 0 1.061790 -0.489026 -1.771747
7 7 0 0.341716 -0.358101 0.167947
8 8 0 -0.811422 -0.973816 0.835355
9 6 0 1.434847 -0.322412 1.159882
10 1 0 1.054574 0.377720 1.917353
11 6 0 1.738493 -1.625784 1.918633
12 1 0 2.403059 -1.408749 2.762685
13 1 0 0.806999 -2.036418 2.313811
14 1 0 2.214953 -2.392405 1.303696
15 6 0 2.637224 0.349640 0.498204
Page 239
Annexure 3
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16 6 0 2.474796 1.627004 -0.062837
17 6 0 3.903559 -0.242721 0.443554
18 6 0 3.543173 2.287298 -0.665231
19 1 0 1.494609 2.094038 -0.028590
20 6 0 4.978837 0.419240 -0.157342
21 1 0 4.065817 -1.223764 0.878363
22 6 0 4.802976 1.684003 -0.715165
23 1 0 3.395066 3.276122 -1.091882
24 1 0 5.954537 -0.059084 -0.185866
25 1 0 5.638995 2.198763 -1.181290
26 1 0 -1.692281 1.506344 0.461355
27 6 0 -2.715159 1.181240 0.296104
28 6 0 -2.956789 -0.159931 -0.030108
29 6 0 -3.773776 2.080634 0.410933
30 6 0 -1.809715 -1.139268 -0.185263
31 6 0 -4.274812 -0.581513 -0.230921
32 6 0 -5.088076 1.654000 0.199061
33 1 0 -3.574683 3.117778 0.669167
34 6 0 -1.042423 -1.010276 -1.531770
35 1 0 -2.195520 -2.158816 -0.062819
36 6 0 -5.336402 0.319849 -0.123166
37 1 0 -4.474603 -1.624622 -0.469295
38 1 0 -5.912124 2.356763 0.290382
39 1 0 -1.250144 -0.038212 -1.986457
40 1 0 -1.326770 -1.790150 -2.244221
41 1 0 -6.355555 -0.023530 -0.281540
---------------------------------------------------------------------------------------
Rotational constants (GHZ): 0.7340377 0.1762062 0.1592351
---------------------------------------------------------------------------------------
Zero-point correction= 0.352109 (Hartree/Particle)
Thermal correction to Energy= 0.369806
Thermal correction to Enthalpy= 0.370750
Thermal correction to Gibbs Free Energy= 0.304171
Sum of electronic and zero-point Energies= -828.122925
Sum of electronic and thermal Energies= -828.105227
Sum of electronic and thermal Enthalpies= -828.104283
Sum of electronic and thermal Free Energies= -828.170862
-------------------------------------------------------------------------------
________________________________________________________________________
Molecule = 1 PRX. Final optimizwd geometry with frequency calculation.
------------------------------------------------------------------------------------------
# opt=calcfc b3lyp/6-31g(d) geom=connectivity
------------------------------------------------------------
E(RB+HF-LYP) = -828.485253757 A.U.
--------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -0.133612 2.519893 -0.563557
2 1 0 0.041393 3.045687 -1.509591
3 1 0 0.737692 2.673943 0.081324
4 1 0 -1.004706 2.965454 -0.073481
5 6 0 -0.364720 1.028364 -0.810297
6 1 0 -1.271882 0.898584 -1.407113
7 7 0 -0.561924 0.327066 0.481934
8 8 0 0.773194 -0.045802 0.863840
9 6 0 -1.416666 -0.884453 0.385373
10 1 0 -1.104868 -1.531752 -0.453437
11 6 0 -1.311715 -1.696813 1.683850
12 1 0 -1.979508 -2.562913 1.632983
13 1 0 -0.289075 -2.044401 1.847309
14 1 0 -1.605585 -1.082032 2.540679
15 6 0 -2.853646 -0.452203 0.129310
16 6 0 -3.627656 -1.101733 -0.839273
17 6 0 -3.443900 0.567109 0.890880
18 6 0 -4.964224 -0.750936 -1.041391
19 1 0 -3.180719 -1.891683 -1.439501
20 6 0 -4.776882 0.922665 0.686943
21 1 0 -2.844141 1.083754 1.633849
22 6 0 -5.542630 0.263554 -0.278302
23 1 0 -5.549818 -1.267463 -1.797541
24 1 0 -5.219871 1.716440 1.283084
25 1 0 -6.581466 0.541487 -0.435543
Page 240
Annexure 3
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26 1 0 3.484893 -2.007708 -1.333304
27 6 0 3.863742 -1.180243 -0.736695
28 6 0 2.962626 -0.311946 -0.109111
29 6 0 5.240685 -0.997569 -0.603350
30 6 0 1.475768 -0.496779 -0.317517
31 6 0 3.464736 0.735356 0.673377
32 6 0 5.733936 0.051644 0.173812
33 1 0 5.926499 -1.679932 -1.098765
34 6 0 0.853429 0.327526 -1.474403
35 1 0 1.274077 -1.566239 -0.475053
36 6 0 4.841263 0.913117 0.814963
37 1 0 2.770140 1.392265 1.186341
38 1 0 6.805777 0.192380 0.285266
39 1 0 1.563453 1.059578 -1.868941
40 1 0 0.554851 -0.323439 -2.301787
41 1 0 5.217560 1.725625 1.431289
---------------------------------------------------------------------------------------
Rotational constants (GHZ): 1.0425217 0.1519429 0.1477526
----------------------------------------------------------------------------------------
Zero-point correction= 0.351931 (Hartree/Particle)
Thermal correction to Energy= 0.369713
Thermal correction to Enthalpy= 0.370657
Thermal correction to Gibbs Free Energy= 0.304069
Sum of electronic and zero-point Energies= -828.133323
Sum of electronic and thermal Energies= -828.115541
Sum of electronic and thermal Enthalpies= -828.114596
Sum of electronic and thermal Free Energies= -828.181185
---------------------------------------------------------------------------------
________________________________________________________________________
Molecule = 1PSN. Final optimized geometry with frequency calculation.
---------------------------------------------------------------------------------------
# opt=calcfc b3lyp/6-31g(d) geom=connectivity
---------------------------------------------------------
E(RB+HF-LYP) = -828.482870341 A.U.
------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.998883 2.725134 -0.354167
2 1 0 2.056081 2.643374 -0.082726
3 1 0 0.449010 3.113483 0.509391
4 1 0 0.923369 3.457356 -1.166046
5 6 0 0.427772 1.377333 -0.817655
6 1 0 1.041539 0.974249 -1.628905
7 7 0 0.322145 0.316548 0.213833
8 8 0 -0.803418 0.799991 1.032227
9 6 0 1.449044 0.154134 1.146262
10 1 0 1.660594 1.104040 1.662191
11 6 0 1.088500 -0.892744 2.213733
12 1 0 1.936320 -1.036166 2.891845
13 1 0 0.220509 -0.569544 2.792490
14 1 0 0.856859 -1.854330 1.743693
15 6 0 2.687518 -0.266253 0.367410
16 6 0 3.922665 0.340315 0.624864
17 6 0 2.630894 -1.299674 -0.579270
18 6 0 5.077335 -0.073947 -0.042486
19 1 0 3.981713 1.141537 1.358574
20 6 0 3.781258 -1.709959 -1.252691
21 1 0 1.675554 -1.771171 -0.790115
22 6 0 5.009305 -1.099875 -0.985406
23 1 0 6.027332 0.408574 0.172328
24 1 0 3.719634 -2.509630 -1.986507
25 1 0 5.905512 -1.421920 -1.509087
26 1 0 -4.475870 1.761265 -0.036005
27 6 0 -4.274323 0.692689 -0.084865
28 6 0 -2.955083 0.235045 -0.008550
29 6 0 -5.335049 -0.206465 -0.216829
30 6 0 -1.810305 1.223921 0.099384
31 6 0 -2.711234 -1.144363 -0.052780
32 6 0 -5.084609 -1.577883 -0.262635
33 1 0 -6.355050 0.165030 -0.273937
34 6 0 -1.049282 1.465175 -1.236412
35 1 0 -2.196111 2.170373 0.496504
Page 241
Annexure 3
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36 6 0 -3.769312 -2.043254 -0.177251
37 1 0 -1.687516 -1.499777 0.014442
38 1 0 -5.907940 -2.280885 -0.358709
39 1 0 -1.290170 0.675892 -1.953429
40 1 0 -1.304231 2.427919 -1.689077
41 1 0 -3.568670 -3.111406 -0.205509
---------------------------------------------------------------------------------------
Rotational constants (GHZ): 0.7924041 0.1723371 0.1599546
----------------------------------------------------------------------------------------
Zero-point correction= 0.351978 (Hartree/Particle)
Thermal correction to Energy= 0.369718
Thermal correction to Enthalpy= 0.370662
Thermal correction to Gibbs Free Energy= 0.304486
Sum of electronic and zero-point Energies= -828.130892
Sum of electronic and thermal Energies= -828.113153
Sum of electronic and thermal Enthalpies= -828.112208
Sum of electronic and thermal Free Energies= -828.178384
----------------------------------------------------------------------------------
________________________________________________________________________
Molecule = 1 PSX. Final optimized geometry with frequency calculation.
----------------------------------------------------------------------------------------
# opt=calcfc b3lyp/6-31g(d) geom=connectivity
----------------------------------------------------------
E(RB+HF-LYP) = -828.478962147 A.U.
-------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.064101 0.542761 1.873621
2 1 0 0.182469 0.319115 2.941207
3 1 0 -0.805465 1.195725 1.753540
4 1 0 0.949515 1.085784 1.530780
5 6 0 -0.128037 -0.752396 1.078712
6 1 0 -1.014376 -1.269098 1.463933
7 7 0 -0.319903 -0.435655 -0.371289
8 8 0 0.729004 -1.163291 -1.115277
9 6 0 -1.591716 -0.905795 -0.977497
10 1 0 -1.465243 -0.674692 -2.043053
11 6 0 -1.845707 -2.416836 -0.876666
12 1 0 -2.739053 -2.692737 -1.447163
13 1 0 -0.991822 -2.951901 -1.298018
14 1 0 -1.991070 -2.756861 0.154857
15 6 0 -2.719383 -0.017390 -0.455841
16 6 0 -2.634626 1.370405 -0.655210
17 6 0 -3.847316 -0.526094 0.196940
18 6 0 -3.646266 2.221074 -0.215971
19 1 0 -1.756823 1.776170 -1.149805
20 6 0 -4.865246 0.325256 0.638437
21 1 0 -3.947059 -1.594236 0.361746
22 6 0 -4.768873 1.700080 0.434370
23 1 0 -3.561071 3.291938 -0.382327
24 1 0 -5.733492 -0.092516 1.141649
25 1 0 -5.560180 2.362016 0.776246
26 1 0 4.155878 -1.381960 1.147893
27 6 0 4.005693 -0.467323 0.576762
28 6 0 2.837901 -0.303279 -0.180198
29 6 0 4.984297 0.525983 0.601425
30 6 0 1.798187 -1.419161 -0.217328
31 6 0 2.672695 0.869159 -0.923686
32 6 0 4.807484 1.699867 -0.134619
33 1 0 5.885182 0.382547 1.192677
34 6 0 1.090365 -1.696584 1.122696
35 1 0 2.278022 -2.330188 -0.597343
36 6 0 3.649957 1.866578 -0.895975
37 1 0 1.771770 0.990012 -1.514964
38 1 0 5.568314 2.475753 -0.116736
39 1 0 1.728089 -1.510454 1.990753
40 1 0 0.766250 -2.741884 1.150366
41 1 0 3.506413 2.775551 -1.474830
---------------------------------------------------------------------------------------
Rotational constants (GHZ): 0.7546344 0.1850000 0.1683392
---------------------------------------------------------------------------------------
Page 242
Annexure 3
93
Zero-point correction= 0.352153 (Hartree/Particle)
Thermal correction to Energy= 0.369737
Thermal correction to Enthalpy= 0.370682
Thermal correction to Gibbs Free Energy= 0.304824
Sum of electronic and zero-point Energies= -828.126809
Sum of electronic and thermal Energies= -828.109225
Sum of electronic and thermal Enthalpies= -828.108280
Sum of electronic and thermal Free Energies= -828.174138
----------------------------------------------------------------------------------
_______________________________________________________________________
Transition state = 1 TRN. Final optimized geometry with frequency calculation.
-----------------------------------------------------------------------------------------
# opt=(calcfc,qst3) freq b3lyp/6-31g(d) geom=connectivity
------------------------------------------------------------------------
E(RB+HF-LYP) = -828.423838630 A.U.
-----------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -0.800252 3.358597 -0.266064
2 1 0 0.112500 3.682381 0.235906
3 1 0 -1.656203 3.645578 0.359898
4 1 0 -0.896593 3.882304 -1.221797
5 6 0 -0.800243 1.864592 -0.479002
6 1 0 -1.614457 1.468446 -1.080807
7 7 0 -0.447061 1.071774 0.556099
8 8 0 0.616477 1.412809 1.204481
9 6 0 -0.771895 -0.396916 0.526586
10 1 0 -0.146314 -0.834193 -0.261646
11 6 0 -0.373207 -1.030598 1.862779
12 1 0 -0.571695 -2.106024 1.819354
13 1 0 0.686070 -0.864178 2.060391
14 1 0 -0.953438 -0.605965 2.688235
15 6 0 -2.232126 -0.635831 0.189025
16 6 0 -2.583744 -1.474358 -0.874867
17 6 0 -3.255101 -0.060876 0.958276
18 6 0 -3.924056 -1.741745 -1.163616
19 1 0 -1.800921 -1.925842 -1.480520
20 6 0 -4.593502 -0.320852 0.668863
21 1 0 -2.998018 0.599548 1.782293
22 6 0 -4.932619 -1.164535 -0.392530
23 1 0 -4.177224 -2.397553 -1.992458
24 1 0 -5.374043 0.134077 1.273097
25 1 0 -5.976371 -1.368000 -0.616291
26 1 0 1.976808 -0.900793 -2.035962
27 6 0 2.658152 -0.879660 -1.189703
28 6 0 2.761054 0.284884 -0.404125
29 6 0 3.433172 -2.004935 -0.916910
30 6 0 1.987441 1.505985 -0.670238
31 6 0 3.696511 0.277348 0.649469
32 6 0 4.347066 -1.996242 0.139382
33 1 0 3.332767 -2.889082 -1.541849
34 6 0 0.969065 1.651835 -1.608803
35 1 0 2.401598 2.407568 -0.229630
36 6 0 4.476397 -0.843629 0.918764
37 1 0 3.791376 1.164454 1.270616
38 1 0 4.955571 -2.872230 0.346992
39 1 0 0.703941 0.813654 -2.249945
40 1 0 0.842897 2.622073 -2.079624
41 1 0 5.186675 -0.819489 1.741486
--------------------------------------------------------------------------------------
Rotational constants (GHZ): 0.5966111 0.2037530 0.1788933
---------------------------------------------------------------------------------------
Zero-point correction= 0.347724 (Hartree/Particle)
Thermal correction to Energy= 0.366175
Thermal correction to Enthalpy= 0.367119
Thermal correction to Gibbs Free Energy= 0.299396
Sum of electronic and zero-point Energies= -828.076115
Sum of electronic and thermal Energies= -828.057664
Sum of electronic and thermal Enthalpies= -828.056720
Sum of electronic and thermal Free Energies= -828.124442
________________________________________________________________________
Page 243
Annexure 3
94
Transition state = 1 TRX. Final optimised geometry with frequency calculation.
-----------------------------------------------------------------------------------------
E(RB+HF-LYP) = -828.425407511 A.U.
-----------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.449403 -1.813582 -1.321284
2 1 0 1.415180 -1.329097 -1.465735
3 1 0 -0.044935 -1.895500 -2.299069
4 1 0 0.602076 -2.828066 -0.940757
5 6 0 -0.419461 -1.023695 -0.376102
6 1 0 -1.344291 -1.500027 -0.062603
7 7 0 -0.523310 0.311097 -0.567115
8 8 0 0.578402 0.948391 -0.798136
9 6 0 -1.584406 1.098960 0.142855
10 1 0 -1.242317 1.182380 1.186047
11 6 0 -1.647981 2.508480 -0.455712
12 1 0 -2.359123 3.112448 0.116360
13 1 0 -0.662034 2.973576 -0.423932
14 1 0 -1.983238 2.477143 -1.497350
15 6 0 -2.933757 0.405630 0.122865
16 6 0 -3.593597 0.106474 1.320357
17 6 0 -3.566184 0.090039 -1.089645
18 6 0 -4.857437 -0.488276 1.312956
19 1 0 -3.115530 0.344861 2.267989
20 6 0 -4.824184 -0.509877 -1.100150
21 1 0 -3.064030 0.308254 -2.028509
22 6 0 -5.475715 -0.798602 0.102062
23 1 0 -5.354865 -0.710277 2.253340
24 1 0 -5.298501 -0.750829 -2.047858
25 1 0 -6.457860 -1.263473 0.092814
26 1 0 3.175287 -2.141217 0.536577
27 6 0 3.686332 -1.202662 0.342724
28 6 0 3.030795 0.017932 0.597004
29 6 0 4.992837 -1.231151 -0.139693
30 6 0 1.666039 0.106996 1.122216
31 6 0 3.749221 1.205730 0.356598
32 6 0 5.686364 -0.041998 -0.375953
33 1 0 5.474914 -2.187937 -0.324827
34 6 0 0.788521 -0.951441 1.337285
35 1 0 1.398963 1.080282 1.521633
36 6 0 5.055307 1.178518 -0.122580
37 1 0 3.257811 2.158958 0.534781
38 1 0 6.706608 -0.066379 -0.749261
39 1 0 1.146994 -1.975133 1.270593
40 1 0 -0.010142 -0.811710 2.062489
41 1 0 5.582406 2.112092 -0.302661
---------------------------------------------------------------------------------
Rotational constants (GHZ): 0.9704071 0.1509260 0.1454273
----------------------------------------------------------------------------------
Zero-point correction= 0.347710 (Hartree/Particle)
Thermal correction to Energy= 0.366140
Thermal correction to Enthalpy= 0.367084
Thermal correction to Gibbs Free Energy= 0.299370
Sum of electronic and zero-point Energies= -828.077698
Sum of electronic and thermal Energies= -828.059267
Sum of electronic and thermal Enthalpies= -828.058323
Sum of electronic and thermal Free Energies= -828.126037
----------------------------------------------------------------------------------
_______________________________________________________________________
Transition state = 1 TSN. Final optimized geometry with frequency calculation.
---------------------------------------------------------------------------------------
# opt=qst3 freq b3lyp/6-31g(d) geom=connectivity
--------------------------------------------------------------
E(RB+HF-LYP) = -828.418011518 A.U.
----------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
Page 244
Annexure 3
95
1 6 0 0.853855 3.474039 -0.705384
2 1 0 1.549518 4.007039 -0.043348
3 1 0 -0.155887 3.826679 -0.491139
4 1 0 1.114673 3.724849 -1.738138
5 6 0 0.970737 1.980295 -0.475572
6 1 0 1.914423 1.538791 -0.785137
7 7 0 0.506453 1.499461 0.703564
8 8 0 -0.671240 1.887325 1.049251
9 6 0 1.110733 0.336899 1.457596
10 1 0 1.658349 0.818913 2.279128
11 6 0 0.013997 -0.523912 2.088295
12 1 0 0.483849 -1.281480 2.723987
13 1 0 -0.645217 0.098947 2.693450
14 1 0 -0.599794 -1.025187 1.336257
15 6 0 2.127568 -0.448048 0.645767
16 6 0 3.495069 -0.189302 0.811931
17 6 0 1.743482 -1.445938 -0.262445
18 6 0 4.455896 -0.896456 0.086901
19 1 0 3.809800 0.573101 1.521508
20 6 0 2.700621 -2.154071 -0.988836
21 1 0 0.691335 -1.676749 -0.397250
22 6 0 4.059917 -1.880801 -0.818753
23 1 0 5.510857 -0.680687 0.233779
24 1 0 2.384410 -2.925871 -1.685766
25 1 0 4.803860 -2.435718 -1.383961
26 1 0 -1.316168 -1.335225 -1.672996
27 6 0 -2.143993 -1.152216 -0.994070
28 6 0 -2.442545 0.167922 -0.596640
29 6 0 -2.923925 -2.229241 -0.571912
30 6 0 -1.672320 1.328749 -1.036473
31 6 0 -3.577431 0.355856 0.221691
32 6 0 -4.033896 -2.020782 0.247775
33 1 0 -2.671217 -3.234594 -0.900340
34 6 0 -0.461146 1.302800 -1.736845
35 1 0 -2.189605 2.279675 -0.953199
36 6 0 -4.357763 -0.716564 0.637388
37 1 0 -3.826546 1.363744 0.544059
38 1 0 -4.644819 -2.859311 0.570666
39 1 0 -0.045090 0.342942 -2.035179
40 1 0 -0.292458 2.087905 -2.469344
41 1 0 -5.222670 -0.537984 1.271515
--------------------------------------------------------------------------------------
Rotational constants (GHZ): 0.5229704 0.2426605 0.2014310
--------------------------------------------------------------------------------------
Zero-point correction= 0.348140 (Hartree/Particle)
Thermal correction to Energy= 0.366400
Thermal correction to Enthalpy= 0.367344
Thermal correction to Gibbs Free Energy= 0.300950
Sum of electronic and zero-point Energies= -828.069872
Sum of electronic and thermal Energies= -828.051612
Sum of electronic and thermal Enthalpies= -828.050668
Sum of electronic and thermal Free Energies= -828.117062
--------------------------------------------------------------------------------
________________________________________________________________________
Transition state = 1 TSX. Final optimized geometry with frequency calculation.
----------------------------------------------------------------------------------------
# opt=qst3 freq b3lyp/6-31g(d) geom=connectivity
-------------------------------------------------------------
E(RB+HF-LYP) = -828.420823447 A.U.
------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -0.360966 -2.129018 -0.359165
2 1 0 -0.515995 -2.862580 0.437864
3 1 0 0.183354 -2.628781 -1.171846
4 1 0 -1.327352 -1.801371 -0.743119
5 6 0 0.449550 -0.957935 0.148149
6 1 0 1.381537 -1.216641 0.644845
7 7 0 0.545214 0.130753 -0.652026
8 8 0 -0.555668 0.584946 -1.152707
9 6 0 1.671985 1.125179 -0.580089
10 1 0 1.711590 1.491585 -1.611847
Page 245
Annexure 3
96
11 6 0 1.308438 2.321013 0.305161
12 1 0 2.077658 3.095158 0.218599
13 1 0 0.357217 2.733603 -0.036584
14 1 0 1.211143 2.051957 1.361207
15 6 0 3.002611 0.454525 -0.279302
16 6 0 3.601163 -0.331220 -1.276741
17 6 0 3.661823 0.585784 0.948896
18 6 0 4.818677 -0.970906 -1.053789
19 1 0 3.101667 -0.439245 -2.236921
20 6 0 4.884203 -0.052432 1.175617
21 1 0 3.230083 1.194219 1.737545
22 6 0 5.465460 -0.832887 0.177063
23 1 0 5.265716 -1.572062 -1.841068
24 1 0 5.381815 0.065428 2.134614
25 1 0 6.417237 -1.326771 0.353251
26 1 0 -3.141934 -1.708548 1.386661
27 6 0 -3.664219 -0.983444 0.769423
28 6 0 -3.046365 0.243485 0.455519
29 6 0 -4.948552 -1.279446 0.318672
30 6 0 -1.709364 0.616317 0.917904
31 6 0 -3.781180 1.161838 -0.321353
32 6 0 -5.658425 -0.356500 -0.452872
33 1 0 -5.401259 -2.233019 0.579194
34 6 0 -0.801546 -0.206744 1.587951
35 1 0 -1.492450 1.677167 0.863907
36 6 0 -5.065555 0.868815 -0.768768
37 1 0 -3.318398 2.108971 -0.586870
38 1 0 -6.661693 -0.587727 -0.800484
39 1 0 -1.139804 -1.162828 1.979742
40 1 0 -0.052312 0.271813 2.213274
41 1 0 -5.605399 1.596285 -1.369794
---------------------------------------------------------------------
Rotational constants (GHZ): 0.9961858 0.1510407 0.1459870
--------------------------------------------------------------------------------
Zero-point correction= 0.348140 (Hartree/Particle)
Thermal correction to Energy= 0.366480
Thermal correction to Enthalpy= 0.367424
Thermal correction to Gibbs Free Energy= 0.299345
Sum of electronic and zero-point Energies= -828.072683
Sum of electronic and thermal Energies= -828.054343
Sum of electronic and thermal Enthalpies= -828.053399
Sum of electronic and thermal Free Energies= -828.121478
--------------------------------------------------------------------------------
________________________________________________________________________
________________________________________________________________________
Molecule = E2. Final optimization geometry with frequency calculation.
-------------------------------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
-----------------------------------------------------
E(RB+HF-LYP) = -193.108432428 A.U.
----------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -1.511830 -0.529368 -0.000005
2 1 0 -1.043184 -1.508005 0.000011
3 1 0 -2.597648 -0.492710 -0.000018
4 6 0 -0.781877 0.584088 -0.000008
5 1 0 -1.264671 1.561721 -0.000023
6 6 0 0.718437 0.630946 0.000010
7 1 0 1.058261 1.200952 -0.883973
8 1 0 1.058231 1.200951 0.884010
9 8 0 1.252798 -0.683462 0.000030
10 1 0 2.218249 -0.609210 -0.000224
-----------------------------------------------------------------------------------------
Rotational constants (GHZ): 17.1606430 5.9856185 4.5639885
-----------------------------------------------------------------------------------------
Zero-point correction= 0.084998 (Hartree/Particle)
Thermal correction to Energy= 0.090004
Thermal correction to Enthalpy= 0.090948
Thermal correction to Gibbs Free Energy= 0.057841
Page 246
Annexure 3
97
Sum of electronic and zero-point Energies= -193.023435
Sum of electronic and thermal Energies= -193.018428
Sum of electronic and thermal Enthalpies= -193.017484
Sum of electronic and thermal Free Energies= -193.050592
----------------------------------------------------------------------------
________________________________________________________________________
Molecule = N2. Final optimization geometry frequency calculation.
-------------------------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------------------
E(RB+HF-LYP) = -479.480661271 A.U.
---------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -1.066102 -0.659969 0.420240
2 1 0 -1.205010 -1.711466 0.154278
3 6 0 0.380561 -0.279463 0.155325
4 6 0 0.814658 1.052840 0.211123
5 6 0 1.313959 -1.286775 -0.117249
6 6 0 2.157156 1.362196 -0.005395
7 1 0 0.089979 1.838230 0.396500
8 6 0 2.659405 -0.976765 -0.322917
9 1 0 0.987938 -2.323969 -0.165133
10 6 0 3.084079 0.350767 -0.268181
11 1 0 2.480448 2.399167 0.032328
12 1 0 3.371049 -1.771540 -0.530348
13 1 0 4.129996 0.596724 -0.431392
14 6 0 -1.503393 -0.438175 1.869233
15 1 0 -2.534868 -0.774861 2.018880
16 1 0 -0.846856 -1.006779 2.534648
17 1 0 -1.443268 0.620818 2.125482
18 7 0 -1.994864 0.124344 -0.486507
19 6 0 -2.503115 -0.462152 -1.536112
20 1 0 -3.147035 0.124549 -2.176678
21 1 0 -2.258943 -1.494024 -1.741519
22 8 0 -2.210330 1.332215 -0.155988
---------------------------------------------------------------------
Rotational constants (GHZ): 2.1416719 0.7223104 0.6921257
--------------------------------------------------------------------------------
Zero-point correction= 0.183894 (Hartree/Particle)
Thermal correction to Energy= 0.193865
Thermal correction to Enthalpy= 0.194809
Thermal correction to Gibbs Free Energy= 0.147835
Sum of electronic and zero-point Energies= -479.296767
Sum of electronic and thermal Energies= -479.286796
Sum of electronic and thermal Enthalpies= -479.285852
Sum of electronic and thermal Free Energies= -479.332826
-------------------------------------------------------------------------------
________________________________________________________________________
Molecule = 2 PRN (PR). Final optimization geometry with frequency calculation.
--------------------------------------------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
------------------------------------------------------
E(RB+HF-LYP) = -672.639134109
-----------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -2.238820 -1.027039 1.197284
2 1 0 -2.426553 -1.941867 0.628526
3 1 0 -2.632266 -1.175402 2.206785
4 6 0 -2.876781 0.190420 0.481631
5 1 0 -3.606734 0.708183 1.117428
6 6 0 -3.520423 -0.168626 -0.863423
7 1 0 -3.872225 0.749602 -1.356797
8 1 0 5.126953 -1.654210 -0.386546
9 6 0 4.201081 -1.095895 -0.275943
Page 247
Annexure 3
98
10 6 0 3.138527 -1.315220 -1.156266
11 6 0 4.064612 -0.158000 0.747686
12 6 0 1.951269 -0.596977 -1.017609
13 1 0 3.235554 -2.046795 -1.954464
14 6 0 2.871470 0.553644 0.890027
15 1 0 4.883549 0.017489 1.440545
16 6 0 1.803930 0.347197 0.009220
17 1 0 1.122279 -0.772993 -1.696832
18 1 0 2.768498 1.279061 1.694128
19 6 0 0.529549 1.168841 0.138408
20 1 0 0.540088 1.686451 1.114236
21 6 0 0.433421 2.226971 -0.971750
22 7 0 -0.630474 0.266872 0.078095
23 1 0 -0.460746 2.840762 -0.842035
24 1 0 1.316530 2.873672 -0.944971
25 1 0 0.387372 1.746515 -1.954630
26 6 0 -0.748998 -0.652640 1.221817
27 8 0 -1.810456 1.123912 0.286967
28 1 0 -0.483235 -0.150220 2.166854
29 1 0 -0.083509 -1.505744 1.073914
30 1 0 -2.764674 -0.627170 -1.506883
31 8 0 -4.563608 -1.127887 -0.723905
32 1 0 -5.298085 -0.699709 -0.256905
---------------------------------------------------------------------
Rotational constants (GHZ): 1.3621612 0.2934313 0.2814692
-----------------------------------------------------------------------------------
Zero-point correction= 0.276010 (Hartree/Particle)
Thermal correction to Energy= 0.290252
Thermal correction to Enthalpy= 0.291196
Thermal correction to Gibbs Free Energy= 0.233869
Sum of electronic and zero-point Energies= -672.363124
Sum of electronic and thermal Energies= -672.348882
Sum of electronic and thermal Enthalpies= -672.347938
Sum of electronic and thermal Free Energies= -672.405265
------------------------------------------------------------------------------
________________________________________________________________________
Molecule = 2 PRX (PR). Final optimized geometry with frequency calculation.
-----------------------------------------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
----------------------------------------------------
E(RB+HF-LYP) = -672.639134131 A.U.
------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -2.238814 -1.026625 1.197981
2 1 0 -2.427062 -1.941798 0.629972
3 1 0 -2.631871 -1.173999 2.207773
4 6 0 -2.876779 0.190573 0.481746
5 1 0 -3.607068 0.708320 1.117142
6 6 0 -3.519793 -0.169075 -0.863508
7 1 0 -3.871916 0.748893 -1.357137
8 1 0 -2.763418 -0.627187 -1.506544
9 8 0 -4.562561 -1.128840 -0.724394
10 1 0 -5.297441 -0.701002 -0.257764
11 1 0 5.126427 -1.654748 -0.386322
12 6 0 4.200674 -1.096203 -0.275824
13 6 0 3.138374 -1.314863 -1.156643
14 6 0 4.064110 -0.158700 0.748142
15 6 0 1.951264 -0.596359 -1.018097
16 1 0 3.235513 -2.046120 -1.955126
17 6 0 2.871097 0.553223 0.890361
18 1 0 4.882860 0.016279 1.441357
19 6 0 1.803822 0.347418 0.009101
20 1 0 1.122463 -0.771888 -1.697680
21 1 0 2.768068 1.278378 1.694694
22 6 0 0.529470 1.169157 0.138252
23 1 0 0.540050 1.686782 1.114052
24 6 0 0.433220 2.227217 -0.971951
25 7 0 -0.630570 0.267114 0.078069
26 1 0 -0.461014 2.840902 -0.842206
27 1 0 1.316262 2.874017 -0.945230
Page 248
Annexure 3
99
28 1 0 0.387175 1.746720 -1.954809
29 6 0 -0.748869 -0.652462 1.221811
30 8 0 -1.810623 1.124178 0.287251
31 1 0 -0.083635 -1.505695 1.073510
32 1 0 -0.482588 -0.150166 2.166748
---------------------------------------------------------------------------------------
Rotational constants (GHZ): 1.3616664 0.2934772 0.2815193
----------------------------------------------------------------------------------------
Zero-point correction= 0.276007 (Hartree/Particle)
Thermal correction to Energy= 0.290250
Thermal correction to Enthalpy= 0.291195
Thermal correction to Gibbs Free Energy= 0.233866
Sum of electronic and zero-point Energies= -672.363127
Sum of electronic and thermal Energies= -672.348884
Sum of electronic and thermal Enthalpies= -672.347940
Sum of electronic and thermal Free Energies= -672.405268
--------------------------------------------------------------------------------
_______________________________________________________________________
Molecule = 2 PSN (PS). Final optimization geometry with frequency calculation.
--------------------------------------------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
-------------------------------------------------
E(RB+HF-LYP) = -672.636684289 A.U.
-----------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -0.040748 0.404095 0.535272
2 1 0 0.441408 1.082024 -0.185618
3 6 0 -1.506081 0.244483 0.159255
4 6 0 -2.306433 -0.733431 0.769075
5 6 0 -2.094644 1.103329 -0.776752
6 6 0 -3.659346 -0.844250 0.449764
7 1 0 -1.854190 -1.412890 1.485022
8 6 0 -3.451104 0.999281 -1.092718
9 1 0 -1.485669 1.865626 -1.258501
10 6 0 -4.237694 0.023307 -0.480389
11 1 0 -4.264993 -1.609368 0.929050
12 1 0 -3.890089 1.677697 -1.819917
13 1 0 -5.292771 -0.063038 -0.726793
14 6 0 0.108096 1.030491 1.928237
15 1 0 1.162182 1.196687 2.157220
16 1 0 -0.417179 1.990664 1.958424
17 1 0 -0.320388 0.374151 2.692988
18 7 0 0.602496 -0.937912 0.528434
19 6 0 0.728248 -1.545195 -0.802544
20 1 0 0.865409 -2.624787 -0.672584
21 1 0 -0.182138 -1.376804 -1.380793
22 8 0 1.978106 -0.808802 0.960519
23 1 0 2.785354 1.849488 -1.315866
24 8 0 2.937859 1.771645 -0.362506
25 6 0 3.683110 0.583785 -0.128588
26 6 0 2.869611 -0.714131 -0.180155
27 1 0 4.099503 0.686021 0.878009
28 1 0 4.528835 0.500117 -0.830368
29 6 0 1.988330 -0.918201 -1.421237
30 1 0 3.583318 -1.545329 -0.077667
31 1 0 1.747903 0.035209 -1.904321
32 1 0 2.460247 -1.564205 -2.166748
---------------------------------------------------------------------------------------
Rotational constants (GHZ): 1.3006881 0.3379495 0.3288958
---------------------------------------------------------------------------------------
Zero-point correction= 0.276015 (Hartree/Particle)
Thermal correction to Energy= 0.290145
Thermal correction to Enthalpy= 0.291089
Thermal correction to Gibbs Free Energy= 0.234323
Sum of electronic and zero-point Energies= -672.360669
Sum of electronic and thermal Energies= -672.346539
Sum of electronic and thermal Enthalpies= -672.345595
Sum of electronic and thermal Free Energies= -672.402362
------------------------------------------------------------------------------
Page 249
Annexure 3
100
Molecule = 2PSX (PS). Final potimized geometry with frequency calculation.
---------------------------------------------------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
---------------------------------------------------
E(RB+HF-LYP) = -672.636686128 A.U.
--------------------------------------------------
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 1.976579 -0.857207 -1.455912
2 1 0 1.726194 0.114725 -1.894767
3 1 0 2.446304 -1.467073 -2.232673
4 6 0 2.865616 -0.702796 -0.213177
5 1 0 3.582710 -1.535088 -0.151750
6 6 0 3.675522 0.594344 -0.107624
7 1 0 4.076124 0.662872 0.908138
8 1 0 4.532239 0.535782 -0.798635
9 8 0 2.932922 1.789332 -0.311643
10 1 0 2.780572 1.890711 -1.262844
11 1 0 -5.284535 -0.023703 -0.745561
12 6 0 -4.230634 0.049750 -0.490140
13 6 0 -3.662760 -0.847662 0.417962
14 6 0 -3.435073 1.038929 -1.068631
15 6 0 -2.311458 -0.753253 0.749040
16 1 0 -4.275367 -1.623227 0.870869
17 6 0 -2.080194 1.126549 -0.741032
18 1 0 -3.865776 1.740684 -1.778429
19 6 0 -1.502140 0.237903 0.173426
20 1 0 -1.867647 -1.455884 1.447764
21 1 0 -1.464281 1.899369 -1.196462
22 6 0 -0.038350 0.377470 0.562538
23 1 0 0.448459 1.085914 -0.124936
24 6 0 0.105614 0.939992 1.983140
25 7 0 0.603395 -0.963992 0.499025
26 1 0 1.159430 1.084913 2.227760
27 1 0 -0.410141 1.903318 2.052047
28 1 0 -0.335008 0.254994 2.715130
29 6 0 0.725356 -1.518267 -0.855268
30 8 0 1.981432 -0.851493 0.928327
31 1 0 -0.189849 -1.337081 -1.421868
32 1 0 0.873510 -2.600512 -0.766368
---------------------------------------------------------------------
Rotational constants (GHZ): 1.2947282 0.3384939 0.3299917
--------------------------------------------------------------------------------------------------------------
Zero-point correction= 0.276046 (Hartree/Particle)
Thermal correction to Energy= 0.290157
Thermal correction to Enthalpy= 0.291101
Thermal correction to Gibbs Free Energy= 0.234434
Sum of electronic and zero-point Energies= -672.360640
Sum of electronic and thermal Energies= -672.346529
Sum of electronic and thermal Enthalpies= -672.345585
Sum of electronic and thermal Free Energies= -672.402253
-------------------------------------------------------------------------------
________________________________________________________________________
Transition state = 2TRN. Final optimized geometry with frequency calculation.
-----------------------------------------------------------------------------------------
# opt=qst3 freq b3lyp/6-31g(d) geom=connectivity
--------------------------------------------------------------
E(RB+HF-LYP) = -672.564967113 A.U.
-----------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -1.779910 0.576650 -1.703294
2 1 0 -1.039112 1.341129 -1.483341
3 1 0 -1.991734 0.454191 -2.761739
4 6 0 -2.795616 0.325444 -0.781702
5 1 0 -3.684486 -0.199730 -1.121314
6 6 0 -3.004522 1.111979 0.492471
7 1 0 -3.951272 1.674734 0.404544
8 1 0 -3.113115 0.447763 1.353115
9 8 0 -1.941922 2.002750 0.829239
Page 250
Annexure 3
101
10 1 0 -1.858869 2.636407 0.098787
11 1 0 4.472131 1.750121 -0.660654
12 6 0 3.619815 1.137325 -0.379213
13 6 0 2.412316 1.737844 -0.013159
14 6 0 3.725760 -0.253282 -0.375766
15 6 0 1.316340 0.957231 0.353579
16 1 0 2.325662 2.821536 -0.007710
17 6 0 2.627664 -1.034483 -0.009418
18 1 0 4.661204 -0.731853 -0.653595
19 6 0 1.411609 -0.443423 0.357386
20 1 0 0.381628 1.431931 0.638035
21 1 0 2.717167 -2.118881 -0.002734
22 6 0 0.242242 -1.322348 0.770370
23 1 0 0.630049 -2.342374 0.892498
24 6 0 -0.393719 -0.911127 2.100083
25 7 0 -0.811496 -1.461412 -0.304656
26 1 0 -1.202391 -1.596721 2.358071
27 1 0 0.373748 -0.950934 2.879938
28 1 0 -0.797193 0.103071 2.060582
29 6 0 -0.614539 -1.144342 -1.593322
30 8 0 -2.057188 -1.538918 0.049539
31 1 0 -1.260366 -1.666940 -2.288018
32 1 0 0.405652 -0.959039 -1.912178
--------------------------------------------------------------------------------------
Rotational constants (GHZ): 0.9770280 0.4177893 0.3789901
---------------------------------------------------------------------------------------
Zero-point correction= 0.272362 (Hartree/Particle)
Thermal correction to Energy= 0.286791
Thermal correction to Enthalpy= 0.287735
Thermal correction to Gibbs Free Energy= 0.231042
Sum of electronic and zero-point Energies= -672.292605
Sum of electronic and thermal Energies= -672.278176
Sum of electronic and thermal Enthalpies= -672.277232
Sum of electronic and thermal Free Energies= -672.333925
-----------------------------------------------------------------------------
________________________________________________________________________
Transition state = 2 TRX. Final optimized geometry with frequency calculation.
-----------------------------------------------------------------------------------------
# opt=qst3 freq b3lyp/6-31g(d) geom=connectivity
-------------------------------------------------------------
E(RB+HF-LYP) = -672.571197863 A.U.
-----------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -2.120684 -1.264115 0.786335
2 1 0 -2.464614 -2.140205 0.244787
3 1 0 -1.421376 -1.466656 1.593727
4 6 0 -2.927363 -0.141431 0.849278
5 1 0 -2.814144 0.567086 1.663802
6 6 0 -4.182092 0.009275 0.022795
7 1 0 -5.040724 0.203159 0.689213
8 1 0 -4.082893 0.875735 -0.637952
9 8 0 -4.449618 -1.094261 -0.837682
10 1 0 -4.651414 -1.856004 -0.271943
11 1 0 5.202067 -1.511928 -0.476291
12 6 0 4.253019 -1.018410 -0.285014
13 6 0 3.642782 -0.258101 -1.286295
14 6 0 3.635984 -1.141708 0.959601
15 6 0 2.427377 0.378730 -1.041254
16 1 0 4.115869 -0.159969 -2.259817
17 6 0 2.414114 -0.508877 1.199509
18 1 0 4.101134 -1.732447 1.744278
19 6 0 1.797039 0.261288 0.207158
20 1 0 1.956889 0.963797 -1.826919
21 1 0 1.935581 -0.611003 2.171063
22 6 0 0.493581 0.980827 0.495891
23 1 0 0.146569 0.701884 1.502094
24 6 0 0.640759 2.505253 0.441750
25 7 0 -0.606996 0.562526 -0.433257
26 1 0 -0.321772 2.978392 0.641066
27 1 0 1.370965 2.826822 1.190857
28 1 0 0.991377 2.831835 -0.542629
Page 251
Annexure 3
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29 6 0 -0.774129 -0.723021 -0.772059
30 8 0 -1.693158 1.267229 -0.359775
31 1 0 -1.530105 -0.900460 -1.525766
32 1 0 0.095441 -1.369722 -0.753286
--------------------------------------------------------------------------------------------
Rotational constants (GHZ): 1.3299882 0.2878460 0.2715446
----------------------------------------------------------------------------------------------
Zero-point correction= 0.271580 (Hartree/Particle)
Thermal correction to Energy= 0.286397
Thermal correction to Enthalpy= 0.287341
Thermal correction to Gibbs Free Energy= 0.228188
Sum of electronic and zero-point Energies= -672.299618
Sum of electronic and thermal Energies= -672.284801
Sum of electronic and thermal Enthalpies= -672.283857
Sum of electronic and thermal Free Energies= -672.343009
-----------------------------------------------------------------------------
________________________________________________________________________
Transition state = 2TSN. Final optimised geometry with frequency calculation.
---------------------------------------------------------------------------------------
# opt=qst3 freq b3lyp/6-31g(d) geom=connectivity
-----------------------------------------------------------------
E(RB+HF-LYP) = -672.570974478 A.U.
------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -0.049623 -0.428486 0.755450
2 1 0 0.528331 0.480251 0.966375
3 6 0 -1.452255 -0.044263 0.326091
4 6 0 -2.390786 -1.013019 -0.061986
5 6 0 -1.846245 1.299044 0.345011
6 6 0 -3.686395 -0.645046 -0.421582
7 1 0 -2.100780 -2.060116 -0.089707
8 6 0 -3.146043 1.670228 -0.006485
9 1 0 -1.128124 2.058937 0.644374
10 6 0 -4.069430 0.698637 -0.392368
11 1 0 -4.399859 -1.407916 -0.722259
12 1 0 -3.434085 2.717917 0.019515
13 1 0 -5.080874 0.984111 -0.668926
14 6 0 -0.043528 -1.315529 2.005753
15 1 0 0.981135 -1.586632 2.264756
16 1 0 -0.495939 -0.769860 2.839510
17 1 0 -0.616818 -2.234635 1.844451
18 7 0 0.711161 -1.128800 -0.335921
19 6 0 0.590847 -0.763667 -1.617659
20 1 0 1.082529 -1.420388 -2.322810
21 1 0 -0.329251 -0.282135 -1.926930
22 8 0 1.880264 -1.581169 0.000504
23 1 0 2.580617 2.451463 0.353066
24 8 0 2.539723 1.733867 1.004289
25 6 0 3.449020 0.723043 0.575687
26 6 0 3.109772 0.078749 -0.749037
27 1 0 3.464820 -0.021332 1.374775
28 1 0 4.469487 1.142531 0.508706
29 6 0 2.233726 0.621025 -1.677017
30 1 0 3.843038 -0.649859 -1.084448
31 1 0 1.698771 1.538415 -1.442292
32 1 0 2.404625 0.454979 -2.736207
---------------------------------------------------------------------------------------
Rotational constants (GHZ): 1.0976850 0.3533219 0.3373883
----------------------------------------------------------------------------------------
Zero-point correction= 0.271905 (Hartree/Particle)
Thermal correction to Energy= 0.286589
Thermal correction to Enthalpy= 0.287533
Thermal correction to Gibbs Free Energy= 0.229450
Sum of electronic and zero-point Energies= -672.299070
Sum of electronic and thermal Energies= -672.284385
Sum of electronic and thermal Enthalpies= -672.283441
Sum of electronic and thermal Free Energies= -672.341524
---------------------------------------------------------------------------------
________________________________________________________________________
Page 252
Annexure 3
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Transition state = 2TSX. Final optimized geometry with frequency calculation.
----------------------------------------------------------------------------------------
# opt=qst3 freq b3lyp/6-31g(d) geom=connectivity
-------------------------------------------------------------
E(RB+HF-LYP) = -672.570343926 A.U.
--------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -1.493065 -0.997640 1.181303
2 1 0 -2.334914 -1.090155 1.860327
3 1 0 -0.519887 -1.242156 1.597470
4 6 0 -1.707234 -1.200884 -0.171724
5 1 0 -0.902106 -1.546104 -0.810210
6 6 0 -3.079556 -1.259211 -0.773793
7 1 0 -3.099618 -0.637613 -1.680619
8 1 0 -3.301887 -2.298495 -1.080502
9 8 0 -4.043179 -0.803907 0.176154
10 1 0 -4.882310 -0.689157 -0.292499
11 1 0 3.864913 -2.655629 -0.233767
12 6 0 3.219767 -1.785576 -0.144639
13 6 0 2.442793 -1.372775 -1.229560
14 6 0 3.164501 -1.072291 1.052960
15 6 0 1.617773 -0.252826 -1.121926
16 1 0 2.481183 -1.923715 -2.165897
17 6 0 2.333843 0.044769 1.161042
18 1 0 3.767003 -1.382189 1.902842
19 6 0 1.551859 0.469446 0.079399
20 1 0 1.006529 0.056129 -1.962260
21 1 0 2.297377 0.597365 2.097808
22 6 0 0.672019 1.701715 0.220034
23 1 0 0.841774 2.134491 1.211508
24 6 0 0.952220 2.771524 -0.841122
25 7 0 -0.785910 1.376242 0.176746
26 1 0 0.366753 3.673683 -0.634551
27 1 0 2.015299 3.031427 -0.844055
28 1 0 0.673091 2.405474 -1.832098
29 6 0 -1.476100 1.088791 1.290309
30 8 0 -1.251984 0.876638 -0.926558
31 1 0 -2.552651 1.120467 1.184836
32 1 0 -1.050795 1.420397 2.233975
----------------------------------------------------------------------------------------
Rotational constants (GHZ): 0.9209061 0.4100940 0.3511866
-----------------------------------------------------------------------------------------
Zero-point correction= 0.271475 (Hartree/Particle)
Thermal correction to Energy= 0.286379
Thermal correction to Enthalpy= 0.287323
Thermal correction to Gibbs Free Energy= 0.228978
Sum of electronic and zero-point Energies= -672.298869
Sum of electronic and thermal Energies= -672.283965
Sum of electronic and thermal Enthalpies= -672.283021
Sum of electronic and thermal Free Energies= -672.341366
--------------------------------------------------------------------------------
_______________________________________________________________________
The image and IRC plot of the Transition states for 1st reactions (Scheme-1):
Fig. 5a. 1TSX image and the corresponding IRC plot
Page 253
Annexure 3
104
Fig. 5b. 1TSN image and the corresponding IRC plot
Fig. 5c. 1TRX image and the corresponding IRC plot
Fig. 5d. 1TRN image and the corresponding IRC plot
The image and IRC plot of the Transition states for 2nd reaction (Scheme-2):
Fig. 5e. 2TSX image and the corresponding IRC plot
Fig. 5f. 2TSN image and the corresponding IRC plot
Page 254
Annexure 3
105
Fig. 5g. 2TRX image and the corresponding IRC plot
Fig. 5h. 2TRN image and the corresponding IRC plot
Page 256
Annexure 4
106
1 trx nbo:
Wiberg bond index matrix in the NAO basis:
Atom 1 2 3 4 5 6 7 8 9
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0000 0.9142 0.9196 1.4421 0.0063 0.0178 0.0610 0.0012 0.0030
2. H 0.9142 0.0000 0.0003 0.0042 0.0102 0.0013 0.0004 0.0001 0.0000
3. H 0.9196 0.0003 0.0000 0.0033 0.0020 0.0089 0.0019 0.0000 0.0001
4. C 1.4421 0.0042 0.0033 0.0000 0.8877 1.1516 0.0524 0.0007 0.0034
5. H 0.0063 0.0102 0.0020 0.8877 0.0000 0.0036 0.0210 0.0000 0.0001
6. C 0.0178 0.0013 0.0089 1.1516 0.0036 0.0000 2.8061 0.0001 0.0001
7. N 0.0610 0.0004 0.0019 0.0524 0.0210 2.8061 0.0000 0.0001 0.0006
8. C 0.0012 0.0001 0.0000 0.0007 0.0000 0.0001 0.0001 0.0000 0.9215
9. H 0.0030 0.0000 0.0001 0.0034 0.0001 0.0001 0.0006 0.9215 0.0000
10. H 0.0004 0.0000 0.0000 0.0005 0.0000 0.0000 0.0002 0.8920 0.0006
11. H 0.0004 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.9210 0.0003
12. N 0.0422 0.0007 0.0008 0.0388 0.0006 0.0018 0.0075 0.9279 0.0049
13. N 0.4342 0.0026 0.0017 0.0497 0.0010 0.0058 0.0134 0.0308 0.0024
14. C 0.0047 0.0002 0.0007 0.0023 0.0001 0.0001 0.0005 0.0043 0.0002
15. O 0.0198 0.0002 0.0005 0.0031 0.0001 0.0007 0.0014 0.0145 0.0006
16. C 0.0018 0.0004 0.0001 0.0004 0.0000 0.0000 0.0000 0.0007 0.0001
17. H 0.0003 0.0001 0.0003 0.0001 0.0000 0.0000 0.0000 0.0002 0.0000
18. H 0.0002 0.0004 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000
19. H 0.0005 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
20. C 0.0025 0.0026 0.0026 0.2137 0.0004 0.0053 0.0312 0.0185 0.0104
21. H 0.0015 0.0000 0.0000 0.0013 0.0000 0.0013 0.0012 0.0135 0.0002
22. C 0.0005 0.0000 0.0000 0.0011 0.0001 0.0006 0.0004 0.0013 0.0003
23. C 0.0001 0.0003 0.0003 0.0121 0.0002 0.0003 0.0024 0.0022 0.0012
24. C 0.0003 0.0004 0.0003 0.0170 0.0000 0.0003 0.0047 0.0005 0.0006
25. C 0.0000 0.0000 0.0000 0.0002 0.0000 0.0001 0.0002 0.0011 0.0001
26. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0010 0.0004
27. C 0.0001 0.0000 0.0000 0.0003 0.0000 0.0000 0.0002 0.0006 0.0000
28. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0001 0.0003 0.0000 0.0000
29. C 0.0002 0.0003 0.0003 0.0115 0.0000 0.0001 0.0027 0.0003 0.0006
30. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
31. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
32. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Atom 10 11 12 13 14 15 16 17 18
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0004 0.0004 0.0422 0.4342 0.0047 0.0198 0.0018 0.0003 0.0002
2. H 0.0000 0.0000 0.0007 0.0026 0.0002 0.0002 0.0004 0.0001 0.0004
3. H 0.0000 0.0000 0.0008 0.0017 0.0007 0.0005 0.0001 0.0003 0.0000
4. C 0.0005 0.0000 0.0388 0.0497 0.0023 0.0031 0.0004 0.0001 0.0000
5. H 0.0000 0.0000 0.0006 0.0010 0.0001 0.0001 0.0000 0.0000 0.0000
6. C 0.0000 0.0000 0.0018 0.0058 0.0001 0.0007 0.0000 0.0000 0.0000
7. N 0.0002 0.0000 0.0075 0.0134 0.0005 0.0014 0.0000 0.0000 0.0000
8. C 0.8920 0.9210 0.9279 0.0308 0.0043 0.0145 0.0007 0.0002 0.0001
9. H 0.0006 0.0003 0.0049 0.0024 0.0002 0.0006 0.0001 0.0000 0.0000
10. H 0.0000 0.0012 0.0019 0.0030 0.0009 0.0150 0.0009 0.0000 0.0000
11. H 0.0012 0.0000 0.0018 0.0092 0.0008 0.0004 0.0002 0.0000 0.0000
12. N 0.0019 0.0018 0.0000 1.1141 0.0098 0.0073 0.0137 0.0001 0.0002
13. N 0.0030 0.0092 1.1141 0.0000 1.1850 0.1561 0.0127 0.0046 0.0015
14. C 0.0009 0.0008 0.0098 1.1850 0.0000 1.6570 0.9934 0.0042 0.0040
15. O 0.0150 0.0004 0.0073 0.1561 1.6570 0.0000 0.0544 0.0138 0.0150
16. C 0.0009 0.0002 0.0137 0.0127 0.9934 0.0544 0.0000 0.9156 0.9168
17. H 0.0000 0.0000 0.0001 0.0046 0.0042 0.0138 0.9156 0.0000 0.0008
18. H 0.0000 0.0000 0.0002 0.0015 0.0040 0.0150 0.9168 0.0008 0.0000
19. H 0.0000 0.0000 0.0007 0.0066 0.0027 0.0032 0.9183 0.0008 0.0007
20. C 0.0072 0.0013 1.3747 0.1172 0.0209 0.0185 0.0007 0.0006 0.0002
21. H 0.0002 0.0002 0.0030 0.0038 0.0003 0.0001 0.0002 0.0000 0.0000
22. C 0.0003 0.0008 0.0128 0.0112 0.0007 0.0004 0.0004 0.0000 0.0000
23. C 0.0008 0.0031 0.0183 0.0109 0.0012 0.0024 0.0001 0.0001 0.0000
24. C 0.0003 0.0001 0.0235 0.0119 0.0015 0.0024 0.0001 0.0001 0.0000
25. C 0.0000 0.0001 0.0011 0.0003 0.0000 0.0001 0.0000 0.0000 0.0000
26. H 0.0001 0.0003 0.0002 0.0002 0.0000 0.0000 0.0000 0.0000 0.0000
27. C 0.0001 0.0001 0.0003 0.0004 0.0001 0.0000 0.0000 0.0000 0.0000
28. H 0.0000 0.0000 0.0003 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
29. C 0.0003 0.0003 0.0127 0.0093 0.0011 0.0021 0.0000 0.0001 0.0000
30. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
31. H 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
32. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Atom 19 20 21 22 23 24 25 26 27
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0005 0.0025 0.0015 0.0005 0.0001 0.0003 0.0000 0.0000 0.0001
2. H 0.0000 0.0026 0.0000 0.0000 0.0003 0.0004 0.0000 0.0000 0.0000
3. H 0.0000 0.0026 0.0000 0.0000 0.0003 0.0003 0.0000 0.0000 0.0000
4. C 0.0000 0.2137 0.0013 0.0011 0.0121 0.0170 0.0002 0.0001 0.0003
5. H 0.0000 0.0004 0.0000 0.0001 0.0002 0.0000 0.0000 0.0000 0.0000
Page 257
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107
6. C 0.0000 0.0053 0.0013 0.0006 0.0003 0.0003 0.0001 0.0000 0.0000
7. N 0.0000 0.0312 0.0012 0.0004 0.0024 0.0047 0.0002 0.0000 0.0002
8. C 0.0000 0.0185 0.0135 0.0013 0.0022 0.0005 0.0011 0.0010 0.0006
9. H 0.0000 0.0104 0.0002 0.0003 0.0012 0.0006 0.0001 0.0004 0.0000
10. H 0.0000 0.0072 0.0002 0.0003 0.0008 0.0003 0.0000 0.0001 0.0001
11. H 0.0000 0.0013 0.0002 0.0008 0.0031 0.0001 0.0001 0.0003 0.0001
12. N 0.0007 1.3747 0.0030 0.0128 0.0183 0.0235 0.0011 0.0002 0.0003
13. N 0.0066 0.1172 0.0038 0.0112 0.0109 0.0119 0.0003 0.0002 0.0004
14. C 0.0027 0.0209 0.0003 0.0007 0.0012 0.0015 0.0000 0.0000 0.0001
15. O 0.0032 0.0185 0.0001 0.0004 0.0024 0.0024 0.0001 0.0000 0.0000
16. C 0.9183 0.0007 0.0002 0.0004 0.0001 0.0001 0.0000 0.0000 0.0000
17. H 0.0008 0.0006 0.0000 0.0000 0.0001 0.0001 0.0000 0.0000 0.0000
18. H 0.0007 0.0002 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
19. H 0.0000 0.0002 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
20. C 0.0002 0.0000 0.8898 1.1214 0.0109 0.0147 0.0105 0.0011 0.0088
21. H 0.0000 0.8898 0.0000 0.0033 0.0069 0.0016 0.0001 0.0000 0.0003
22. C 0.0001 1.1214 0.0033 0.0000 1.3467 1.3504 0.0118 0.0030 0.0107
23. C 0.0000 0.0109 0.0069 1.3467 0.0000 0.0138 1.4608 0.9146 0.1042
24. C 0.0000 0.0147 0.0016 1.3504 0.0138 0.0000 0.1015 0.0085 1.4531
25. C 0.0000 0.0105 0.0001 0.0118 1.4608 0.1015 0.0000 0.0040 0.0109
26. H 0.0000 0.0011 0.0000 0.0030 0.9146 0.0085 0.0040 0.0000 0.0003
27. C 0.0000 0.0088 0.0003 0.0107 0.1042 1.4531 0.0109 0.0003 0.0000
28. H 0.0000 0.0017 0.0005 0.0028 0.0083 0.9095 0.0003 0.0004 0.0039
29. C 0.0000 0.0027 0.0003 0.0947 0.0114 0.0121 1.4182 0.0084 1.4269
30. H 0.0000 0.0003 0.0003 0.0081 0.0033 0.0003 0.9130 0.0021 0.0084
31. H 0.0000 0.0002 0.0001 0.0082 0.0003 0.0034 0.0083 0.0004 0.9111
32. H 0.0000 0.0003 0.0000 0.0002 0.0082 0.0084 0.0032 0.0003 0.0034
Atom 28 29 30 31 32
---- ------ ------ ------ ------ ------
1. C 0.0000 0.0002 0.0000 0.0000 0.0000
2. H 0.0000 0.0003 0.0000 0.0000 0.0000
3. H 0.0000 0.0003 0.0000 0.0000 0.0000
4. C 0.0001 0.0115 0.0000 0.0000 0.0000
5. H 0.0000 0.0000 0.0000 0.0000 0.0000
6. C 0.0001 0.0001 0.0000 0.0000 0.0000
7. N 0.0003 0.0027 0.0000 0.0000 0.0000
8. C 0.0000 0.0003 0.0000 0.0000 0.0000
9. H 0.0000 0.0006 0.0000 0.0000 0.0000
10. H 0.0000 0.0003 0.0000 0.0000 0.0000
11. H 0.0000 0.0003 0.0000 0.0000 0.0000
12. N 0.0003 0.0127 0.0000 0.0002 0.0000
13. N 0.0001 0.0093 0.0000 0.0000 0.0000
14. C 0.0000 0.0011 0.0000 0.0000 0.0000
15. O 0.0000 0.0021 0.0000 0.0000 0.0000
16. C 0.0000 0.0000 0.0000 0.0000 0.0000
17. H 0.0000 0.0001 0.0000 0.0000 0.0000
18. H 0.0000 0.0000 0.0000 0.0000 0.0000
19. H 0.0000 0.0000 0.0000 0.0000 0.0000
20. C 0.0017 0.0027 0.0003 0.0002 0.0003
21. H 0.0005 0.0003 0.0003 0.0001 0.0000
22. C 0.0028 0.0947 0.0081 0.0082 0.0002
23. C 0.0083 0.0114 0.0033 0.0003 0.0082
24. C 0.9095 0.0121 0.0003 0.0034 0.0084
25. C 0.0003 1.4182 0.9130 0.0083 0.0032
26. H 0.0004 0.0084 0.0021 0.0004 0.0003
27. C 0.0039 1.4269 0.0084 0.9111 0.0034
28. H 0.0000 0.0084 0.0004 0.0022 0.0004
29. C 0.0084 0.0000 0.0034 0.0034 0.9136
30. H 0.0004 0.0034 0.0000 0.0004 0.0020
31. H 0.0022 0.0034 0.0004 0.0000 0.0020
32. H 0.0004 0.9136 0.0020 0.0020 0.0000
Wiberg bond index, Totals by atom:
Atom 1
---- ------
1. C 3.8751
2. H 0.9390
3. H 0.9438
4. C 3.8978
5. H 0.9338
6. C 4.0062
7. N 3.0099
8. C 3.7545
9. H 0.9519
10. H 0.9261
11. H 0.9417
12. N 3.6220
13. N 3.1998
14. C 3.8969
15. O 1.9896
Page 258
Annexure 4
108
16. C 3.8314
17. H 0.9417
18. H 0.9401
19. H 0.9341
20. C 3.8911
21. H 0.9301
22. C 3.9926
23. C 3.9454
24. C 3.9413
25. C 3.9461
26. H 0.9457
27. C 3.9441
28. H 0.9396
29. C 3.9453
30. H 0.9421
31. H 0.9404
32. H 0.9421
-----------------------------0----------------------------o-------------------------
1trn nbo:
Wiberg bond index matrix in the NAO basis:
Atom 1 2 3 4 5 6 7 8 9
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0000 0.9196 0.9227 0.9061 0.9231 0.0323 0.0043 0.0056 0.0013
2. H 0.9196 0.0000 0.0009 0.0004 0.0017 0.0103 0.0005 0.0010 0.0000
3. H 0.9227 0.0009 0.0000 0.0005 0.0017 0.0015 0.0006 0.0002 0.0013
4. H 0.9061 0.0004 0.0005 0.0000 0.0032 0.0020 0.0001 0.0001 0.0001
5. N 0.9231 0.0017 0.0017 0.0032 0.0000 1.1325 0.0089 0.0196 0.0027
6. N 0.0323 0.0103 0.0015 0.0020 1.1325 0.0000 1.1788 0.1672 0.0108
7. C 0.0043 0.0005 0.0006 0.0001 0.0089 1.1788 0.0000 1.6798 0.9826
8. O 0.0056 0.0010 0.0002 0.0001 0.0196 0.1672 1.6798 0.0000 0.0602
9. C 0.0013 0.0000 0.0013 0.0001 0.0027 0.0108 0.9826 0.0602 0.0000
10. H 0.0002 0.0000 0.0001 0.0001 0.0007 0.0009 0.0026 0.0127 0.9296
11. H 0.0012 0.0000 0.0001 0.0000 0.0003 0.0088 0.0044 0.0069 0.9054
12. H 0.0003 0.0000 0.0003 0.0000 0.0001 0.0079 0.0038 0.0083 0.9131
13. C 0.0189 0.0009 0.0074 0.0121 1.3878 0.1519 0.0180 0.0187 0.0054
14. H 0.0140 0.0002 0.0003 0.0001 0.0021 0.0031 0.0003 0.0006 0.0000
15. C 0.0013 0.0010 0.0004 0.0004 0.0149 0.0111 0.0006 0.0009 0.0001
16. C 0.0021 0.0032 0.0008 0.0012 0.0194 0.0157 0.0009 0.0018 0.0008
17. C 0.0006 0.0001 0.0003 0.0008 0.0246 0.0148 0.0011 0.0019 0.0007
18. C 0.0011 0.0001 0.0001 0.0000 0.0007 0.0003 0.0000 0.0001 0.0000
19. H 0.0010 0.0002 0.0002 0.0003 0.0001 0.0001 0.0000 0.0000 0.0000
20. C 0.0006 0.0002 0.0001 0.0000 0.0007 0.0004 0.0001 0.0000 0.0000
21. H 0.0000 0.0000 0.0000 0.0000 0.0003 0.0001 0.0000 0.0000 0.0000
22. C 0.0004 0.0002 0.0002 0.0007 0.0137 0.0126 0.0008 0.0016 0.0007
23. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000
24. H 0.0000 0.0000 0.0000 0.0000 0.0002 0.0001 0.0000 0.0000 0.0000
25. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
26. C 0.0008 0.0002 0.0003 0.0017 0.0315 0.3734 0.0045 0.0084 0.0110
27. H 0.0000 0.0000 0.0000 0.0001 0.0011 0.0015 0.0005 0.0015 0.0001
28. H 0.0001 0.0000 0.0000 0.0000 0.0006 0.0021 0.0003 0.0009 0.0001
29. C 0.0007 0.0000 0.0004 0.0018 0.0313 0.0433 0.0019 0.0021 0.0019
30. H 0.0000 0.0000 0.0000 0.0001 0.0003 0.0007 0.0000 0.0000 0.0000
31. C 0.0006 0.0000 0.0000 0.0016 0.0005 0.0077 0.0002 0.0002 0.0004
32. N 0.0018 0.0000 0.0003 0.0017 0.0063 0.0137 0.0004 0.0004 0.0007
Atom 10 11 12 13 14 15 16 17 18
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0002 0.0012 0.0003 0.0189 0.0140 0.0013 0.0021 0.0006 0.0011
2. H 0.0000 0.0000 0.0000 0.0009 0.0002 0.0010 0.0032 0.0001 0.0001
3. H 0.0001 0.0001 0.0003 0.0074 0.0003 0.0004 0.0008 0.0003 0.0001
4. H 0.0001 0.0000 0.0000 0.0121 0.0001 0.0004 0.0012 0.0008 0.0000
5. N 0.0007 0.0003 0.0001 1.3878 0.0021 0.0149 0.0194 0.0246 0.0007
6. N 0.0009 0.0088 0.0079 0.1519 0.0031 0.0111 0.0157 0.0148 0.0003
7. C 0.0026 0.0044 0.0038 0.0180 0.0003 0.0006 0.0009 0.0011 0.0000
8. O 0.0127 0.0069 0.0083 0.0187 0.0006 0.0009 0.0018 0.0019 0.0001
9. C 0.9296 0.9054 0.9131 0.0054 0.0000 0.0001 0.0008 0.0007 0.0000
10. H 0.0000 0.0007 0.0005 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
11. H 0.0007 0.0000 0.0012 0.0002 0.0000 0.0000 0.0000 0.0000 0.0000
12. H 0.0005 0.0012 0.0000 0.0009 0.0000 0.0000 0.0001 0.0001 0.0000
13. C 0.0001 0.0002 0.0009 0.0000 0.8993 1.1334 0.0107 0.0140 0.0098
14. H 0.0000 0.0000 0.0000 0.8993 0.0000 0.0033 0.0077 0.0019 0.0001
15. C 0.0000 0.0000 0.0000 1.1334 0.0033 0.0000 1.3440 1.3407 0.0111
16. C 0.0000 0.0000 0.0001 0.0107 0.0077 1.3440 0.0000 0.0144 1.4508
17. C 0.0000 0.0000 0.0001 0.0140 0.0019 1.3407 0.0144 0.0000 0.1032
18. C 0.0000 0.0000 0.0000 0.0098 0.0001 0.0111 1.4508 0.1032 0.0000
19. H 0.0000 0.0000 0.0000 0.0013 0.0001 0.0031 0.9006 0.0080 0.0042
20. C 0.0000 0.0000 0.0000 0.0105 0.0003 0.0113 0.1010 1.4649 0.0109
21. H 0.0000 0.0000 0.0000 0.0016 0.0005 0.0028 0.0085 0.9147 0.0003
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22. C 0.0000 0.0000 0.0001 0.0025 0.0007 0.0924 0.0122 0.0116 1.4279
23. H 0.0000 0.0000 0.0000 0.0002 0.0003 0.0081 0.0035 0.0003 0.9108
24. H 0.0000 0.0000 0.0000 0.0002 0.0000 0.0083 0.0003 0.0034 0.0083
25. H 0.0000 0.0000 0.0000 0.0004 0.0000 0.0002 0.0084 0.0082 0.0034
26. C 0.0003 0.0001 0.0005 0.0032 0.0003 0.0003 0.0003 0.0002 0.0000
27. H 0.0000 0.0000 0.0000 0.0032 0.0000 0.0000 0.0005 0.0004 0.0000
28. H 0.0000 0.0000 0.0000 0.0014 0.0000 0.0000 0.0002 0.0002 0.0000
29. C 0.0001 0.0004 0.0001 0.1493 0.0005 0.0005 0.0142 0.0125 0.0001
30. H 0.0000 0.0000 0.0000 0.0006 0.0000 0.0000 0.0000 0.0000 0.0000
31. C 0.0000 0.0000 0.0000 0.0046 0.0001 0.0006 0.0017 0.0004 0.0004
32. N 0.0000 0.0001 0.0000 0.0303 0.0003 0.0008 0.0097 0.0024 0.0006
Atom 19 20 21 22 23 24 25 26 27
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0010 0.0006 0.0000 0.0004 0.0000 0.0000 0.0000 0.0008 0.0000
2. H 0.0002 0.0002 0.0000 0.0002 0.0000 0.0000 0.0000 0.0002 0.0000
3. H 0.0002 0.0001 0.0000 0.0002 0.0000 0.0000 0.0000 0.0003 0.0000
4. H 0.0003 0.0000 0.0000 0.0007 0.0000 0.0000 0.0000 0.0017 0.0001
5. N 0.0001 0.0007 0.0003 0.0137 0.0000 0.0002 0.0000 0.0315 0.0011
6. N 0.0001 0.0004 0.0001 0.0126 0.0001 0.0001 0.0000 0.3734 0.0015
7. C 0.0000 0.0001 0.0000 0.0008 0.0000 0.0000 0.0000 0.0045 0.0005
8. O 0.0000 0.0000 0.0000 0.0016 0.0000 0.0000 0.0000 0.0084 0.0015
9. C 0.0000 0.0000 0.0000 0.0007 0.0000 0.0000 0.0000 0.0110 0.0001
10. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0003 0.0000
11. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000
12. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0005 0.0000
13. C 0.0013 0.0105 0.0016 0.0025 0.0002 0.0002 0.0004 0.0032 0.0032
14. H 0.0001 0.0003 0.0005 0.0007 0.0003 0.0000 0.0000 0.0003 0.0000
15. C 0.0031 0.0113 0.0028 0.0924 0.0081 0.0083 0.0002 0.0003 0.0000
16. C 0.9006 0.1010 0.0085 0.0122 0.0035 0.0003 0.0084 0.0003 0.0005
17. C 0.0080 1.4649 0.9147 0.0116 0.0003 0.0034 0.0082 0.0002 0.0004
18. C 0.0042 0.0109 0.0003 1.4279 0.9108 0.0083 0.0034 0.0000 0.0000
19. H 0.0000 0.0003 0.0004 0.0079 0.0021 0.0004 0.0003 0.0001 0.0000
20. C 0.0003 0.0000 0.0039 1.4151 0.0084 0.9125 0.0032 0.0000 0.0000
21. H 0.0004 0.0039 0.0000 0.0086 0.0004 0.0022 0.0004 0.0000 0.0000
22. C 0.0079 1.4151 0.0086 0.0000 0.0033 0.0035 0.9139 0.0002 0.0004
23. H 0.0021 0.0084 0.0004 0.0033 0.0000 0.0004 0.0020 0.0000 0.0000
24. H 0.0004 0.9125 0.0022 0.0035 0.0004 0.0000 0.0020 0.0000 0.0000
25. H 0.0003 0.0032 0.0004 0.9139 0.0020 0.0020 0.0000 0.0000 0.0000
26. C 0.0001 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000 0.0000 0.9127
27. H 0.0000 0.0000 0.0000 0.0004 0.0000 0.0000 0.0000 0.9127 0.0000
28. H 0.0000 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000 0.9121 0.0004
29. C 0.0003 0.0002 0.0000 0.0109 0.0001 0.0000 0.0000 1.5055 0.0035
30. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0074 0.0110
31. C 0.0009 0.0002 0.0000 0.0002 0.0000 0.0000 0.0000 0.0198 0.0012
32. N 0.0051 0.0005 0.0000 0.0031 0.0001 0.0000 0.0000 0.0711 0.0003
Atom 28 29 30 31 32
---- ------ ------ ------ ------ ------
1. C 0.0001 0.0007 0.0000 0.0006 0.0018
2. H 0.0000 0.0000 0.0000 0.0000 0.0000
3. H 0.0000 0.0004 0.0000 0.0000 0.0003
4. H 0.0000 0.0018 0.0001 0.0016 0.0017
5. N 0.0006 0.0313 0.0003 0.0005 0.0063
6. N 0.0021 0.0433 0.0007 0.0077 0.0137
7. C 0.0003 0.0019 0.0000 0.0002 0.0004
8. O 0.0009 0.0021 0.0000 0.0002 0.0004
9. C 0.0001 0.0019 0.0000 0.0004 0.0007
10. H 0.0000 0.0001 0.0000 0.0000 0.0000
11. H 0.0000 0.0004 0.0000 0.0000 0.0001
12. H 0.0000 0.0001 0.0000 0.0000 0.0000
13. C 0.0014 0.1493 0.0006 0.0046 0.0303
14. H 0.0000 0.0005 0.0000 0.0001 0.0003
15. C 0.0000 0.0005 0.0000 0.0006 0.0008
16. C 0.0002 0.0142 0.0000 0.0017 0.0097
17. C 0.0002 0.0125 0.0000 0.0004 0.0024
18. C 0.0000 0.0001 0.0000 0.0004 0.0006
19. H 0.0000 0.0003 0.0000 0.0009 0.0051
20. C 0.0000 0.0002 0.0000 0.0002 0.0005
21. H 0.0000 0.0000 0.0000 0.0000 0.0000
22. C 0.0002 0.0109 0.0000 0.0002 0.0031
23. H 0.0000 0.0001 0.0000 0.0000 0.0001
24. H 0.0000 0.0000 0.0000 0.0000 0.0000
25. H 0.0000 0.0000 0.0000 0.0000 0.0000
26. C 0.9121 1.5055 0.0074 0.0198 0.0711
27. H 0.0004 0.0035 0.0110 0.0012 0.0003
28. H 0.0000 0.0032 0.0021 0.0095 0.0019
29. C 0.0032 0.0000 0.8873 1.1694 0.0549
30. H 0.0021 0.8873 0.0000 0.0036 0.0207
31. C 0.0095 1.1694 0.0036 0.0000 2.7791
32. N 0.0019 0.0549 0.0207 2.7791 0.0000
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Wiberg bond index, Totals by atom:
Atom 1
---- ------
1. C 3.7610
2. H 0.9407
3. H 0.9408
4. H 0.9353
5. N 3.6309
6. N 3.2056
7. C 3.8962
8. O 2.0008
9. C 3.8292
10. H 0.9488
11. H 0.9297
12. H 0.9375
13. C 3.8987
14. H 0.9359
15. C 3.9918
16. C 3.9345
17. C 3.9466
18. C 3.9444
19. H 0.9369
20. C 3.9454
21. H 0.9448
22. C 3.9456
23. H 0.9401
24. H 0.9419
25. H 0.9424
26. C 3.8660
27. H 0.9383
28. H 0.9354
29. C 3.8964
30. H 0.9340
31. C 4.0030
32. N 3.0066
--------------------------------o---------------------------------------------o----
1 tsx nbo:
Wiberg bond index matrix in the NAO basis:
Atom 1 2 3 4 5 6 7 8 9
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0000 0.9183 0.9197 0.9125 0.9292 0.0315 0.0042 0.0058 0.0014
2. H 0.9183 0.0000 0.0010 0.0003 0.0021 0.0103 0.0005 0.0011 0.0000
3. H 0.9197 0.0010 0.0000 0.0007 0.0014 0.0017 0.0007 0.0002 0.0011
4. H 0.9125 0.0003 0.0007 0.0000 0.0048 0.0029 0.0001 0.0001 0.0002
5. N 0.9292 0.0021 0.0014 0.0048 0.0000 1.1298 0.0093 0.0196 0.0027
6. N 0.0315 0.0103 0.0017 0.0029 1.1298 0.0000 1.1849 0.1693 0.0108
7. C 0.0042 0.0005 0.0007 0.0001 0.0093 1.1849 0.0000 1.6762 0.9813
8. O 0.0058 0.0011 0.0002 0.0001 0.0196 0.1693 1.6762 0.0000 0.0606
9. C 0.0014 0.0000 0.0011 0.0002 0.0027 0.0108 0.9813 0.0606 0.0000
10. H 0.0002 0.0000 0.0001 0.0002 0.0008 0.0009 0.0027 0.0127 0.9278
11. H 0.0011 0.0000 0.0000 0.0000 0.0004 0.0089 0.0044 0.0067 0.9027
12. H 0.0003 0.0000 0.0003 0.0000 0.0001 0.0080 0.0038 0.0083 0.9125
13. C 0.0193 0.0015 0.0061 0.0098 1.3722 0.1537 0.0175 0.0182 0.0056
14. H 0.0138 0.0001 0.0003 0.0001 0.0024 0.0035 0.0002 0.0006 0.0000
15. C 0.0013 0.0007 0.0002 0.0005 0.0140 0.0114 0.0006 0.0009 0.0001
16. C 0.0025 0.0026 0.0010 0.0018 0.0204 0.0172 0.0011 0.0021 0.0009
17. C 0.0005 0.0001 0.0002 0.0008 0.0272 0.0184 0.0013 0.0023 0.0010
18. C 0.0008 0.0001 0.0000 0.0001 0.0014 0.0003 0.0001 0.0001 0.0000
19. H 0.0013 0.0006 0.0001 0.0004 0.0002 0.0003 0.0000 0.0001 0.0000
20. C 0.0005 0.0002 0.0000 0.0000 0.0003 0.0004 0.0000 0.0001 0.0000
21. H 0.0000 0.0000 0.0000 0.0000 0.0003 0.0001 0.0000 0.0000 0.0000
22. C 0.0003 0.0003 0.0002 0.0008 0.0154 0.0155 0.0010 0.0021 0.0009
23. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
24. H 0.0000 0.0000 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000 0.0000
25. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
26. C 0.0010 0.0003 0.0001 0.0025 0.0324 0.3617 0.0044 0.0080 0.0111
27. H 0.0001 0.0000 0.0000 0.0000 0.0008 0.0023 0.0004 0.0013 0.0001
28. H 0.0000 0.0000 0.0000 0.0001 0.0007 0.0014 0.0005 0.0010 0.0001
29. C 0.0008 0.0001 0.0003 0.0035 0.0307 0.0422 0.0021 0.0025 0.0018
30. H 0.0000 0.0000 0.0000 0.0001 0.0003 0.0005 0.0001 0.0000 0.0000
31. C 0.0001 0.0000 0.0000 0.0000 0.0010 0.0062 0.0001 0.0002 0.0004
32. N 0.0001 0.0000 0.0001 0.0007 0.0053 0.0131 0.0004 0.0004 0.0007
Atom 10 11 12 13 14 15 16 17 18
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0002 0.0011 0.0003 0.0193 0.0138 0.0013 0.0025 0.0005 0.0008
2. H 0.0000 0.0000 0.0000 0.0015 0.0001 0.0007 0.0026 0.0001 0.0001
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3. H 0.0001 0.0000 0.0003 0.0061 0.0003 0.0002 0.0010 0.0002 0.0000
4. H 0.0002 0.0000 0.0000 0.0098 0.0001 0.0005 0.0018 0.0008 0.0001
5. N 0.0008 0.0004 0.0001 1.3722 0.0024 0.0140 0.0204 0.0272 0.0014
6. N 0.0009 0.0089 0.0080 0.1537 0.0035 0.0114 0.0172 0.0184 0.0003
7. C 0.0027 0.0044 0.0038 0.0175 0.0002 0.0006 0.0011 0.0013 0.0001
8. O 0.0127 0.0067 0.0083 0.0182 0.0006 0.0009 0.0021 0.0023 0.0001
9. C 0.9278 0.9027 0.9125 0.0056 0.0000 0.0001 0.0009 0.0010 0.0000
10. H 0.0000 0.0008 0.0006 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
11. H 0.0008 0.0000 0.0012 0.0002 0.0000 0.0000 0.0000 0.0000 0.0000
12. H 0.0006 0.0012 0.0000 0.0009 0.0000 0.0000 0.0001 0.0001 0.0000
13. C 0.0001 0.0002 0.0009 0.0000 0.8892 1.1512 0.0101 0.0144 0.0115
14. H 0.0000 0.0000 0.0000 0.8892 0.0000 0.0036 0.0068 0.0017 0.0001
15. C 0.0000 0.0000 0.0000 1.1512 0.0036 0.0000 1.3351 1.3352 0.0119
16. C 0.0000 0.0000 0.0001 0.0101 0.0068 1.3351 0.0000 0.0135 1.4646
17. C 0.0000 0.0000 0.0001 0.0144 0.0017 1.3352 0.0135 0.0000 0.0992
18. C 0.0000 0.0000 0.0000 0.0115 0.0001 0.0119 1.4646 0.0992 0.0000
19. H 0.0000 0.0000 0.0000 0.0011 0.0000 0.0031 0.9148 0.0086 0.0041
20. C 0.0000 0.0000 0.0000 0.0093 0.0004 0.0104 0.1022 1.4588 0.0108
21. H 0.0000 0.0000 0.0000 0.0017 0.0006 0.0028 0.0081 0.9046 0.0004
22. C 0.0000 0.0000 0.0001 0.0022 0.0001 0.0903 0.0112 0.0123 1.4154
23. H 0.0000 0.0000 0.0000 0.0002 0.0003 0.0082 0.0033 0.0003 0.9115
24. H 0.0000 0.0000 0.0000 0.0002 0.0001 0.0084 0.0003 0.0036 0.0084
25. H 0.0000 0.0000 0.0000 0.0004 0.0000 0.0002 0.0083 0.0084 0.0033
26. C 0.0003 0.0001 0.0005 0.0026 0.0008 0.0003 0.0002 0.0003 0.0000
27. H 0.0000 0.0000 0.0000 0.0017 0.0000 0.0000 0.0003 0.0003 0.0000
28. H 0.0000 0.0000 0.0000 0.0022 0.0000 0.0000 0.0003 0.0003 0.0000
29. C 0.0001 0.0005 0.0001 0.1544 0.0009 0.0008 0.0133 0.0166 0.0001
30. H 0.0000 0.0000 0.0000 0.0003 0.0000 0.0001 0.0001 0.0000 0.0000
31. C 0.0000 0.0000 0.0000 0.0055 0.0017 0.0005 0.0004 0.0005 0.0001
32. N 0.0000 0.0001 0.0000 0.0278 0.0012 0.0007 0.0028 0.0065 0.0002
Atom 19 20 21 22 23 24 25 26 27
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0013 0.0005 0.0000 0.0003 0.0000 0.0000 0.0000 0.0010 0.0001
2. H 0.0006 0.0002 0.0000 0.0003 0.0000 0.0000 0.0000 0.0003 0.0000
3. H 0.0001 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000 0.0001 0.0000
4. H 0.0004 0.0000 0.0000 0.0008 0.0000 0.0000 0.0000 0.0025 0.0000
5. N 0.0002 0.0003 0.0003 0.0154 0.0000 0.0002 0.0000 0.0324 0.0008
6. N 0.0003 0.0004 0.0001 0.0155 0.0000 0.0000 0.0000 0.3617 0.0023
7. C 0.0000 0.0000 0.0000 0.0010 0.0000 0.0000 0.0000 0.0044 0.0004
8. O 0.0001 0.0001 0.0000 0.0021 0.0000 0.0000 0.0000 0.0080 0.0013
9. C 0.0000 0.0000 0.0000 0.0009 0.0000 0.0000 0.0000 0.0111 0.0001
10. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0003 0.0000
11. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000
12. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0005 0.0000
13. C 0.0011 0.0093 0.0017 0.0022 0.0002 0.0002 0.0004 0.0026 0.0017
14. H 0.0000 0.0004 0.0006 0.0001 0.0003 0.0001 0.0000 0.0008 0.0000
15. C 0.0031 0.0104 0.0028 0.0903 0.0082 0.0084 0.0002 0.0003 0.0000
16. C 0.9148 0.1022 0.0081 0.0112 0.0033 0.0003 0.0083 0.0002 0.0003
17. C 0.0086 1.4588 0.9046 0.0123 0.0003 0.0036 0.0084 0.0003 0.0003
18. C 0.0041 0.0108 0.0004 1.4154 0.9115 0.0084 0.0033 0.0000 0.0000
19. H 0.0000 0.0003 0.0005 0.0084 0.0021 0.0004 0.0003 0.0000 0.0000
20. C 0.0003 0.0000 0.0040 1.4228 0.0084 0.9086 0.0034 0.0001 0.0000
21. H 0.0005 0.0040 0.0000 0.0083 0.0004 0.0022 0.0004 0.0001 0.0000
22. C 0.0084 1.4228 0.0083 0.0000 0.0035 0.0034 0.9119 0.0002 0.0002
23. H 0.0021 0.0084 0.0004 0.0035 0.0000 0.0004 0.0020 0.0000 0.0000
24. H 0.0004 0.9086 0.0022 0.0034 0.0004 0.0000 0.0020 0.0000 0.0000
25. H 0.0003 0.0034 0.0004 0.9119 0.0020 0.0020 0.0000 0.0000 0.0000
26. C 0.0000 0.0001 0.0001 0.0002 0.0000 0.0000 0.0000 0.0000 0.9072
27. H 0.0000 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000 0.9072 0.0000
28. H 0.0000 0.0000 0.0000 0.0003 0.0000 0.0000 0.0000 0.9152 0.0004
29. C 0.0001 0.0002 0.0002 0.0128 0.0000 0.0000 0.0000 1.5164 0.0038
30. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0072 0.0113
31. C 0.0000 0.0001 0.0003 0.0001 0.0000 0.0000 0.0000 0.0188 0.0012
32. N 0.0000 0.0002 0.0014 0.0033 0.0000 0.0000 0.0000 0.0702 0.0003
Atom 28 29 30 31 32
---- ------ ------ ------ ------ ------
1. C 0.0000 0.0008 0.0000 0.0001 0.0001
2. H 0.0000 0.0001 0.0000 0.0000 0.0000
3. H 0.0000 0.0003 0.0000 0.0000 0.0001
4. H 0.0001 0.0035 0.0001 0.0000 0.0007
5. N 0.0007 0.0307 0.0003 0.0010 0.0053
6. N 0.0014 0.0422 0.0005 0.0062 0.0131
7. C 0.0005 0.0021 0.0001 0.0001 0.0004
8. O 0.0010 0.0025 0.0000 0.0002 0.0004
9. C 0.0001 0.0018 0.0000 0.0004 0.0007
10. H 0.0000 0.0001 0.0000 0.0000 0.0000
11. H 0.0000 0.0005 0.0000 0.0000 0.0001
12. H 0.0000 0.0001 0.0000 0.0000 0.0000
13. C 0.0022 0.1544 0.0003 0.0055 0.0278
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14. H 0.0000 0.0009 0.0000 0.0017 0.0012
15. C 0.0000 0.0008 0.0001 0.0005 0.0007
16. C 0.0003 0.0133 0.0001 0.0004 0.0028
17. C 0.0003 0.0166 0.0000 0.0005 0.0065
18. C 0.0000 0.0001 0.0000 0.0001 0.0002
19. H 0.0000 0.0001 0.0000 0.0000 0.0000
20. C 0.0000 0.0002 0.0000 0.0001 0.0002
21. H 0.0000 0.0002 0.0000 0.0003 0.0014
22. C 0.0003 0.0128 0.0000 0.0001 0.0033
23. H 0.0000 0.0000 0.0000 0.0000 0.0000
24. H 0.0000 0.0000 0.0000 0.0000 0.0000
25. H 0.0000 0.0000 0.0000 0.0000 0.0000
26. C 0.9152 1.5164 0.0072 0.0188 0.0702
27. H 0.0004 0.0038 0.0113 0.0012 0.0003
28. H 0.0000 0.0030 0.0020 0.0095 0.0018
29. C 0.0030 0.0000 0.8878 1.1552 0.0510
30. H 0.0020 0.8878 0.0000 0.0035 0.0213
31. C 0.0095 1.1552 0.0035 0.0000 2.8001
32. N 0.0018 0.0510 0.0213 2.8001 0.0000
Wiberg bond index, Totals by atom:
Atom 1
---- ------
1. C 3.7667
2. H 0.9401
3. H 0.9356
4. H 0.9429
5. N 3.6250
6. N 3.2074
7. C 3.8980
8. O 2.0004
9. C 3.8240
10. H 0.9473
11. H 0.9272
12. H 0.9371
13. C 3.8911
14. H 0.9286
15. C 3.9926
16. C 3.9453
17. C 3.9370
18. C 3.9446
19. H 0.9469
20. C 3.9416
21. H 0.9362
22. C 3.9435
23. H 0.9408
24. H 0.9382
25. H 0.9406
26. C 3.8623
27. H 0.9318
28. H 0.9389
29. C 3.9011
30. H 0.9347
31. C 4.0057
32. N 3.0098
----------------------------o----------------------------------------o----------------------------------------------------
1 tsn nbo:
Wiberg bond index matrix in the NAO basis:
Atom 1 2 3 4 5 6 7 8 9
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0000 0.9059 0.9227 0.9196 0.9231 0.0322 0.0044 0.0057 0.0013
2. H 0.9059 0.0000 0.0005 0.0004 0.0032 0.0020 0.0001 0.0001 0.0001
3. H 0.9227 0.0005 0.0000 0.0009 0.0017 0.0015 0.0006 0.0002 0.0013
4. H 0.9196 0.0004 0.0009 0.0000 0.0017 0.0103 0.0005 0.0010 0.0000
5. N 0.9231 0.0032 0.0017 0.0017 0.0000 1.1324 0.0089 0.0196 0.0027
6. N 0.0322 0.0020 0.0015 0.0103 1.1324 0.0000 1.1777 0.1670 0.0108
7. C 0.0044 0.0001 0.0006 0.0005 0.0089 1.1777 0.0000 1.6808 0.9826
8. O 0.0057 0.0001 0.0002 0.0010 0.0196 0.1670 1.6808 0.0000 0.0604
9. C 0.0013 0.0001 0.0013 0.0000 0.0027 0.0108 0.9826 0.0604 0.0000
10. H 0.0003 0.0000 0.0002 0.0000 0.0001 0.0079 0.0038 0.0080 0.9131
11. H 0.0012 0.0000 0.0001 0.0000 0.0003 0.0087 0.0045 0.0071 0.9051
12. H 0.0002 0.0001 0.0001 0.0000 0.0008 0.0009 0.0026 0.0126 0.9297
13. C 0.0189 0.0121 0.0075 0.0009 1.3876 0.1517 0.0180 0.0185 0.0054
14. H 0.0140 0.0001 0.0003 0.0002 0.0021 0.0031 0.0003 0.0006 0.0000
15. C 0.0013 0.0004 0.0004 0.0010 0.0149 0.0111 0.0006 0.0009 0.0001
16. C 0.0006 0.0008 0.0003 0.0001 0.0246 0.0148 0.0011 0.0019 0.0007
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17. C 0.0021 0.0012 0.0008 0.0032 0.0194 0.0157 0.0009 0.0017 0.0008
18. C 0.0006 0.0000 0.0001 0.0002 0.0007 0.0004 0.0001 0.0000 0.0000
19. H 0.0010 0.0003 0.0002 0.0002 0.0001 0.0001 0.0000 0.0000 0.0000
20. C 0.0011 0.0000 0.0001 0.0001 0.0007 0.0003 0.0000 0.0001 0.0000
21. H 0.0000 0.0000 0.0000 0.0000 0.0003 0.0001 0.0000 0.0000 0.0000
22. C 0.0004 0.0007 0.0002 0.0002 0.0138 0.0126 0.0008 0.0016 0.0007
23. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000
24. H 0.0000 0.0000 0.0000 0.0000 0.0002 0.0001 0.0000 0.0000 0.0000
25. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
26. C 0.0008 0.0017 0.0003 0.0002 0.0314 0.3747 0.0045 0.0084 0.0110
27. H 0.0000 0.0001 0.0000 0.0000 0.0011 0.0015 0.0005 0.0015 0.0001
28. H 0.0001 0.0000 0.0000 0.0000 0.0006 0.0021 0.0003 0.0009 0.0001
29. C 0.0007 0.0018 0.0004 0.0000 0.0314 0.0433 0.0019 0.0021 0.0019
30. H 0.0000 0.0001 0.0000 0.0000 0.0003 0.0007 0.0000 0.0000 0.0000
31. C 0.0006 0.0016 0.0000 0.0000 0.0005 0.0077 0.0002 0.0002 0.0004
32. N 0.0018 0.0018 0.0003 0.0000 0.0063 0.0137 0.0004 0.0004 0.0007
Atom 10 11 12 13 14 15 16 17 18
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0003 0.0012 0.0002 0.0189 0.0140 0.0013 0.0006 0.0021 0.0006
2. H 0.0000 0.0000 0.0001 0.0121 0.0001 0.0004 0.0008 0.0012 0.0000
3. H 0.0002 0.0001 0.0001 0.0075 0.0003 0.0004 0.0003 0.0008 0.0001
4. H 0.0000 0.0000 0.0000 0.0009 0.0002 0.0010 0.0001 0.0032 0.0002
5. N 0.0001 0.0003 0.0008 1.3876 0.0021 0.0149 0.0246 0.0194 0.0007
6. N 0.0079 0.0087 0.0009 0.1517 0.0031 0.0111 0.0148 0.0157 0.0004
7. C 0.0038 0.0045 0.0026 0.0180 0.0003 0.0006 0.0011 0.0009 0.0001
8. O 0.0080 0.0071 0.0126 0.0185 0.0006 0.0009 0.0019 0.0017 0.0000
9. C 0.9131 0.9051 0.9297 0.0054 0.0000 0.0001 0.0007 0.0008 0.0000
10. H 0.0000 0.0012 0.0005 0.0009 0.0000 0.0000 0.0001 0.0001 0.0000
11. H 0.0012 0.0000 0.0007 0.0002 0.0000 0.0000 0.0000 0.0000 0.0000
12. H 0.0005 0.0007 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
13. C 0.0009 0.0002 0.0001 0.0000 0.8993 1.1337 0.0140 0.0107 0.0105
14. H 0.0000 0.0000 0.0000 0.8993 0.0000 0.0033 0.0019 0.0077 0.0003
15. C 0.0000 0.0000 0.0000 1.1337 0.0033 0.0000 1.3406 1.3438 0.0113
16. C 0.0001 0.0000 0.0000 0.0140 0.0019 1.3406 0.0000 0.0144 1.4650
17. C 0.0001 0.0000 0.0000 0.0107 0.0077 1.3438 0.0144 0.0000 0.1010
18. C 0.0000 0.0000 0.0000 0.0105 0.0003 0.0113 1.4650 0.1010 0.0000
19. H 0.0000 0.0000 0.0000 0.0013 0.0001 0.0031 0.0080 0.9006 0.0003
20. C 0.0000 0.0000 0.0000 0.0098 0.0001 0.0111 0.1032 1.4509 0.0109
21. H 0.0000 0.0000 0.0000 0.0016 0.0005 0.0028 0.9147 0.0085 0.0039
22. C 0.0001 0.0000 0.0000 0.0025 0.0007 0.0923 0.0116 0.0122 1.4150
23. H 0.0000 0.0000 0.0000 0.0002 0.0003 0.0081 0.0003 0.0035 0.0084
24. H 0.0000 0.0000 0.0000 0.0002 0.0000 0.0083 0.0034 0.0003 0.9125
25. H 0.0000 0.0000 0.0000 0.0004 0.0000 0.0002 0.0082 0.0084 0.0032
26. C 0.0005 0.0001 0.0003 0.0033 0.0003 0.0003 0.0002 0.0003 0.0000
27. H 0.0000 0.0000 0.0000 0.0032 0.0000 0.0000 0.0004 0.0005 0.0000
28. H 0.0000 0.0000 0.0000 0.0014 0.0000 0.0000 0.0002 0.0002 0.0000
29. C 0.0001 0.0003 0.0001 0.1494 0.0005 0.0006 0.0126 0.0143 0.0002
30. H 0.0000 0.0000 0.0000 0.0006 0.0000 0.0000 0.0000 0.0000 0.0000
31. C 0.0000 0.0000 0.0000 0.0046 0.0001 0.0006 0.0004 0.0017 0.0002
32. N 0.0000 0.0001 0.0000 0.0304 0.0003 0.0008 0.0025 0.0098 0.0005
Atom 19 20 21 22 23 24 25 26 27
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0010 0.0011 0.0000 0.0004 0.0000 0.0000 0.0000 0.0008 0.0000
2. H 0.0003 0.0000 0.0000 0.0007 0.0000 0.0000 0.0000 0.0017 0.0001
3. H 0.0002 0.0001 0.0000 0.0002 0.0000 0.0000 0.0000 0.0003 0.0000
4. H 0.0002 0.0001 0.0000 0.0002 0.0000 0.0000 0.0000 0.0002 0.0000
5. N 0.0001 0.0007 0.0003 0.0138 0.0000 0.0002 0.0000 0.0314 0.0011
6. N 0.0001 0.0003 0.0001 0.0126 0.0001 0.0001 0.0000 0.3747 0.0015
7. C 0.0000 0.0000 0.0000 0.0008 0.0000 0.0000 0.0000 0.0045 0.0005
8. O 0.0000 0.0001 0.0000 0.0016 0.0000 0.0000 0.0000 0.0084 0.0015
9. C 0.0000 0.0000 0.0000 0.0007 0.0000 0.0000 0.0000 0.0110 0.0001
10. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0005 0.0000
11. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000
12. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0003 0.0000
13. C 0.0013 0.0098 0.0016 0.0025 0.0002 0.0002 0.0004 0.0033 0.0032
14. H 0.0001 0.0001 0.0005 0.0007 0.0003 0.0000 0.0000 0.0003 0.0000
15. C 0.0031 0.0111 0.0028 0.0923 0.0081 0.0083 0.0002 0.0003 0.0000
16. C 0.0080 0.1032 0.9147 0.0116 0.0003 0.0034 0.0082 0.0002 0.0004
17. C 0.9006 1.4509 0.0085 0.0122 0.0035 0.0003 0.0084 0.0003 0.0005
18. C 0.0003 0.0109 0.0039 1.4150 0.0084 0.9125 0.0032 0.0000 0.0000
19. H 0.0000 0.0042 0.0004 0.0079 0.0021 0.0004 0.0003 0.0001 0.0000
20. C 0.0042 0.0000 0.0003 1.4279 0.9108 0.0083 0.0034 0.0000 0.0000
21. H 0.0004 0.0003 0.0000 0.0086 0.0004 0.0022 0.0004 0.0000 0.0000
22. C 0.0079 1.4279 0.0086 0.0000 0.0033 0.0035 0.9139 0.0002 0.0004
23. H 0.0021 0.9108 0.0004 0.0033 0.0000 0.0004 0.0020 0.0000 0.0000
24. H 0.0004 0.0083 0.0022 0.0035 0.0004 0.0000 0.0020 0.0000 0.0000
25. H 0.0003 0.0034 0.0004 0.9139 0.0020 0.0020 0.0000 0.0000 0.0000
26. C 0.0001 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000 0.0000 0.9127
27. H 0.0000 0.0000 0.0000 0.0004 0.0000 0.0000 0.0000 0.9127 0.0000
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28. H 0.0000 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000 0.9120 0.0004
29. C 0.0003 0.0001 0.0000 0.0109 0.0001 0.0000 0.0000 1.5046 0.0035
30. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0074 0.0110
31. C 0.0009 0.0004 0.0000 0.0002 0.0000 0.0000 0.0000 0.0198 0.0012
32. N 0.0051 0.0006 0.0000 0.0032 0.0001 0.0000 0.0000 0.0710 0.0003
Atom 28 29 30 31 32
---- ------ ------ ------ ------ ------
1. C 0.0001 0.0007 0.0000 0.0006 0.0018
2. H 0.0000 0.0018 0.0001 0.0016 0.0018
3. H 0.0000 0.0004 0.0000 0.0000 0.0003
4. H 0.0000 0.0000 0.0000 0.0000 0.0000
5. N 0.0006 0.0314 0.0003 0.0005 0.0063
6. N 0.0021 0.0433 0.0007 0.0077 0.0137
7. C 0.0003 0.0019 0.0000 0.0002 0.0004
8. O 0.0009 0.0021 0.0000 0.0002 0.0004
9. C 0.0001 0.0019 0.0000 0.0004 0.0007
10. H 0.0000 0.0001 0.0000 0.0000 0.0000
11. H 0.0000 0.0003 0.0000 0.0000 0.0001
12. H 0.0000 0.0001 0.0000 0.0000 0.0000
13. C 0.0014 0.1494 0.0006 0.0046 0.0304
14. H 0.0000 0.0005 0.0000 0.0001 0.0003
15. C 0.0000 0.0006 0.0000 0.0006 0.0008
16. C 0.0002 0.0126 0.0000 0.0004 0.0025
17. C 0.0002 0.0143 0.0000 0.0017 0.0098
18. C 0.0000 0.0002 0.0000 0.0002 0.0005
19. H 0.0000 0.0003 0.0000 0.0009 0.0051
20. C 0.0000 0.0001 0.0000 0.0004 0.0006
21. H 0.0000 0.0000 0.0000 0.0000 0.0000
22. C 0.0002 0.0109 0.0000 0.0002 0.0032
23. H 0.0000 0.0001 0.0000 0.0000 0.0001
24. H 0.0000 0.0000 0.0000 0.0000 0.0000
25. H 0.0000 0.0000 0.0000 0.0000 0.0000
26. C 0.9120 1.5046 0.0074 0.0198 0.0710
27. H 0.0004 0.0035 0.0110 0.0012 0.0003
28. H 0.0000 0.0032 0.0021 0.0095 0.0019
29. C 0.0032 0.0000 0.8873 1.1697 0.0550
30. H 0.0021 0.8873 0.0000 0.0036 0.0207
31. C 0.0095 1.1697 0.0036 0.0000 2.7788
32. N 0.0019 0.0550 0.0207 2.7788 0.0000
Wiberg bond index, Totals by atom:
Atom 1
---- ------
1. C 3.7609
2. H 0.9352
3. H 0.9408
4. H 0.9407
5. N 3.6306
6. N 3.2052
7. C 3.8961
8. O 2.0012
9. C 3.8292
10. H 0.9373
11. H 0.9297
12. H 0.9489
13. C 3.8987
14. H 0.9360
15. C 3.9918
16. C 3.9466
17. C 3.9345
18. C 3.9454
19. H 0.9369
20. C 3.9444
21. H 0.9448
22. C 3.9456
23. H 0.9401
24. H 0.9419
25. H 0.9424
26. C 3.8662
27. H 0.9383
28. H 0.9354
29. C 3.8962
30. H 0.9340
31. C 4.0030
32. N 3.0065
------------------------------o------------------------------------------------o-----------------------------------------
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2 trx nbo:
Wiberg bond index matrix in the NAO basis:
Atom 1 2 3 4 5 6 7 8 9
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0000 0.9096 0.9187 1.4682 0.0062 0.0230 0.0436 0.0087 0.0004
2. H 0.9096 0.0000 0.0003 0.0046 0.0113 0.0017 0.0005 0.0023 0.0001
3. H 0.9187 0.0003 0.0000 0.0036 0.0022 0.0079 0.0016 0.0014 0.0001
4. C 1.4682 0.0046 0.0036 0.0000 0.9029 1.1011 0.0608 0.0187 0.0159
5. H 0.0062 0.0113 0.0022 0.9029 0.0000 0.0033 0.0019 0.0070 0.0008
6. C 0.0230 0.0017 0.0079 1.1011 0.0033 0.0000 1.6910 0.9687 0.0096
7. O 0.0436 0.0005 0.0016 0.0608 0.0019 1.6910 0.0000 0.1454 0.0142
8. O 0.0087 0.0023 0.0014 0.0187 0.0070 0.9687 0.1454 0.0000 0.8894
9. C 0.0004 0.0001 0.0001 0.0159 0.0008 0.0096 0.0142 0.8894 0.0000
10. H 0.0001 0.0000 0.0000 0.0001 0.0003 0.0082 0.0025 0.0058 0.9352
11. H 0.0002 0.0001 0.0001 0.0004 0.0000 0.0019 0.0047 0.0176 0.9302
12. H 0.0003 0.0000 0.0000 0.0005 0.0000 0.0019 0.0039 0.0173 0.9295
13. C 0.0012 0.0001 0.0000 0.0008 0.0000 0.0002 0.0001 0.0001 0.0000
14. H 0.0004 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
15. H 0.0004 0.0000 0.0000 0.0005 0.0000 0.0001 0.0001 0.0000 0.0000
16. H 0.0033 0.0000 0.0001 0.0035 0.0001 0.0002 0.0004 0.0001 0.0000
17. N 0.0446 0.0005 0.0008 0.0382 0.0004 0.0043 0.0052 0.0012 0.0001
18. N 0.4071 0.0022 0.0016 0.0438 0.0008 0.0097 0.0109 0.0021 0.0001
19. C 0.0048 0.0002 0.0006 0.0021 0.0001 0.0002 0.0004 0.0001 0.0000
20. O 0.0196 0.0002 0.0004 0.0027 0.0001 0.0012 0.0012 0.0002 0.0000
21. C 0.0019 0.0003 0.0002 0.0004 0.0000 0.0000 0.0000 0.0000 0.0000
22. H 0.0003 0.0005 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
23. H 0.0002 0.0000 0.0003 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
24. H 0.0005 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
25. C 0.0025 0.0019 0.0029 0.2194 0.0003 0.0120 0.0205 0.0065 0.0003
26. H 0.0013 0.0000 0.0000 0.0014 0.0000 0.0005 0.0004 0.0051 0.0001
27. C 0.0007 0.0000 0.0000 0.0012 0.0001 0.0005 0.0005 0.0003 0.0000
28. C 0.0002 0.0002 0.0003 0.0098 0.0003 0.0009 0.0009 0.0005 0.0000
29. C 0.0002 0.0002 0.0003 0.0152 0.0000 0.0006 0.0020 0.0006 0.0000
30. C 0.0000 0.0000 0.0000 0.0002 0.0000 0.0000 0.0001 0.0000 0.0000
31. H 0.0001 0.0000 0.0000 0.0002 0.0001 0.0000 0.0000 0.0000 0.0000
32. C 0.0002 0.0000 0.0000 0.0003 0.0000 0.0000 0.0001 0.0000 0.0000
33. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
34. C 0.0001 0.0002 0.0003 0.0093 0.0000 0.0005 0.0009 0.0004 0.0000
35. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
36. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
37. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Atom 10 11 12 13 14 15 16 17 18
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0001 0.0002 0.0003 0.0012 0.0004 0.0004 0.0033 0.0446 0.4071
2. H 0.0000 0.0001 0.0000 0.0001 0.0000 0.0000 0.0000 0.0005 0.0022
3. H 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0001 0.0008 0.0016
4. C 0.0001 0.0004 0.0005 0.0008 0.0000 0.0005 0.0035 0.0382 0.0438
5. H 0.0003 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0004 0.0008
6. C 0.0082 0.0019 0.0019 0.0002 0.0000 0.0001 0.0002 0.0043 0.0097
7. O 0.0025 0.0047 0.0039 0.0001 0.0000 0.0001 0.0004 0.0052 0.0109
8. O 0.0058 0.0176 0.0173 0.0001 0.0000 0.0000 0.0001 0.0012 0.0021
9. C 0.9352 0.9302 0.9295 0.0000 0.0000 0.0000 0.0000 0.0001 0.0001
10. H 0.0000 0.0003 0.0004 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
11. H 0.0003 0.0000 0.0003 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
12. H 0.0004 0.0003 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0001
13. C 0.0000 0.0000 0.0000 0.0000 0.9198 0.8895 0.9196 0.9275 0.0314
14. H 0.0000 0.0000 0.0000 0.9198 0.0000 0.0012 0.0004 0.0017 0.0092
15. H 0.0000 0.0000 0.0000 0.8895 0.0012 0.0000 0.0006 0.0020 0.0029
16. H 0.0000 0.0000 0.0000 0.9196 0.0004 0.0006 0.0000 0.0048 0.0023
17. N 0.0000 0.0000 0.0001 0.9275 0.0017 0.0020 0.0048 0.0000 1.1199
18. N 0.0000 0.0000 0.0001 0.0314 0.0092 0.0029 0.0023 1.1199 0.0000
19. C 0.0000 0.0000 0.0000 0.0044 0.0009 0.0009 0.0002 0.0097 1.1970
20. O 0.0000 0.0000 0.0000 0.0148 0.0004 0.0157 0.0005 0.0076 0.1570
21. C 0.0000 0.0000 0.0000 0.0007 0.0002 0.0009 0.0001 0.0138 0.0128
22. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0003 0.0012
23. H 0.0000 0.0000 0.0000 0.0002 0.0001 0.0000 0.0000 0.0001 0.0056
24. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0007 0.0070
25. C 0.0000 0.0001 0.0002 0.0184 0.0011 0.0075 0.0108 1.3759 0.1232
26. H 0.0000 0.0000 0.0002 0.0135 0.0002 0.0002 0.0002 0.0029 0.0037
27. C 0.0000 0.0000 0.0000 0.0013 0.0009 0.0003 0.0002 0.0117 0.0114
28. C 0.0000 0.0000 0.0000 0.0021 0.0033 0.0008 0.0010 0.0179 0.0107
29. C 0.0000 0.0000 0.0000 0.0006 0.0001 0.0004 0.0006 0.0220 0.0115
30. C 0.0000 0.0000 0.0000 0.0012 0.0001 0.0001 0.0001 0.0009 0.0003
31. H 0.0000 0.0000 0.0000 0.0009 0.0002 0.0001 0.0004 0.0002 0.0002
32. C 0.0000 0.0000 0.0000 0.0007 0.0001 0.0001 0.0000 0.0004 0.0004
33. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0003 0.0001
34. C 0.0000 0.0000 0.0000 0.0004 0.0003 0.0003 0.0005 0.0117 0.0088
35. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000
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36. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0001
37. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Atom 19 20 21 22 23 24 25 26 27
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0048 0.0196 0.0019 0.0003 0.0002 0.0005 0.0025 0.0013 0.0007
2. H 0.0002 0.0002 0.0003 0.0005 0.0000 0.0000 0.0019 0.0000 0.0000
3. H 0.0006 0.0004 0.0002 0.0001 0.0003 0.0000 0.0029 0.0000 0.0000
4. C 0.0021 0.0027 0.0004 0.0001 0.0000 0.0000 0.2194 0.0014 0.0012
5. H 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000 0.0003 0.0000 0.0001
6. C 0.0002 0.0012 0.0000 0.0000 0.0000 0.0000 0.0120 0.0005 0.0005
7. O 0.0004 0.0012 0.0000 0.0000 0.0000 0.0000 0.0205 0.0004 0.0005
8. O 0.0001 0.0002 0.0000 0.0000 0.0000 0.0000 0.0065 0.0051 0.0003
9. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0003 0.0001 0.0000
10. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
11. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000
12. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0002 0.0000
13. C 0.0044 0.0148 0.0007 0.0001 0.0002 0.0000 0.0184 0.0135 0.0013
14. H 0.0009 0.0004 0.0002 0.0000 0.0001 0.0000 0.0011 0.0002 0.0009
15. H 0.0009 0.0157 0.0009 0.0000 0.0000 0.0000 0.0075 0.0002 0.0003
16. H 0.0002 0.0005 0.0001 0.0000 0.0000 0.0000 0.0108 0.0002 0.0002
17. N 0.0097 0.0076 0.0138 0.0003 0.0001 0.0007 1.3759 0.0029 0.0117
18. N 1.1970 0.1570 0.0128 0.0012 0.0056 0.0070 0.1232 0.0037 0.0114
19. C 0.0000 1.6471 0.9925 0.0038 0.0043 0.0028 0.0222 0.0003 0.0006
20. O 1.6471 0.0000 0.0551 0.0144 0.0133 0.0033 0.0203 0.0001 0.0004
21. C 0.9925 0.0551 0.0000 0.9177 0.9128 0.9171 0.0007 0.0002 0.0004
22. H 0.0038 0.0144 0.9177 0.0000 0.0008 0.0007 0.0001 0.0000 0.0000
23. H 0.0043 0.0133 0.9128 0.0008 0.0000 0.0009 0.0008 0.0000 0.0000
24. H 0.0028 0.0033 0.9171 0.0007 0.0009 0.0000 0.0003 0.0000 0.0001
25. C 0.0222 0.0203 0.0007 0.0001 0.0008 0.0003 0.0000 0.8868 1.1068
26. H 0.0003 0.0001 0.0002 0.0000 0.0000 0.0000 0.8868 0.0000 0.0032
27. C 0.0006 0.0004 0.0004 0.0000 0.0000 0.0001 1.1068 0.0032 0.0000
28. C 0.0012 0.0024 0.0001 0.0000 0.0001 0.0000 0.0110 0.0071 1.3530
29. C 0.0014 0.0023 0.0001 0.0000 0.0001 0.0000 0.0141 0.0016 1.3575
30. C 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0099 0.0001 0.0116
31. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0012 0.0000 0.0031
32. C 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0087 0.0003 0.0110
33. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0016 0.0005 0.0029
34. C 0.0010 0.0021 0.0000 0.0000 0.0001 0.0000 0.0023 0.0006 0.0970
35. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0003 0.0003 0.0081
36. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0000 0.0082
37. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0004 0.0000 0.0002
Atom 28 29 30 31 32 33 34 35 36
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0002 0.0002 0.0000 0.0001 0.0002 0.0000 0.0001 0.0000 0.0000
2. H 0.0002 0.0002 0.0000 0.0000 0.0000 0.0000 0.0002 0.0000 0.0000
3. H 0.0003 0.0003 0.0000 0.0000 0.0000 0.0000 0.0003 0.0000 0.0000
4. C 0.0098 0.0152 0.0002 0.0002 0.0003 0.0000 0.0093 0.0000 0.0000
5. H 0.0003 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
6. C 0.0009 0.0006 0.0000 0.0000 0.0000 0.0000 0.0005 0.0000 0.0000
7. O 0.0009 0.0020 0.0001 0.0000 0.0001 0.0000 0.0009 0.0000 0.0000
8. O 0.0005 0.0006 0.0000 0.0000 0.0000 0.0000 0.0004 0.0000 0.0000
9. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
10. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
11. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
12. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
13. C 0.0021 0.0006 0.0012 0.0009 0.0007 0.0000 0.0004 0.0000 0.0000
14. H 0.0033 0.0001 0.0001 0.0002 0.0001 0.0000 0.0003 0.0000 0.0000
15. H 0.0008 0.0004 0.0001 0.0001 0.0001 0.0000 0.0003 0.0000 0.0000
16. H 0.0010 0.0006 0.0001 0.0004 0.0000 0.0000 0.0005 0.0000 0.0000
17. N 0.0179 0.0220 0.0009 0.0002 0.0004 0.0003 0.0117 0.0001 0.0002
18. N 0.0107 0.0115 0.0003 0.0002 0.0004 0.0001 0.0088 0.0000 0.0001
19. C 0.0012 0.0014 0.0000 0.0000 0.0001 0.0000 0.0010 0.0000 0.0000
20. O 0.0024 0.0023 0.0001 0.0000 0.0000 0.0000 0.0021 0.0000 0.0000
21. C 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
22. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
23. H 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000
24. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
25. C 0.0110 0.0141 0.0099 0.0012 0.0087 0.0016 0.0023 0.0003 0.0002
26. H 0.0071 0.0016 0.0001 0.0000 0.0003 0.0005 0.0006 0.0003 0.0000
27. C 1.3530 1.3575 0.0116 0.0031 0.0110 0.0029 0.0970 0.0081 0.0082
28. C 0.0000 0.0135 1.4571 0.9121 0.1047 0.0085 0.0114 0.0034 0.0003
29. C 0.0135 0.0000 0.1030 0.0085 1.4514 0.9119 0.0117 0.0003 0.0034
30. C 1.4571 0.1030 0.0000 0.0040 0.0109 0.0004 1.4207 0.9115 0.0084
31. H 0.9121 0.0085 0.0040 0.0000 0.0003 0.0004 0.0084 0.0021 0.0004
32. C 0.1047 1.4514 0.0109 0.0003 0.0000 0.0039 1.4271 0.0084 0.9110
33. H 0.0085 0.9119 0.0004 0.0004 0.0039 0.0000 0.0085 0.0004 0.0022
34. C 0.0114 0.0117 1.4207 0.0084 1.4271 0.0085 0.0000 0.0035 0.0035
35. H 0.0034 0.0003 0.9115 0.0021 0.0084 0.0004 0.0035 0.0000 0.0004
36. H 0.0003 0.0034 0.0084 0.0004 0.9110 0.0022 0.0035 0.0004 0.0000
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37. H 0.0083 0.0084 0.0033 0.0003 0.0034 0.0004 0.9124 0.0020 0.0020
Atom 37
---- ------
1. C 0.0000
2. H 0.0000
3. H 0.0000
4. C 0.0000
5. H 0.0000
6. C 0.0000
7. O 0.0000
8. O 0.0000
9. C 0.0000
10. H 0.0000
11. H 0.0000
12. H 0.0000
13. C 0.0000
14. H 0.0000
15. H 0.0000
16. H 0.0000
17. N 0.0000
18. N 0.0000
19. C 0.0000
20. O 0.0000
21. C 0.0000
22. H 0.0000
23. H 0.0000
24. H 0.0000
25. C 0.0004
26. H 0.0000
27. C 0.0002
28. C 0.0083
29. C 0.0084
30. C 0.0033
31. H 0.0003
32. C 0.0034
33. H 0.0004
34. C 0.9124
35. H 0.0020
36. H 0.0020
37. H 0.0000
---------------------------------o------------------------------------------o------------------------------------------------
2 trn nbo:
Wiberg bond index matrix in the NAO basis:
Atom 1 2 3 4 5 6 7 8 9
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0000 0.9114 0.9156 1.4518 0.0063 0.0237 0.0436 0.0088 0.0004
2. H 0.9114 0.0000 0.0003 0.0043 0.0112 0.0016 0.0004 0.0024 0.0001
3. H 0.9156 0.0003 0.0000 0.0040 0.0023 0.0079 0.0015 0.0013 0.0001
4. C 1.4518 0.0043 0.0040 0.0000 0.9004 1.1233 0.0619 0.0195 0.0155
5. H 0.0063 0.0112 0.0023 0.9004 0.0000 0.0036 0.0020 0.0071 0.0008
6. C 0.0237 0.0016 0.0079 1.1233 0.0036 0.0000 1.6857 0.9496 0.0095
7. O 0.0436 0.0004 0.0015 0.0619 0.0020 1.6857 0.0000 0.1407 0.0148
8. O 0.0088 0.0024 0.0013 0.0195 0.0071 0.9496 0.1407 0.0000 0.8905
9. C 0.0004 0.0001 0.0001 0.0155 0.0008 0.0095 0.0148 0.8905 0.0000
10. H 0.0001 0.0000 0.0000 0.0001 0.0003 0.0084 0.0026 0.0056 0.9355
11. H 0.0002 0.0000 0.0000 0.0005 0.0000 0.0017 0.0039 0.0176 0.9284
12. H 0.0003 0.0001 0.0001 0.0004 0.0000 0.0018 0.0044 0.0184 0.9304
13. C 0.0011 0.0000 0.0001 0.0007 0.0000 0.0003 0.0005 0.0034 0.0002
14. H 0.0004 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
15. H 0.0005 0.0000 0.0000 0.0007 0.0000 0.0000 0.0000 0.0003 0.0000
16. H 0.0023 0.0001 0.0000 0.0021 0.0000 0.0002 0.0018 0.0052 0.0002
17. N 0.0421 0.0009 0.0007 0.0405 0.0004 0.0030 0.0060 0.0016 0.0001
18. N 0.4274 0.0015 0.0028 0.0447 0.0010 0.0114 0.0110 0.0021 0.0000
19. C 0.0048 0.0006 0.0003 0.0022 0.0000 0.0002 0.0004 0.0001 0.0000
20. O 0.0194 0.0004 0.0002 0.0027 0.0001 0.0013 0.0011 0.0002 0.0000
21. C 0.0020 0.0002 0.0004 0.0004 0.0001 0.0000 0.0000 0.0000 0.0000
22. H 0.0002 0.0001 0.0005 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
23. H 0.0003 0.0003 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
24. H 0.0005 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
25. C 0.0024 0.0028 0.0025 0.2061 0.0008 0.0111 0.0246 0.0042 0.0002
26. H 0.0008 0.0000 0.0000 0.0009 0.0001 0.0004 0.0003 0.0002 0.0000
27. C 0.0004 0.0000 0.0000 0.0009 0.0001 0.0008 0.0006 0.0002 0.0001
28. C 0.0002 0.0004 0.0003 0.0136 0.0000 0.0009 0.0043 0.0014 0.0004
29. C 0.0002 0.0003 0.0003 0.0133 0.0000 0.0012 0.0013 0.0004 0.0000
30. C 0.0000 0.0000 0.0000 0.0001 0.0000 0.0001 0.0005 0.0001 0.0001
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31. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0004 0.0002 0.0016 0.0002
32. C 0.0000 0.0000 0.0000 0.0002 0.0000 0.0001 0.0005 0.0000 0.0000
33. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
34. C 0.0001 0.0003 0.0002 0.0102 0.0000 0.0005 0.0015 0.0003 0.0000
35. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
36. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
37. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Atom 10 11 12 13 14 15 16 17 18
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0001 0.0002 0.0003 0.0011 0.0004 0.0005 0.0023 0.0421 0.4274
2. H 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0001 0.0009 0.0015
3. H 0.0000 0.0000 0.0001 0.0001 0.0000 0.0000 0.0000 0.0007 0.0028
4. C 0.0001 0.0005 0.0004 0.0007 0.0000 0.0007 0.0021 0.0405 0.0447
5. H 0.0003 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0004 0.0010
6. C 0.0084 0.0017 0.0018 0.0003 0.0000 0.0000 0.0002 0.0030 0.0114
7. O 0.0026 0.0039 0.0044 0.0005 0.0000 0.0000 0.0018 0.0060 0.0110
8. O 0.0056 0.0176 0.0184 0.0034 0.0000 0.0003 0.0052 0.0016 0.0021
9. C 0.9355 0.9284 0.9304 0.0002 0.0000 0.0000 0.0002 0.0001 0.0000
10. H 0.0000 0.0004 0.0003 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000
11. H 0.0004 0.0000 0.0003 0.0001 0.0000 0.0000 0.0002 0.0001 0.0001
12. H 0.0003 0.0003 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
13. C 0.0000 0.0001 0.0000 0.0000 0.9216 0.8924 0.9088 0.9228 0.0312
14. H 0.0000 0.0000 0.0000 0.9216 0.0000 0.0012 0.0004 0.0017 0.0090
15. H 0.0000 0.0000 0.0000 0.8924 0.0012 0.0000 0.0006 0.0020 0.0028
16. H 0.0001 0.0002 0.0000 0.9088 0.0004 0.0006 0.0000 0.0036 0.0019
17. N 0.0000 0.0001 0.0000 0.9228 0.0017 0.0020 0.0036 0.0000 1.1181
18. N 0.0000 0.0001 0.0000 0.0312 0.0090 0.0028 0.0019 1.1181 0.0000
19. C 0.0000 0.0000 0.0000 0.0044 0.0009 0.0009 0.0002 0.0098 1.1910
20. O 0.0000 0.0000 0.0000 0.0143 0.0004 0.0146 0.0005 0.0074 0.1577
21. C 0.0000 0.0000 0.0000 0.0007 0.0002 0.0009 0.0001 0.0137 0.0127
22. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0003 0.0015
23. H 0.0000 0.0000 0.0000 0.0002 0.0001 0.0000 0.0000 0.0001 0.0049
24. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0007 0.0067
25. C 0.0000 0.0002 0.0001 0.0184 0.0011 0.0076 0.0112 1.3860 0.1185
26. H 0.0000 0.0000 0.0000 0.0138 0.0002 0.0002 0.0001 0.0027 0.0034
27. C 0.0000 0.0000 0.0000 0.0013 0.0009 0.0003 0.0003 0.0127 0.0113
28. C 0.0000 0.0001 0.0002 0.0019 0.0033 0.0007 0.0010 0.0180 0.0111
29. C 0.0000 0.0000 0.0000 0.0005 0.0001 0.0004 0.0007 0.0228 0.0107
30. C 0.0000 0.0000 0.0001 0.0012 0.0001 0.0001 0.0000 0.0007 0.0003
31. H 0.0000 0.0001 0.0002 0.0008 0.0002 0.0001 0.0003 0.0001 0.0001
32. C 0.0000 0.0000 0.0000 0.0007 0.0001 0.0001 0.0000 0.0005 0.0003
33. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0003 0.0001
34. C 0.0000 0.0000 0.0000 0.0003 0.0002 0.0003 0.0006 0.0122 0.0087
35. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
36. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0001
37. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Atom 19 20 21 22 23 24 25 26 27
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0048 0.0194 0.0020 0.0002 0.0003 0.0005 0.0024 0.0008 0.0004
2. H 0.0006 0.0004 0.0002 0.0001 0.0003 0.0000 0.0028 0.0000 0.0000
3. H 0.0003 0.0002 0.0004 0.0005 0.0001 0.0000 0.0025 0.0000 0.0000
4. C 0.0022 0.0027 0.0004 0.0001 0.0000 0.0000 0.2061 0.0009 0.0009
5. H 0.0000 0.0001 0.0001 0.0000 0.0000 0.0000 0.0008 0.0001 0.0001
6. C 0.0002 0.0013 0.0000 0.0000 0.0000 0.0000 0.0111 0.0004 0.0008
7. O 0.0004 0.0011 0.0000 0.0000 0.0000 0.0000 0.0246 0.0003 0.0006
8. O 0.0001 0.0002 0.0000 0.0000 0.0000 0.0000 0.0042 0.0002 0.0002
9. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0000 0.0001
10. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
11. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0000 0.0000
12. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000
13. C 0.0044 0.0143 0.0007 0.0001 0.0002 0.0000 0.0184 0.0138 0.0013
14. H 0.0009 0.0004 0.0002 0.0000 0.0001 0.0000 0.0011 0.0002 0.0009
15. H 0.0009 0.0146 0.0009 0.0000 0.0000 0.0000 0.0076 0.0002 0.0003
16. H 0.0002 0.0005 0.0001 0.0000 0.0000 0.0000 0.0112 0.0001 0.0003
17. N 0.0098 0.0074 0.0137 0.0003 0.0001 0.0007 1.3860 0.0027 0.0127
18. N 1.1910 0.1577 0.0127 0.0015 0.0049 0.0067 0.1185 0.0034 0.0113
19. C 0.0000 1.6527 0.9925 0.0039 0.0042 0.0027 0.0213 0.0003 0.0006
20. O 1.6527 0.0000 0.0547 0.0150 0.0137 0.0033 0.0188 0.0001 0.0004
21. C 0.9925 0.0547 0.0000 0.9173 0.9128 0.9173 0.0007 0.0002 0.0004
22. H 0.0039 0.0150 0.9173 0.0000 0.0009 0.0007 0.0001 0.0000 0.0000
23. H 0.0042 0.0137 0.9128 0.0009 0.0000 0.0009 0.0007 0.0000 0.0000
24. H 0.0027 0.0033 0.9173 0.0007 0.0009 0.0000 0.0002 0.0000 0.0001
25. C 0.0213 0.0188 0.0007 0.0001 0.0007 0.0002 0.0000 0.8949 1.1125
26. H 0.0003 0.0001 0.0002 0.0000 0.0000 0.0000 0.8949 0.0000 0.0032
27. C 0.0006 0.0004 0.0004 0.0000 0.0000 0.0001 1.1125 0.0032 0.0000
28. C 0.0011 0.0024 0.0001 0.0000 0.0001 0.0000 0.0109 0.0074 1.3518
29. C 0.0014 0.0021 0.0001 0.0000 0.0001 0.0000 0.0142 0.0017 1.3529
30. C 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0094 0.0001 0.0114
31. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0012 0.0001 0.0032
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32. C 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0095 0.0003 0.0111
33. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0016 0.0005 0.0029
34. C 0.0010 0.0019 0.0000 0.0000 0.0001 0.0000 0.0025 0.0007 0.0959
35. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0003 0.0081
36. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0000 0.0082
37. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0004 0.0000 0.0002
Atom 28 29 30 31 32 33 34 35 36
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0002 0.0002 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000
2. H 0.0004 0.0003 0.0000 0.0000 0.0000 0.0000 0.0003 0.0000 0.0000
3. H 0.0003 0.0003 0.0000 0.0000 0.0000 0.0000 0.0002 0.0000 0.0000
4. C 0.0136 0.0133 0.0001 0.0000 0.0002 0.0000 0.0102 0.0000 0.0000
5. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
6. C 0.0009 0.0012 0.0001 0.0004 0.0001 0.0000 0.0005 0.0000 0.0000
7. O 0.0043 0.0013 0.0005 0.0002 0.0005 0.0000 0.0015 0.0000 0.0000
8. O 0.0014 0.0004 0.0001 0.0016 0.0000 0.0000 0.0003 0.0000 0.0000
9. C 0.0004 0.0000 0.0001 0.0002 0.0000 0.0000 0.0000 0.0000 0.0000
10. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
11. H 0.0001 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
12. H 0.0002 0.0000 0.0001 0.0002 0.0000 0.0000 0.0000 0.0000 0.0000
13. C 0.0019 0.0005 0.0012 0.0008 0.0007 0.0000 0.0003 0.0000 0.0000
14. H 0.0033 0.0001 0.0001 0.0002 0.0001 0.0000 0.0002 0.0000 0.0000
15. H 0.0007 0.0004 0.0001 0.0001 0.0001 0.0000 0.0003 0.0000 0.0000
16. H 0.0010 0.0007 0.0000 0.0003 0.0000 0.0000 0.0006 0.0000 0.0000
17. N 0.0180 0.0228 0.0007 0.0001 0.0005 0.0003 0.0122 0.0000 0.0002
18. N 0.0111 0.0107 0.0003 0.0001 0.0003 0.0001 0.0087 0.0000 0.0001
19. C 0.0011 0.0014 0.0000 0.0000 0.0001 0.0000 0.0010 0.0000 0.0000
20. O 0.0024 0.0021 0.0001 0.0000 0.0000 0.0000 0.0019 0.0000 0.0000
21. C 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
22. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
23. H 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000
24. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
25. C 0.0109 0.0142 0.0094 0.0012 0.0095 0.0016 0.0025 0.0002 0.0002
26. H 0.0074 0.0017 0.0001 0.0001 0.0003 0.0005 0.0007 0.0003 0.0000
27. C 1.3518 1.3529 0.0114 0.0032 0.0111 0.0029 0.0959 0.0081 0.0082
28. C 0.0000 0.0136 1.4519 0.9088 0.1033 0.0085 0.0117 0.0034 0.0003
29. C 0.0136 0.0000 0.1039 0.0084 1.4572 0.9126 0.0116 0.0003 0.0034
30. C 1.4519 0.1039 0.0000 0.0041 0.0108 0.0004 1.4255 0.9114 0.0084
31. H 0.9088 0.0084 0.0041 0.0000 0.0003 0.0004 0.0082 0.0021 0.0004
32. C 0.1033 1.4572 0.0108 0.0003 0.0000 0.0039 1.4216 0.0084 0.9111
33. H 0.0085 0.9126 0.0004 0.0004 0.0039 0.0000 0.0086 0.0004 0.0022
34. C 0.0117 0.0116 1.4255 0.0082 1.4216 0.0086 0.0000 0.0035 0.0035
35. H 0.0034 0.0003 0.9114 0.0021 0.0084 0.0004 0.0035 0.0000 0.0004
36. H 0.0003 0.0034 0.0084 0.0004 0.9111 0.0022 0.0035 0.0004 0.0000
37. H 0.0083 0.0083 0.0034 0.0003 0.0033 0.0004 0.9125 0.0020 0.0020
Atom 37
---- ------
1. C 0.0000
2. H 0.0000
3. H 0.0000
4. C 0.0000
5. H 0.0000
6. C 0.0000
7. O 0.0000
8. O 0.0000
9. C 0.0000
10. H 0.0000
11. H 0.0000
12. H 0.0000
13. C 0.0000
14. H 0.0000
15. H 0.0000
16. H 0.0000
17. N 0.0000
18. N 0.0000
19. C 0.0000
20. O 0.0000
21. C 0.0000
22. H 0.0000
23. H 0.0000
24. H 0.0000
25. C 0.0004
26. H 0.0000
27. C 0.0002
28. C 0.0083
29. C 0.0083
30. C 0.0034
31. H 0.0003
32. C 0.0033
Page 270
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33. H 0.0004
34. C 0.9125
35. H 0.0020
36. H 0.0020
37. H 0.0000
------------------------------------o--------------------------------------o------------------------------------------------
2 tsx nbo: Wiberg bond index matrix in the NAO basis:
Atom 1 2 3 4 5 6 7 8 9
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0000 0.9067 0.9183 1.4299 0.0061 0.0247 0.0420 0.0094 0.0005
2. H 0.9067 0.0000 0.0004 0.0047 0.0107 0.0017 0.0005 0.0026 0.0001
3. H 0.9183 0.0004 0.0000 0.0036 0.0021 0.0079 0.0017 0.0014 0.0001
4. C 1.4299 0.0047 0.0036 0.0000 0.9026 1.1314 0.0660 0.0207 0.0158
5. H 0.0061 0.0107 0.0021 0.9026 0.0000 0.0035 0.0018 0.0070 0.0008
6. C 0.0247 0.0017 0.0079 1.1314 0.0035 0.0000 1.6446 0.9760 0.0097
7. O 0.0420 0.0005 0.0017 0.0660 0.0018 1.6446 0.0000 0.1402 0.0142
8. O 0.0094 0.0026 0.0014 0.0207 0.0070 0.9760 0.1402 0.0000 0.8883
9. C 0.0005 0.0001 0.0001 0.0158 0.0008 0.0097 0.0142 0.8883 0.0000
10. H 0.0001 0.0000 0.0000 0.0001 0.0003 0.0081 0.0025 0.0058 0.9349
11. H 0.0003 0.0000 0.0000 0.0005 0.0000 0.0020 0.0037 0.0170 0.9296
12. H 0.0003 0.0001 0.0001 0.0004 0.0000 0.0019 0.0045 0.0173 0.9299
13. C 0.0009 0.0003 0.0001 0.0018 0.0000 0.0003 0.0002 0.0001 0.0000
14. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
15. H 0.0028 0.0000 0.0003 0.0021 0.0000 0.0001 0.0002 0.0001 0.0000
16. H 0.0007 0.0000 0.0000 0.0006 0.0000 0.0001 0.0001 0.0001 0.0000
17. N 0.0369 0.0009 0.0011 0.0419 0.0004 0.0048 0.0057 0.0019 0.0001
18. N 0.4536 0.0026 0.0018 0.0448 0.0009 0.0109 0.0115 0.0022 0.0001
19. C 0.0048 0.0002 0.0007 0.0023 0.0001 0.0002 0.0005 0.0001 0.0000
20. O 0.0201 0.0002 0.0006 0.0028 0.0001 0.0014 0.0013 0.0003 0.0000
21. C 0.0019 0.0004 0.0002 0.0005 0.0000 0.0001 0.0000 0.0000 0.0000
22. H 0.0002 0.0004 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
23. H 0.0005 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
24. H 0.0003 0.0000 0.0003 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
25. C 0.0030 0.0029 0.0034 0.2149 0.0003 0.0127 0.0205 0.0083 0.0003
26. H 0.0007 0.0000 0.0000 0.0009 0.0000 0.0004 0.0004 0.0046 0.0001
27. C 0.0002 0.0000 0.0000 0.0008 0.0001 0.0002 0.0001 0.0001 0.0000
28. C 0.0002 0.0002 0.0002 0.0112 0.0000 0.0006 0.0018 0.0003 0.0000
29. C 0.0002 0.0001 0.0001 0.0061 0.0002 0.0020 0.0073 0.0009 0.0000
30. C 0.0001 0.0000 0.0000 0.0003 0.0000 0.0001 0.0001 0.0000 0.0000
31. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
32. C 0.0001 0.0000 0.0000 0.0004 0.0000 0.0001 0.0002 0.0001 0.0000
33. H 0.0002 0.0000 0.0000 0.0002 0.0000 0.0012 0.0137 0.0016 0.0000
34. C 0.0001 0.0001 0.0001 0.0057 0.0000 0.0005 0.0011 0.0002 0.0000
35. H 0.0000 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000 0.0000 0.0000
36. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0002 0.0000 0.0000
37. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Atom 10 11 12 13 14 15 16 17 18
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0001 0.0003 0.0003 0.0009 0.0000 0.0028 0.0007 0.0369 0.4536
2. H 0.0000 0.0000 0.0001 0.0003 0.0000 0.0000 0.0000 0.0009 0.0026
3. H 0.0000 0.0000 0.0001 0.0001 0.0000 0.0003 0.0000 0.0011 0.0018
4. C 0.0001 0.0005 0.0004 0.0018 0.0001 0.0021 0.0006 0.0419 0.0448
5. H 0.0003 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0004 0.0009
6. C 0.0081 0.0020 0.0019 0.0003 0.0000 0.0001 0.0001 0.0048 0.0109
7. O 0.0025 0.0037 0.0045 0.0002 0.0000 0.0002 0.0001 0.0057 0.0115
8. O 0.0058 0.0170 0.0173 0.0001 0.0000 0.0001 0.0001 0.0019 0.0022
9. C 0.9349 0.9296 0.9299 0.0000 0.0000 0.0000 0.0000 0.0001 0.0001
10. H 0.0000 0.0004 0.0004 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
11. H 0.0004 0.0000 0.0003 0.0000 0.0000 0.0000 0.0000 0.0001 0.0001
12. H 0.0004 0.0003 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
13. C 0.0000 0.0000 0.0000 0.0000 0.9191 0.9178 0.8976 0.9217 0.0320
14. H 0.0000 0.0000 0.0000 0.9191 0.0000 0.0008 0.0008 0.0011 0.0081
15. H 0.0000 0.0000 0.0000 0.9178 0.0008 0.0000 0.0005 0.0030 0.0013
16. H 0.0000 0.0000 0.0000 0.8976 0.0008 0.0005 0.0000 0.0026 0.0014
17. N 0.0000 0.0001 0.0000 0.9217 0.0011 0.0030 0.0026 0.0000 1.1114
18. N 0.0000 0.0001 0.0000 0.0320 0.0081 0.0013 0.0014 1.1114 0.0000
19. C 0.0000 0.0000 0.0000 0.0046 0.0014 0.0003 0.0005 0.0092 1.1788
20. O 0.0000 0.0000 0.0000 0.0115 0.0013 0.0001 0.0096 0.0074 0.1565
21. C 0.0000 0.0000 0.0000 0.0008 0.0006 0.0000 0.0008 0.0136 0.0124
22. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0003 0.0012
23. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0006 0.0068
24. H 0.0000 0.0000 0.0000 0.0001 0.0001 0.0000 0.0000 0.0001 0.0053
25. C 0.0000 0.0003 0.0002 0.0183 0.0005 0.0122 0.0106 1.4120 0.1166
26. H 0.0000 0.0002 0.0000 0.0138 0.0004 0.0001 0.0002 0.0017 0.0037
27. C 0.0000 0.0000 0.0000 0.0015 0.0018 0.0005 0.0001 0.0105 0.0116
28. C 0.0000 0.0000 0.0000 0.0016 0.0039 0.0008 0.0004 0.0148 0.0069
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29. C 0.0000 0.0000 0.0000 0.0009 0.0001 0.0006 0.0002 0.0174 0.0055
30. C 0.0000 0.0000 0.0000 0.0016 0.0001 0.0001 0.0000 0.0010 0.0004
31. H 0.0000 0.0000 0.0000 0.0004 0.0002 0.0001 0.0000 0.0001 0.0001
32. C 0.0000 0.0000 0.0000 0.0008 0.0002 0.0002 0.0000 0.0006 0.0005
33. H 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0002 0.0001
34. C 0.0000 0.0000 0.0000 0.0006 0.0001 0.0004 0.0001 0.0074 0.0040
35. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0001
36. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0001
37. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Atom 19 20 21 22 23 24 25 26 27
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0048 0.0201 0.0019 0.0002 0.0005 0.0003 0.0030 0.0007 0.0002
2. H 0.0002 0.0002 0.0004 0.0004 0.0000 0.0000 0.0029 0.0000 0.0000
3. H 0.0007 0.0006 0.0002 0.0001 0.0000 0.0003 0.0034 0.0000 0.0000
4. C 0.0023 0.0028 0.0005 0.0000 0.0001 0.0001 0.2149 0.0009 0.0008
5. H 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000 0.0003 0.0000 0.0001
6. C 0.0002 0.0014 0.0001 0.0000 0.0000 0.0000 0.0127 0.0004 0.0002
7. O 0.0005 0.0013 0.0000 0.0000 0.0000 0.0000 0.0205 0.0004 0.0001
8. O 0.0001 0.0003 0.0000 0.0000 0.0000 0.0000 0.0083 0.0046 0.0001
9. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0003 0.0001 0.0000
10. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
11. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0003 0.0002 0.0000
12. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0000 0.0000
13. C 0.0046 0.0115 0.0008 0.0001 0.0000 0.0001 0.0183 0.0138 0.0015
14. H 0.0014 0.0013 0.0006 0.0000 0.0000 0.0001 0.0005 0.0004 0.0018
15. H 0.0003 0.0001 0.0000 0.0000 0.0000 0.0000 0.0122 0.0001 0.0005
16. H 0.0005 0.0096 0.0008 0.0000 0.0000 0.0000 0.0106 0.0002 0.0001
17. N 0.0092 0.0074 0.0136 0.0003 0.0006 0.0001 1.4120 0.0017 0.0105
18. N 1.1788 0.1565 0.0124 0.0012 0.0068 0.0053 0.1166 0.0037 0.0116
19. C 0.0000 1.6632 0.9936 0.0039 0.0028 0.0044 0.0220 0.0004 0.0006
20. O 1.6632 0.0000 0.0547 0.0147 0.0034 0.0136 0.0190 0.0001 0.0005
21. C 0.9936 0.0547 0.0000 0.9160 0.9166 0.9125 0.0006 0.0002 0.0005
22. H 0.0039 0.0147 0.9160 0.0000 0.0007 0.0009 0.0001 0.0000 0.0000
23. H 0.0028 0.0034 0.9166 0.0007 0.0000 0.0009 0.0002 0.0000 0.0001
24. H 0.0044 0.0136 0.9125 0.0009 0.0009 0.0000 0.0008 0.0000 0.0000
25. C 0.0220 0.0190 0.0006 0.0001 0.0002 0.0008 0.0000 0.8801 1.0734
26. H 0.0004 0.0001 0.0002 0.0000 0.0000 0.0000 0.8801 0.0000 0.0032
27. C 0.0006 0.0005 0.0005 0.0000 0.0001 0.0000 1.0734 0.0032 0.0000
28. C 0.0011 0.0018 0.0001 0.0000 0.0000 0.0001 0.0115 0.0087 1.3687
29. C 0.0011 0.0017 0.0001 0.0000 0.0000 0.0001 0.0124 0.0042 1.3719
30. C 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0086 0.0001 0.0122
31. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0013 0.0001 0.0029
32. C 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000 0.0094 0.0001 0.0109
33. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0013 0.0001 0.0034
34. C 0.0007 0.0014 0.0000 0.0000 0.0000 0.0000 0.0021 0.0028 0.1015
35. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0003 0.0001 0.0080
36. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0000 0.0082
37. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0004 0.0000 0.0002
Atom 28 29 30 31 32 33 34 35 36
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0002 0.0002 0.0001 0.0000 0.0001 0.0002 0.0001 0.0000 0.0000
2. H 0.0002 0.0001 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000
3. H 0.0002 0.0001 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000
4. C 0.0112 0.0061 0.0003 0.0000 0.0004 0.0002 0.0057 0.0002 0.0001
5. H 0.0000 0.0002 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
6. C 0.0006 0.0020 0.0001 0.0000 0.0001 0.0012 0.0005 0.0000 0.0000
7. O 0.0018 0.0073 0.0001 0.0000 0.0002 0.0137 0.0011 0.0000 0.0002
8. O 0.0003 0.0009 0.0000 0.0000 0.0001 0.0016 0.0002 0.0000 0.0000
9. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
10. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
11. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
12. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000
13. C 0.0016 0.0009 0.0016 0.0004 0.0008 0.0000 0.0006 0.0000 0.0000
14. H 0.0039 0.0001 0.0001 0.0002 0.0002 0.0000 0.0001 0.0000 0.0000
15. H 0.0008 0.0006 0.0001 0.0001 0.0002 0.0000 0.0004 0.0000 0.0000
16. H 0.0004 0.0002 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000
17. N 0.0148 0.0174 0.0010 0.0001 0.0006 0.0002 0.0074 0.0002 0.0002
18. N 0.0069 0.0055 0.0004 0.0001 0.0005 0.0001 0.0040 0.0001 0.0001
19. C 0.0011 0.0011 0.0001 0.0000 0.0001 0.0000 0.0007 0.0000 0.0000
20. O 0.0018 0.0017 0.0000 0.0000 0.0001 0.0000 0.0014 0.0000 0.0000
21. C 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
22. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
23. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
24. H 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
25. C 0.0115 0.0124 0.0086 0.0013 0.0094 0.0013 0.0021 0.0003 0.0002
26. H 0.0087 0.0042 0.0001 0.0001 0.0001 0.0001 0.0028 0.0001 0.0000
27. C 1.3687 1.3719 0.0122 0.0029 0.0109 0.0034 0.1015 0.0080 0.0082
28. C 0.0000 0.0146 1.4448 0.9105 0.1057 0.0076 0.0113 0.0034 0.0003
29. C 0.0146 0.0000 0.1073 0.0086 1.4495 0.8849 0.0119 0.0003 0.0037
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30. C 1.4448 0.1073 0.0000 0.0040 0.0109 0.0003 1.4294 0.9114 0.0084
31. H 0.9105 0.0086 0.0040 0.0000 0.0003 0.0004 0.0084 0.0021 0.0004
32. C 0.1057 1.4495 0.0109 0.0003 0.0000 0.0041 1.4271 0.0084 0.9103
33. H 0.0076 0.8849 0.0003 0.0004 0.0041 0.0000 0.0077 0.0003 0.0020
34. C 0.0113 0.0119 1.4294 0.0084 1.4271 0.0077 0.0000 0.0036 0.0033
35. H 0.0034 0.0003 0.9114 0.0021 0.0084 0.0003 0.0036 0.0000 0.0004
36. H 0.0003 0.0037 0.0084 0.0004 0.9103 0.0020 0.0033 0.0004 0.0000
37. H 0.0084 0.0085 0.0033 0.0004 0.0035 0.0003 0.9129 0.0020 0.0020
Atom 37
---- ------
1. C 0.0000
2. H 0.0000
3. H 0.0000
4. C 0.0000
5. H 0.0000
6. C 0.0000
7. O 0.0000
8. O 0.0000
9. C 0.0000
10. H 0.0000
11. H 0.0000
12. H 0.0000
13. C 0.0000
14. H 0.0000
15. H 0.0000
16. H 0.0000
17. N 0.0000
18. N 0.0000
19. C 0.0000
20. O 0.0000
21. C 0.0000
22. H 0.0000
23. H 0.0000
24. H 0.0000
25. C 0.0004
26. H 0.0000
27. C 0.0002
28. C 0.0084
29. C 0.0085
30. C 0.0033
31. H 0.0004
32. C 0.0035
33. H 0.0003
34. C 0.9129
35. H 0.0020
36. H 0.0020
37. H 0.0000
------------------------------------o-----------------------------------o------------------------------------
2 tsn nbo: Wiberg bond index matrix in the NAO basis:
Atom 1 2 3 4 5 6 7 8 9
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0000 0.9125 0.9158 1.4218 0.0062 0.0234 0.0415 0.0087 0.0004
2. H 0.9125 0.0000 0.0003 0.0042 0.0110 0.0016 0.0004 0.0024 0.0001
3. H 0.9158 0.0003 0.0000 0.0040 0.0022 0.0077 0.0015 0.0012 0.0001
4. C 1.4218 0.0042 0.0040 0.0000 0.9050 1.1388 0.0653 0.0210 0.0154
5. H 0.0062 0.0110 0.0022 0.9050 0.0000 0.0036 0.0020 0.0072 0.0008
6. C 0.0234 0.0016 0.0077 1.1388 0.0036 0.0000 1.6516 0.9639 0.0096
7. O 0.0415 0.0004 0.0015 0.0653 0.0020 1.6516 0.0000 0.1380 0.0145
8. O 0.0087 0.0024 0.0012 0.0210 0.0072 0.9639 0.1380 0.0000 0.8889
9. C 0.0004 0.0001 0.0001 0.0154 0.0008 0.0096 0.0145 0.8889 0.0000
10. H 0.0001 0.0000 0.0000 0.0001 0.0003 0.0082 0.0025 0.0056 0.9376
11. H 0.0003 0.0001 0.0001 0.0005 0.0000 0.0019 0.0041 0.0176 0.9314
12. H 0.0002 0.0000 0.0000 0.0005 0.0000 0.0018 0.0040 0.0173 0.9304
13. C 0.0008 0.0001 0.0002 0.0017 0.0000 0.0005 0.0007 0.0030 0.0002
14. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0001 0.0000
15. H 0.0023 0.0002 0.0000 0.0015 0.0001 0.0001 0.0011 0.0037 0.0002
16. H 0.0009 0.0000 0.0000 0.0009 0.0000 0.0001 0.0000 0.0008 0.0000
17. N 0.0383 0.0011 0.0010 0.0456 0.0003 0.0034 0.0060 0.0017 0.0001
18. N 0.4635 0.0015 0.0029 0.0437 0.0008 0.0124 0.0118 0.0022 0.0000
19. C 0.0049 0.0007 0.0002 0.0022 0.0000 0.0002 0.0004 0.0001 0.0000
20. O 0.0202 0.0006 0.0002 0.0026 0.0001 0.0014 0.0012 0.0002 0.0000
21. C 0.0020 0.0002 0.0004 0.0005 0.0000 0.0000 0.0001 0.0000 0.0000
22. H 0.0002 0.0001 0.0005 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
23. H 0.0005 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
24. H 0.0003 0.0003 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
25. C 0.0030 0.0033 0.0032 0.2131 0.0006 0.0141 0.0253 0.0058 0.0001
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26. H 0.0004 0.0000 0.0000 0.0009 0.0001 0.0005 0.0001 0.0001 0.0000
27. C 0.0002 0.0000 0.0000 0.0007 0.0001 0.0006 0.0007 0.0001 0.0000
28. C 0.0002 0.0002 0.0002 0.0106 0.0000 0.0009 0.0013 0.0003 0.0000
29. C 0.0003 0.0002 0.0002 0.0094 0.0001 0.0012 0.0087 0.0006 0.0001
30. C 0.0000 0.0000 0.0000 0.0002 0.0000 0.0001 0.0004 0.0000 0.0000
31. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
32. C 0.0000 0.0000 0.0000 0.0003 0.0000 0.0003 0.0006 0.0001 0.0000
33. H 0.0001 0.0000 0.0000 0.0004 0.0001 0.0004 0.0076 0.0011 0.0000
34. C 0.0001 0.0001 0.0001 0.0064 0.0000 0.0004 0.0013 0.0002 0.0000
35. H 0.0000 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000 0.0000 0.0000
36. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0001 0.0000 0.0000
37. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Atom 10 11 12 13 14 15 16 17 18
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0001 0.0003 0.0002 0.0008 0.0000 0.0023 0.0009 0.0383 0.4635
2. H 0.0000 0.0001 0.0000 0.0001 0.0000 0.0002 0.0000 0.0011 0.0015
3. H 0.0000 0.0001 0.0000 0.0002 0.0000 0.0000 0.0000 0.0010 0.0029
4. C 0.0001 0.0005 0.0005 0.0017 0.0001 0.0015 0.0009 0.0456 0.0437
5. H 0.0003 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0003 0.0008
6. C 0.0082 0.0019 0.0018 0.0005 0.0000 0.0001 0.0001 0.0034 0.0124
7. O 0.0025 0.0041 0.0040 0.0007 0.0000 0.0011 0.0000 0.0060 0.0118
8. O 0.0056 0.0176 0.0173 0.0030 0.0001 0.0037 0.0008 0.0017 0.0022
9. C 0.9376 0.9314 0.9304 0.0002 0.0000 0.0002 0.0000 0.0001 0.0000
10. H 0.0000 0.0003 0.0003 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
11. H 0.0003 0.0000 0.0002 0.0000 0.0000 0.0000 0.0000 0.0001 0.0001
12. H 0.0003 0.0002 0.0000 0.0001 0.0000 0.0001 0.0000 0.0001 0.0001
13. C 0.0000 0.0000 0.0001 0.0000 0.9225 0.9109 0.9020 0.9181 0.0318
14. H 0.0000 0.0000 0.0000 0.9225 0.0000 0.0009 0.0007 0.0011 0.0079
15. H 0.0000 0.0000 0.0001 0.9109 0.0009 0.0000 0.0004 0.0025 0.0011
16. H 0.0000 0.0000 0.0000 0.9020 0.0007 0.0004 0.0000 0.0026 0.0015
17. N 0.0000 0.0001 0.0001 0.9181 0.0011 0.0025 0.0026 0.0000 1.1128
18. N 0.0000 0.0001 0.0001 0.0318 0.0079 0.0011 0.0015 1.1128 0.0000
19. C 0.0000 0.0000 0.0000 0.0045 0.0014 0.0003 0.0005 0.0094 1.1760
20. O 0.0000 0.0000 0.0000 0.0113 0.0013 0.0001 0.0091 0.0073 0.1573
21. C 0.0000 0.0000 0.0000 0.0008 0.0005 0.0000 0.0007 0.0135 0.0122
22. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0003 0.0013
23. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0006 0.0066
24. H 0.0000 0.0000 0.0000 0.0001 0.0001 0.0000 0.0000 0.0001 0.0049
25. C 0.0000 0.0002 0.0002 0.0181 0.0005 0.0122 0.0102 1.4121 0.1138
26. H 0.0000 0.0000 0.0000 0.0139 0.0004 0.0001 0.0002 0.0015 0.0034
27. C 0.0000 0.0000 0.0000 0.0014 0.0017 0.0004 0.0001 0.0111 0.0115
28. C 0.0000 0.0000 0.0000 0.0015 0.0035 0.0007 0.0004 0.0148 0.0067
29. C 0.0000 0.0001 0.0000 0.0009 0.0001 0.0006 0.0002 0.0166 0.0061
30. C 0.0000 0.0000 0.0000 0.0015 0.0001 0.0001 0.0000 0.0011 0.0004
31. H 0.0000 0.0000 0.0000 0.0004 0.0002 0.0001 0.0000 0.0001 0.0001
32. C 0.0000 0.0000 0.0000 0.0008 0.0001 0.0001 0.0000 0.0005 0.0005
33. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0001
34. C 0.0000 0.0000 0.0000 0.0006 0.0001 0.0004 0.0001 0.0072 0.0040
35. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0001
36. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0001
37. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Atom 19 20 21 22 23 24 25 26 27
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0049 0.0202 0.0020 0.0002 0.0005 0.0003 0.0030 0.0004 0.0002
2. H 0.0007 0.0006 0.0002 0.0001 0.0000 0.0003 0.0033 0.0000 0.0000
3. H 0.0002 0.0002 0.0004 0.0005 0.0000 0.0001 0.0032 0.0000 0.0000
4. C 0.0022 0.0026 0.0005 0.0000 0.0000 0.0001 0.2131 0.0009 0.0007
5. H 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0006 0.0001 0.0001
6. C 0.0002 0.0014 0.0000 0.0000 0.0000 0.0000 0.0141 0.0005 0.0006
7. O 0.0004 0.0012 0.0001 0.0000 0.0000 0.0000 0.0253 0.0001 0.0007
8. O 0.0001 0.0002 0.0000 0.0000 0.0000 0.0000 0.0058 0.0001 0.0001
9. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000
10. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
11. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0000 0.0000
12. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0000 0.0000
13. C 0.0045 0.0113 0.0008 0.0001 0.0000 0.0001 0.0181 0.0139 0.0014
14. H 0.0014 0.0013 0.0005 0.0000 0.0000 0.0001 0.0005 0.0004 0.0017
15. H 0.0003 0.0001 0.0000 0.0000 0.0000 0.0000 0.0122 0.0001 0.0004
16. H 0.0005 0.0091 0.0007 0.0000 0.0000 0.0000 0.0102 0.0002 0.0001
17. N 0.0094 0.0073 0.0135 0.0003 0.0006 0.0001 1.4121 0.0015 0.0111
18. N 1.1760 0.1573 0.0122 0.0013 0.0066 0.0049 0.1138 0.0034 0.0115
19. C 0.0000 1.6664 0.9934 0.0039 0.0027 0.0042 0.0215 0.0004 0.0007
20. O 1.6664 0.0000 0.0545 0.0151 0.0033 0.0138 0.0183 0.0001 0.0005
21. C 0.9934 0.0545 0.0000 0.9185 0.9187 0.9142 0.0006 0.0002 0.0005
22. H 0.0039 0.0151 0.9185 0.0000 0.0007 0.0008 0.0001 0.0000 0.0000
23. H 0.0027 0.0033 0.9187 0.0007 0.0000 0.0008 0.0002 0.0000 0.0001
24. H 0.0042 0.0138 0.9142 0.0008 0.0008 0.0000 0.0007 0.0000 0.0000
25. C 0.0215 0.0183 0.0006 0.0001 0.0002 0.0007 0.0000 0.8877 1.0766
26. H 0.0004 0.0001 0.0002 0.0000 0.0000 0.0000 0.8877 0.0000 0.0031
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27. C 0.0007 0.0005 0.0005 0.0000 0.0001 0.0000 1.0766 0.0031 0.0000
28. C 0.0010 0.0017 0.0001 0.0000 0.0000 0.0000 0.0117 0.0088 1.3650
29. C 0.0011 0.0017 0.0001 0.0000 0.0000 0.0000 0.0124 0.0044 1.3713
30. C 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0091 0.0001 0.0122
31. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0013 0.0001 0.0028
32. C 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000 0.0088 0.0001 0.0109
33. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0013 0.0001 0.0031
34. C 0.0007 0.0013 0.0000 0.0000 0.0000 0.0000 0.0020 0.0028 0.1009
35. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0003 0.0001 0.0080
36. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0000 0.0081
37. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0004 0.0000 0.0002
Atom 28 29 30 31 32 33 34 35 36
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0002 0.0003 0.0000 0.0000 0.0000 0.0001 0.0001 0.0000 0.0000
2. H 0.0002 0.0002 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000
3. H 0.0002 0.0002 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000
4. C 0.0106 0.0094 0.0002 0.0000 0.0003 0.0004 0.0064 0.0002 0.0001
5. H 0.0000 0.0001 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000
6. C 0.0009 0.0012 0.0001 0.0000 0.0003 0.0004 0.0004 0.0000 0.0000
7. O 0.0013 0.0087 0.0004 0.0000 0.0006 0.0076 0.0013 0.0000 0.0001
8. O 0.0003 0.0006 0.0000 0.0000 0.0001 0.0011 0.0002 0.0000 0.0000
9. C 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
10. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
11. H 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
12. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
13. C 0.0015 0.0009 0.0015 0.0004 0.0008 0.0000 0.0006 0.0000 0.0000
14. H 0.0035 0.0001 0.0001 0.0002 0.0001 0.0000 0.0001 0.0000 0.0000
15. H 0.0007 0.0006 0.0001 0.0001 0.0001 0.0000 0.0004 0.0000 0.0000
16. H 0.0004 0.0002 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000
17. N 0.0148 0.0166 0.0011 0.0001 0.0005 0.0001 0.0072 0.0002 0.0002
18. N 0.0067 0.0061 0.0004 0.0001 0.0005 0.0001 0.0040 0.0001 0.0001
19. C 0.0010 0.0011 0.0001 0.0000 0.0001 0.0000 0.0007 0.0000 0.0000
20. O 0.0017 0.0017 0.0000 0.0000 0.0001 0.0000 0.0013 0.0000 0.0000
21. C 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
22. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
23. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
24. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
25. C 0.0117 0.0124 0.0091 0.0013 0.0088 0.0013 0.0020 0.0003 0.0002
26. H 0.0088 0.0044 0.0001 0.0001 0.0001 0.0001 0.0028 0.0001 0.0000
27. C 1.3650 1.3713 0.0122 0.0028 0.0109 0.0031 0.1009 0.0080 0.0081
28. C 0.0000 0.0145 1.4489 0.9122 0.1067 0.0079 0.0113 0.0033 0.0003
29. C 0.0145 0.0000 0.1063 0.0085 1.4454 0.8958 0.0118 0.0003 0.0035
30. C 1.4489 0.1063 0.0000 0.0039 0.0109 0.0003 1.4258 0.9131 0.0084
31. H 0.9122 0.0085 0.0039 0.0000 0.0003 0.0004 0.0084 0.0021 0.0004
32. C 0.1067 1.4454 0.0109 0.0003 0.0000 0.0041 1.4309 0.0084 0.9118
33. H 0.0079 0.8958 0.0003 0.0004 0.0041 0.0000 0.0079 0.0003 0.0021
34. C 0.0113 0.0118 1.4258 0.0084 1.4309 0.0079 0.0000 0.0035 0.0033
35. H 0.0033 0.0003 0.9131 0.0021 0.0084 0.0003 0.0035 0.0000 0.0004
36. H 0.0003 0.0035 0.0084 0.0004 0.9118 0.0021 0.0033 0.0004 0.0000
37. H 0.0083 0.0084 0.0032 0.0004 0.0034 0.0003 0.9146 0.0020 0.0020
Atom 37
---- ------
1. C 0.0000
2. H 0.0000
3. H 0.0000
4. C 0.0000
5. H 0.0000
6. C 0.0000
7. O 0.0000
8. O 0.0000
9. C 0.0000
10. H 0.0000
11. H 0.0000
12. H 0.0000
13. C 0.0000
14. H 0.0000
15. H 0.0000
16. H 0.0000
17. N 0.0000
18. N 0.0000
19. C 0.0000
20. O 0.0000
21. C 0.0000
22. H 0.0000
23. H 0.0000
24. H 0.0000
25. C 0.0004
26. H 0.0000
27. C 0.0002
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28. C 0.0083
29. C 0.0084
30. C 0.0032
31. H 0.0004
32. C 0.0034
33. H 0.0003
34. C 0.9146
35. H 0.0020
36. H 0.0020
37. H 0.0000
------------------------------------o---------------------------o--------------
3 trx nbo: Wiberg bond index matrix in the NAO basis:
Atom 1 2 3 4 5 6 7 8 9
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0000 0.9200 0.9211 0.9144 0.9260 0.0324 0.0045 0.0058 0.0013
2. H 0.9200 0.0000 0.0009 0.0003 0.0016 0.0108 0.0006 0.0013 0.0000
3. H 0.9211 0.0009 0.0000 0.0005 0.0018 0.0015 0.0004 0.0002 0.0014
4. H 0.9144 0.0003 0.0005 0.0000 0.0042 0.0022 0.0001 0.0001 0.0002
5. N 0.9260 0.0016 0.0018 0.0042 0.0000 1.1368 0.0093 0.0198 0.0030
6. N 0.0324 0.0108 0.0015 0.0022 1.1368 0.0000 1.1994 0.1729 0.0107
7. C 0.0045 0.0006 0.0004 0.0001 0.0093 1.1994 0.0000 1.6627 0.9793
8. O 0.0058 0.0013 0.0002 0.0001 0.0198 0.1729 1.6627 0.0000 0.0595
9. C 0.0013 0.0000 0.0014 0.0002 0.0030 0.0107 0.9793 0.0595 0.0000
10. H 0.0002 0.0000 0.0001 0.0002 0.0007 0.0011 0.0026 0.0130 0.9301
11. H 0.0011 0.0000 0.0000 0.0000 0.0004 0.0090 0.0041 0.0058 0.9065
12. H 0.0003 0.0000 0.0004 0.0000 0.0001 0.0080 0.0037 0.0088 0.9151
13. C 0.0193 0.0008 0.0074 0.0116 1.3879 0.1649 0.0184 0.0205 0.0060
14. H 0.0132 0.0002 0.0002 0.0001 0.0024 0.0027 0.0002 0.0005 0.0000
15. C 0.0014 0.0009 0.0003 0.0003 0.0121 0.0116 0.0006 0.0010 0.0001
16. C 0.0023 0.0030 0.0009 0.0013 0.0197 0.0161 0.0009 0.0021 0.0008
17. C 0.0006 0.0001 0.0003 0.0008 0.0247 0.0171 0.0012 0.0022 0.0009
18. C 0.0011 0.0001 0.0001 0.0001 0.0009 0.0003 0.0000 0.0001 0.0000
19. H 0.0010 0.0002 0.0001 0.0004 0.0002 0.0002 0.0000 0.0000 0.0000
20. C 0.0006 0.0002 0.0001 0.0000 0.0004 0.0004 0.0000 0.0001 0.0000
21. H 0.0000 0.0000 0.0000 0.0000 0.0003 0.0001 0.0000 0.0000 0.0000
22. C 0.0004 0.0002 0.0002 0.0007 0.0137 0.0139 0.0009 0.0020 0.0008
23. H 0.0000 0.0000 0.0000 0.0000 0.0001 0.0001 0.0000 0.0000 0.0000
24. H 0.0000 0.0000 0.0000 0.0000 0.0002 0.0001 0.0000 0.0000 0.0000
25. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
26. C 0.0014 0.0003 0.0002 0.0023 0.0326 0.3239 0.0037 0.0053 0.0100
27. H 0.0000 0.0000 0.0000 0.0000 0.0010 0.0019 0.0004 0.0017 0.0002
28. C 0.0011 0.0000 0.0003 0.0030 0.0260 0.0458 0.0026 0.0038 0.0019
29. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0002 0.0000 0.0000 0.0000
30. C 0.0002 0.0000 0.0000 0.0001 0.0029 0.0118 0.0002 0.0004 0.0007
31. C 0.0002 0.0000 0.0000 0.0000 0.0010 0.0053 0.0008 0.0042 0.0006
32. O 0.0001 0.0000 0.0001 0.0003 0.0025 0.0094 0.0003 0.0004 0.0006
33. O 0.0003 0.0000 0.0000 0.0002 0.0018 0.0122 0.0006 0.0014 0.0008
34. O 0.0001 0.0000 0.0000 0.0001 0.0011 0.0046 0.0002 0.0002 0.0003
35. O 0.0002 0.0001 0.0000 0.0000 0.0006 0.0020 0.0008 0.0008 0.0001
36. C 0.0000 0.0000 0.0000 0.0000 0.0001 0.0002 0.0000 0.0000 0.0000
37. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000
38. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000
39. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
40. C 0.0000 0.0000 0.0000 0.0000 0.0001 0.0008 0.0001 0.0001 0.0000
41. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000
42. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000
43. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000
Atom 10 11 12 13 14 15 16 17 18
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0002 0.0011 0.0003 0.0193 0.0132 0.0014 0.0023 0.0006 0.0011
2. H 0.0000 0.0000 0.0000 0.0008 0.0002 0.0009 0.0030 0.0001 0.0001
3. H 0.0001 0.0000 0.0004 0.0074 0.0002 0.0003 0.0009 0.0003 0.0001
4. H 0.0002 0.0000 0.0000 0.0116 0.0001 0.0003 0.0013 0.0008 0.0001
5. N 0.0007 0.0004 0.0001 1.3879 0.0024 0.0121 0.0197 0.0247 0.0009
6. N 0.0011 0.0090 0.0080 0.1649 0.0027 0.0116 0.0161 0.0171 0.0003
7. C 0.0026 0.0041 0.0037 0.0184 0.0002 0.0006 0.0009 0.0012 0.0000
8. O 0.0130 0.0058 0.0088 0.0205 0.0005 0.0010 0.0021 0.0022 0.0001
9. C 0.9301 0.9065 0.9151 0.0060 0.0000 0.0001 0.0008 0.0009 0.0000
10. H 0.0000 0.0007 0.0005 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
11. H 0.0007 0.0000 0.0011 0.0002 0.0000 0.0000 0.0000 0.0000 0.0000
12. H 0.0005 0.0011 0.0000 0.0009 0.0000 0.0000 0.0001 0.0001 0.0000
13. C 0.0001 0.0002 0.0009 0.0000 0.8823 1.1229 0.0106 0.0138 0.0104
14. H 0.0000 0.0000 0.0000 0.8823 0.0000 0.0033 0.0070 0.0017 0.0001
15. C 0.0000 0.0000 0.0000 1.1229 0.0033 0.0000 1.3476 1.3482 0.0116
16. C 0.0000 0.0000 0.0001 0.0106 0.0070 1.3476 0.0000 0.0134 1.4586
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17. C 0.0000 0.0000 0.0001 0.0138 0.0017 1.3482 0.0134 0.0000 0.1019
18. C 0.0000 0.0000 0.0000 0.0104 0.0001 0.0116 1.4586 0.1019 0.0000
19. H 0.0000 0.0000 0.0000 0.0012 0.0000 0.0030 0.9142 0.0085 0.0040
20. C 0.0000 0.0000 0.0000 0.0092 0.0003 0.0108 0.1033 1.4561 0.0109
21. H 0.0000 0.0000 0.0000 0.0017 0.0004 0.0029 0.0083 0.9103 0.0003
22. C 0.0000 0.0000 0.0001 0.0019 0.0005 0.0949 0.0114 0.0117 1.4204
23. H 0.0000 0.0000 0.0000 0.0003 0.0003 0.0081 0.0033 0.0003 0.9128
24. H 0.0000 0.0000 0.0000 0.0002 0.0000 0.0082 0.0003 0.0034 0.0084
25. H 0.0000 0.0000 0.0000 0.0003 0.0000 0.0002 0.0083 0.0083 0.0033
26. C 0.0002 0.0001 0.0004 0.0026 0.0006 0.0005 0.0002 0.0002 0.0000
27. H 0.0000 0.0000 0.0000 0.0030 0.0000 0.0000 0.0004 0.0004 0.0000
28. C 0.0000 0.0006 0.0000 0.1484 0.0010 0.0006 0.0088 0.0129 0.0001
29. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0001 0.0000 0.0000
30. C 0.0000 0.0001 0.0000 0.0127 0.0005 0.0007 0.0008 0.0005 0.0000
31. C 0.0000 0.0000 0.0000 0.0005 0.0002 0.0000 0.0000 0.0000 0.0000
32. O 0.0000 0.0001 0.0000 0.0145 0.0036 0.0007 0.0009 0.0021 0.0002
33. O 0.0000 0.0000 0.0000 0.0005 0.0005 0.0000 0.0001 0.0001 0.0000
34. O 0.0000 0.0000 0.0000 0.0069 0.0005 0.0005 0.0006 0.0002 0.0001
35. O 0.0000 0.0001 0.0000 0.0019 0.0035 0.0001 0.0001 0.0000 0.0000
36. C 0.0000 0.0000 0.0000 0.0001 0.0000 0.0001 0.0000 0.0002 0.0001
37. H 0.0000 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000 0.0000 0.0000
38. H 0.0000 0.0000 0.0000 0.0002 0.0000 0.0000 0.0001 0.0004 0.0000
39. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
40. C 0.0000 0.0000 0.0000 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000
41. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
42. H 0.0000 0.0000 0.0000 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000
43. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Atom 19 20 21 22 23 24 25 26 27
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0010 0.0006 0.0000 0.0004 0.0000 0.0000 0.0000 0.0014 0.0000
2. H 0.0002 0.0002 0.0000 0.0002 0.0000 0.0000 0.0000 0.0003 0.0000
3. H 0.0001 0.0001 0.0000 0.0002 0.0000 0.0000 0.0000 0.0002 0.0000
4. H 0.0004 0.0000 0.0000 0.0007 0.0000 0.0000 0.0000 0.0023 0.0000
5. N 0.0002 0.0004 0.0003 0.0137 0.0001 0.0002 0.0000 0.0326 0.0010
6. N 0.0002 0.0004 0.0001 0.0139 0.0001 0.0001 0.0000 0.3239 0.0019
7. C 0.0000 0.0000 0.0000 0.0009 0.0000 0.0000 0.0000 0.0037 0.0004
8. O 0.0000 0.0001 0.0000 0.0020 0.0000 0.0000 0.0000 0.0053 0.0017
9. C 0.0000 0.0000 0.0000 0.0008 0.0000 0.0000 0.0000 0.0100 0.0002
10. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0000
11. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000
12. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0004 0.0000
13. C 0.0012 0.0092 0.0017 0.0019 0.0003 0.0002 0.0003 0.0026 0.0030
14. H 0.0000 0.0003 0.0004 0.0005 0.0003 0.0000 0.0000 0.0006 0.0000
15. C 0.0030 0.0108 0.0029 0.0949 0.0081 0.0082 0.0002 0.0005 0.0000
16. C 0.9142 0.1033 0.0083 0.0114 0.0033 0.0003 0.0083 0.0002 0.0004
17. C 0.0085 1.4561 0.9103 0.0117 0.0003 0.0034 0.0083 0.0002 0.0004
18. C 0.0040 0.0109 0.0003 1.4204 0.9128 0.0084 0.0033 0.0000 0.0000
19. H 0.0000 0.0003 0.0004 0.0084 0.0021 0.0004 0.0003 0.0000 0.0000
20. C 0.0003 0.0000 0.0038 1.4237 0.0084 0.9118 0.0033 0.0001 0.0000
21. H 0.0004 0.0038 0.0000 0.0084 0.0004 0.0022 0.0004 0.0000 0.0000
22. C 0.0084 1.4237 0.0084 0.0000 0.0034 0.0034 0.9138 0.0001 0.0003
23. H 0.0021 0.0084 0.0004 0.0034 0.0000 0.0004 0.0020 0.0000 0.0000
24. H 0.0004 0.9118 0.0022 0.0034 0.0004 0.0000 0.0020 0.0000 0.0000
25. H 0.0003 0.0033 0.0004 0.9138 0.0020 0.0020 0.0000 0.0000 0.0000
26. C 0.0000 0.0001 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.8797
27. H 0.0000 0.0000 0.0000 0.0003 0.0000 0.0000 0.0000 0.8797 0.0000
28. C 0.0002 0.0002 0.0000 0.0086 0.0000 0.0000 0.0000 1.5136 0.0048
29. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0058 0.0025
30. C 0.0000 0.0000 0.0000 0.0004 0.0000 0.0000 0.0000 0.0244 0.0082
31. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.9701 0.0033
32. O 0.0000 0.0001 0.0002 0.0011 0.0000 0.0000 0.0000 0.0325 0.0005
33. O 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0605 0.0050
34. O 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0204 0.0002
35. O 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0129 0.0062
36. C 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0010 0.0003
37. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0005 0.0000
38. H 0.0000 0.0002 0.0000 0.0000 0.0000 0.0000 0.0000 0.0006 0.0000
39. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000
40. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0186 0.0005
41. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0001
42. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0003 0.0001
43. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0001
Atom 28 29 30 31 32 33 34 35 36
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0011 0.0000 0.0002 0.0002 0.0001 0.0003 0.0001 0.0002 0.0000
2. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000
3. H 0.0003 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000
4. H 0.0030 0.0001 0.0001 0.0000 0.0003 0.0002 0.0001 0.0000 0.0000
5. N 0.0260 0.0000 0.0029 0.0010 0.0025 0.0018 0.0011 0.0006 0.0001
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6. N 0.0458 0.0002 0.0118 0.0053 0.0094 0.0122 0.0046 0.0020 0.0002
7. C 0.0026 0.0000 0.0002 0.0008 0.0003 0.0006 0.0002 0.0008 0.0000
8. O 0.0038 0.0000 0.0004 0.0042 0.0004 0.0014 0.0002 0.0008 0.0000
9. C 0.0019 0.0000 0.0007 0.0006 0.0006 0.0008 0.0003 0.0001 0.0000
10. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
11. H 0.0006 0.0000 0.0001 0.0000 0.0001 0.0000 0.0000 0.0001 0.0000
12. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
13. C 0.1484 0.0001 0.0127 0.0005 0.0145 0.0005 0.0069 0.0019 0.0001
14. H 0.0010 0.0000 0.0005 0.0002 0.0036 0.0005 0.0005 0.0035 0.0000
15. C 0.0006 0.0000 0.0007 0.0000 0.0007 0.0000 0.0005 0.0001 0.0001
16. C 0.0088 0.0001 0.0008 0.0000 0.0009 0.0001 0.0006 0.0001 0.0000
17. C 0.0129 0.0000 0.0005 0.0000 0.0021 0.0001 0.0002 0.0000 0.0002
18. C 0.0001 0.0000 0.0000 0.0000 0.0002 0.0000 0.0001 0.0000 0.0001
19. H 0.0002 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
20. C 0.0002 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0001
21. H 0.0000 0.0000 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000 0.0000
22. C 0.0086 0.0000 0.0004 0.0000 0.0011 0.0001 0.0001 0.0000 0.0000
23. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
24. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
25. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
26. C 1.5136 0.0058 0.0244 0.9701 0.0325 0.0605 0.0204 0.0129 0.0010
27. H 0.0048 0.0025 0.0082 0.0033 0.0005 0.0050 0.0002 0.0062 0.0003
28. C 0.0000 0.9046 1.0976 0.0139 0.0658 0.0256 0.0153 0.0052 0.0157
29. H 0.9046 0.0000 0.0036 0.0103 0.0099 0.0015 0.0008 0.0006 0.0003
30. C 1.0976 0.0036 0.0000 0.0016 1.6636 0.0020 0.9946 0.0007 0.0097
31. C 0.0139 0.0103 0.0016 0.0000 0.0088 1.7425 0.0019 1.0459 0.0001
32. O 0.0658 0.0099 1.6636 0.0088 0.0000 0.0037 0.1484 0.0022 0.0132
33. O 0.0256 0.0015 0.0020 1.7425 0.0037 0.0000 0.0017 0.1679 0.0001
34. O 0.0153 0.0008 0.9946 0.0019 0.1484 0.0017 0.0000 0.0004 0.8912
35. O 0.0052 0.0006 0.0007 1.0459 0.0022 0.1679 0.0004 0.0000 0.0001
36. C 0.0157 0.0003 0.0097 0.0001 0.0132 0.0001 0.8912 0.0001 0.0000
37. H 0.0004 0.0000 0.0020 0.0000 0.0043 0.0000 0.0166 0.0000 0.9303
38. H 0.0003 0.0000 0.0022 0.0000 0.0042 0.0001 0.0169 0.0000 0.9321
39. H 0.0000 0.0001 0.0081 0.0000 0.0022 0.0000 0.0059 0.0000 0.9369
40. C 0.0006 0.0005 0.0002 0.0106 0.0012 0.0127 0.0002 0.8777 0.0000
41. H 0.0001 0.0000 0.0000 0.0028 0.0009 0.0043 0.0001 0.0147 0.0000
42. H 0.0001 0.0000 0.0000 0.0023 0.0000 0.0049 0.0000 0.0150 0.0000
43. H 0.0002 0.0000 0.0000 0.0075 0.0000 0.0022 0.0000 0.0058 0.0000
Atom 37 38 39 40 41 42 43
---- ------ ------ ------ ------ ------ ------ ------
1. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
2. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
3. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
4. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
5. N 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000
6. N 0.0002 0.0001 0.0000 0.0008 0.0001 0.0000 0.0001
7. C 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000
8. O 0.0000 0.0000 0.0000 0.0001 0.0000 0.0001 0.0000
9. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
10. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
11. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
12. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
13. C 0.0002 0.0002 0.0000 0.0001 0.0000 0.0001 0.0000
14. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0001 0.0000
15. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
16. C 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
17. C 0.0000 0.0004 0.0000 0.0000 0.0000 0.0000 0.0000
18. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
19. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
20. C 0.0000 0.0002 0.0000 0.0000 0.0000 0.0000 0.0000
21. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
22. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
23. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
24. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
25. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
26. C 0.0005 0.0006 0.0001 0.0186 0.0002 0.0003 0.0001
27. H 0.0000 0.0000 0.0000 0.0005 0.0001 0.0001 0.0001
28. C 0.0004 0.0003 0.0000 0.0006 0.0001 0.0001 0.0002
29. H 0.0000 0.0000 0.0001 0.0005 0.0000 0.0000 0.0000
30. C 0.0020 0.0022 0.0081 0.0002 0.0000 0.0000 0.0000
31. C 0.0000 0.0000 0.0000 0.0106 0.0028 0.0023 0.0075
32. O 0.0043 0.0042 0.0022 0.0012 0.0009 0.0000 0.0000
33. O 0.0000 0.0001 0.0000 0.0127 0.0043 0.0049 0.0022
34. O 0.0166 0.0169 0.0059 0.0002 0.0001 0.0000 0.0000
35. O 0.0000 0.0000 0.0000 0.8777 0.0147 0.0150 0.0058
36. C 0.9303 0.9321 0.9369 0.0000 0.0000 0.0000 0.0000
37. H 0.0000 0.0002 0.0003 0.0000 0.0000 0.0000 0.0000
38. H 0.0002 0.0000 0.0003 0.0000 0.0000 0.0000 0.0000
39. H 0.0003 0.0003 0.0000 0.0000 0.0000 0.0000 0.0000
40. C 0.0000 0.0000 0.0000 0.0000 0.9291 0.9299 0.9378
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41. H 0.0000 0.0000 0.0000 0.9291 0.0000 0.0002 0.0003
42. H 0.0000 0.0000 0.0000 0.9299 0.0002 0.0000 0.0003
43. H 0.0000 0.0000 0.0000 0.9378 0.0003 0.0003 0.0000
Wiberg bond index, Totals by atom:
Atom 1
---- ------
1. C 3.7709
2. H 0.9418
3. H 0.9388
4. H 0.9436
5. N 3.6359
6. N 3.2307
7. C 3.8990
8. O 1.9968
9. C 3.8309
10. H 0.9497
11. H 0.9300
12. H 0.9396
13. C 3.8847
14. H 0.9263
15. C 3.9935
16. C 3.9457
17. C 3.9426
18. C 3.9459
19. H 0.9455
20. C 3.9448
21. H 0.9402
22. C 3.9457
23. H 0.9419
24. H 0.9411
25. H 0.9423
26. C 3.9261
27. H 0.9209
28. C 3.9300
29. H 0.9413
30. C 3.8508
31. C 3.8349
32. O 1.9984
33. O 2.0533
34. O 2.1299
35. O 2.1652
36. C 3.7320
37. H 0.9553
38. H 0.9581
39. H 0.9541
40. C 3.7209
41. H 0.9530
42. H 0.9535
43. H 0.9545
---------------------------o---------------------------o----------------------------
3 trn nbo: Wiberg bond index matrix in the NAO basis:
Atom 1 2 3 4 5 6 7 8 9
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0000 0.9233 0.9225 0.8904 0.9194 0.0333 0.0045 0.0056 0.0014
2. H 0.9233 0.0000 0.0009 0.0005 0.0017 0.0097 0.0005 0.0010 0.0000
3. H 0.9225 0.0009 0.0000 0.0007 0.0016 0.0016 0.0006 0.0002 0.0014
4. H 0.8904 0.0005 0.0007 0.0000 0.0027 0.0025 0.0001 0.0001 0.0001
5. N 0.9194 0.0017 0.0016 0.0027 0.0000 1.1485 0.0089 0.0196 0.0030
6. N 0.0333 0.0097 0.0016 0.0025 1.1485 0.0000 1.1751 0.1629 0.0109
7. C 0.0045 0.0005 0.0006 0.0001 0.0089 1.1751 0.0000 1.6769 0.9829
8. O 0.0056 0.0010 0.0002 0.0001 0.0196 0.1629 1.6769 0.0000 0.0588
9. C 0.0014 0.0000 0.0014 0.0001 0.0030 0.0109 0.9829 0.0588 0.0000
10. H 0.0002 0.0000 0.0001 0.0001 0.0006 0.0008 0.0027 0.0126 0.9293
11. H 0.0013 0.0000 0.0001 0.0000 0.0003 0.0088 0.0044 0.0066 0.9062
12. H 0.0003 0.0000 0.0003 0.0000 0.0001 0.0076 0.0040 0.0087 0.9119
13. C 0.0194 0.0009 0.0077 0.0109 1.3824 0.1519 0.0180 0.0179 0.0053
14. H 0.0137 0.0002 0.0003 0.0001 0.0022 0.0032 0.0003 0.0006 0.0000
15. C 0.0013 0.0009 0.0003 0.0003 0.0129 0.0113 0.0005 0.0008 0.0001
16. C 0.0022 0.0032 0.0008 0.0011 0.0191 0.0152 0.0008 0.0017 0.0007
17. C 0.0007 0.0001 0.0004 0.0007 0.0244 0.0147 0.0011 0.0018 0.0007
18. C 0.0012 0.0001 0.0001 0.0000 0.0008 0.0003 0.0000 0.0001 0.0000
19. H 0.0010 0.0002 0.0001 0.0003 0.0001 0.0001 0.0000 0.0000 0.0000
20. C 0.0007 0.0001 0.0001 0.0000 0.0005 0.0004 0.0000 0.0000 0.0000
21. H 0.0000 0.0000 0.0000 0.0000 0.0003 0.0001 0.0000 0.0000 0.0000
22. C 0.0004 0.0002 0.0003 0.0006 0.0135 0.0123 0.0007 0.0015 0.0006
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23. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000
24. H 0.0000 0.0000 0.0000 0.0000 0.0002 0.0001 0.0000 0.0000 0.0000
25. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
26. C 0.0006 0.0000 0.0004 0.0016 0.0286 0.0445 0.0019 0.0022 0.0021
27. H 0.0000 0.0000 0.0000 0.0000 0.0001 0.0005 0.0000 0.0000 0.0000
28. C 0.0007 0.0003 0.0004 0.0021 0.0345 0.3477 0.0039 0.0078 0.0100
29. H 0.0001 0.0000 0.0000 0.0000 0.0007 0.0022 0.0004 0.0015 0.0002
30. C 0.0006 0.0001 0.0000 0.0001 0.0022 0.0075 0.0019 0.0071 0.0012
31. C 0.0002 0.0000 0.0000 0.0001 0.0018 0.0114 0.0002 0.0003 0.0007
32. O 0.0058 0.0015 0.0002 0.0079 0.0014 0.0056 0.0013 0.0025 0.0004
33. O 0.0003 0.0000 0.0000 0.0010 0.0035 0.0117 0.0003 0.0004 0.0007
34. O 0.0007 0.0001 0.0000 0.0007 0.0012 0.0064 0.0009 0.0013 0.0004
35. O 0.0015 0.0000 0.0002 0.0022 0.0011 0.0025 0.0001 0.0001 0.0002
36. C 0.0000 0.0000 0.0000 0.0000 0.0001 0.0012 0.0001 0.0003 0.0000
37. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
38. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0001 0.0003 0.0000
39. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000
40. C 0.0001 0.0000 0.0000 0.0001 0.0001 0.0001 0.0000 0.0000 0.0000
41. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0001 0.0000 0.0000 0.0000
42. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000
43. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Atom 10 11 12 13 14 15 16 17 18
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0002 0.0013 0.0003 0.0194 0.0137 0.0013 0.0022 0.0007 0.0012
2. H 0.0000 0.0000 0.0000 0.0009 0.0002 0.0009 0.0032 0.0001 0.0001
3. H 0.0001 0.0001 0.0003 0.0077 0.0003 0.0003 0.0008 0.0004 0.0001
4. H 0.0001 0.0000 0.0000 0.0109 0.0001 0.0003 0.0011 0.0007 0.0000
5. N 0.0006 0.0003 0.0001 1.3824 0.0022 0.0129 0.0191 0.0244 0.0008
6. N 0.0008 0.0088 0.0076 0.1519 0.0032 0.0113 0.0152 0.0147 0.0003
7. C 0.0027 0.0044 0.0040 0.0180 0.0003 0.0005 0.0008 0.0011 0.0000
8. O 0.0126 0.0066 0.0087 0.0179 0.0006 0.0008 0.0017 0.0018 0.0001
9. C 0.9293 0.9062 0.9119 0.0053 0.0000 0.0001 0.0007 0.0007 0.0000
10. H 0.0000 0.0007 0.0005 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
11. H 0.0007 0.0000 0.0012 0.0002 0.0000 0.0000 0.0000 0.0000 0.0000
12. H 0.0005 0.0012 0.0000 0.0009 0.0000 0.0000 0.0001 0.0001 0.0000
13. C 0.0001 0.0002 0.0009 0.0000 0.8980 1.1240 0.0105 0.0137 0.0099
14. H 0.0000 0.0000 0.0000 0.8980 0.0000 0.0032 0.0075 0.0018 0.0001
15. C 0.0000 0.0000 0.0000 1.1240 0.0032 0.0000 1.3462 1.3484 0.0115
16. C 0.0000 0.0000 0.0001 0.0105 0.0075 1.3462 0.0000 0.0136 1.4552
17. C 0.0000 0.0000 0.0001 0.0137 0.0018 1.3484 0.0136 0.0000 0.1027
18. C 0.0000 0.0000 0.0000 0.0099 0.0001 0.0115 1.4552 0.1027 0.0000
19. H 0.0000 0.0000 0.0000 0.0012 0.0000 0.0031 0.9092 0.0083 0.0041
20. C 0.0000 0.0000 0.0000 0.0097 0.0003 0.0111 0.1026 1.4586 0.0109
21. H 0.0000 0.0000 0.0000 0.0016 0.0005 0.0028 0.0085 0.9144 0.0003
22. C 0.0000 0.0000 0.0001 0.0020 0.0007 0.0947 0.0117 0.0117 1.4232
23. H 0.0000 0.0000 0.0000 0.0002 0.0003 0.0081 0.0034 0.0003 0.9132
24. H 0.0000 0.0000 0.0000 0.0002 0.0000 0.0082 0.0003 0.0034 0.0083
25. H 0.0000 0.0000 0.0000 0.0004 0.0000 0.0002 0.0083 0.0083 0.0033
26. C 0.0001 0.0003 0.0001 0.1682 0.0006 0.0007 0.0132 0.0126 0.0001
27. H 0.0000 0.0000 0.0000 0.0004 0.0001 0.0001 0.0000 0.0000 0.0000
28. C 0.0003 0.0001 0.0005 0.0030 0.0005 0.0002 0.0002 0.0002 0.0000
29. H 0.0000 0.0000 0.0000 0.0022 0.0000 0.0000 0.0003 0.0003 0.0000
30. C 0.0001 0.0000 0.0001 0.0021 0.0001 0.0000 0.0002 0.0002 0.0000
31. C 0.0000 0.0001 0.0000 0.0100 0.0002 0.0008 0.0008 0.0012 0.0001
32. O 0.0000 0.0000 0.0002 0.0006 0.0000 0.0000 0.0001 0.0000 0.0000
33. O 0.0000 0.0001 0.0000 0.0217 0.0001 0.0005 0.0026 0.0013 0.0003
34. O 0.0000 0.0000 0.0000 0.0004 0.0000 0.0000 0.0001 0.0001 0.0000
35. O 0.0000 0.0000 0.0000 0.0043 0.0001 0.0003 0.0021 0.0003 0.0002
36. C 0.0000 0.0000 0.0000 0.0003 0.0000 0.0000 0.0000 0.0000 0.0000
37. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
38. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
39. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
40. C 0.0000 0.0000 0.0000 0.0001 0.0000 0.0001 0.0003 0.0000 0.0002
41. H 0.0000 0.0000 0.0000 0.0002 0.0000 0.0000 0.0001 0.0000 0.0000
42. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0004 0.0001 0.0003
43. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Atom 19 20 21 22 23 24 25 26 27
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0010 0.0007 0.0000 0.0004 0.0000 0.0000 0.0000 0.0006 0.0000
2. H 0.0002 0.0001 0.0000 0.0002 0.0000 0.0000 0.0000 0.0000 0.0000
3. H 0.0001 0.0001 0.0000 0.0003 0.0000 0.0000 0.0000 0.0004 0.0000
4. H 0.0003 0.0000 0.0000 0.0006 0.0000 0.0000 0.0000 0.0016 0.0000
5. N 0.0001 0.0005 0.0003 0.0135 0.0000 0.0002 0.0000 0.0286 0.0001
6. N 0.0001 0.0004 0.0001 0.0123 0.0001 0.0001 0.0000 0.0445 0.0005
7. C 0.0000 0.0000 0.0000 0.0007 0.0000 0.0000 0.0000 0.0019 0.0000
8. O 0.0000 0.0000 0.0000 0.0015 0.0000 0.0000 0.0000 0.0022 0.0000
9. C 0.0000 0.0000 0.0000 0.0006 0.0000 0.0000 0.0000 0.0021 0.0000
10. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000
11. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0003 0.0000
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12. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0001 0.0000
13. C 0.0012 0.0097 0.0016 0.0020 0.0002 0.0002 0.0004 0.1682 0.0004
14. H 0.0000 0.0003 0.0005 0.0007 0.0003 0.0000 0.0000 0.0006 0.0001
15. C 0.0031 0.0111 0.0028 0.0947 0.0081 0.0082 0.0002 0.0007 0.0001
16. C 0.9092 0.1026 0.0085 0.0117 0.0034 0.0003 0.0083 0.0132 0.0000
17. C 0.0083 1.4586 0.9144 0.0117 0.0003 0.0034 0.0083 0.0126 0.0000
18. C 0.0041 0.0109 0.0003 1.4232 0.9132 0.0083 0.0033 0.0001 0.0000
19. H 0.0000 0.0003 0.0004 0.0082 0.0021 0.0004 0.0003 0.0000 0.0000
20. C 0.0003 0.0000 0.0039 1.4212 0.0084 0.9126 0.0033 0.0002 0.0000
21. H 0.0004 0.0039 0.0000 0.0086 0.0004 0.0022 0.0004 0.0000 0.0000
22. C 0.0082 1.4212 0.0086 0.0000 0.0034 0.0034 0.9142 0.0101 0.0000
23. H 0.0021 0.0084 0.0004 0.0034 0.0000 0.0004 0.0020 0.0000 0.0000
24. H 0.0004 0.9126 0.0022 0.0034 0.0004 0.0000 0.0020 0.0000 0.0000
25. H 0.0003 0.0033 0.0004 0.9142 0.0020 0.0020 0.0000 0.0000 0.0000
26. C 0.0000 0.0002 0.0000 0.0101 0.0000 0.0000 0.0000 0.0000 0.9004
27. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.9004 0.0000
28. C 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 1.4986 0.0057
29. H 0.0000 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000 0.0055 0.0031
30. C 0.0000 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000 0.0163 0.0098
31. C 0.0002 0.0000 0.0000 0.0005 0.0000 0.0000 0.0000 1.1030 0.0037
32. O 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0161 0.0010
33. O 0.0004 0.0003 0.0000 0.0013 0.0000 0.0000 0.0000 0.0587 0.0023
34. O 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0113 0.0003
35. O 0.0021 0.0001 0.0000 0.0003 0.0000 0.0000 0.0000 0.0183 0.0071
36. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0017 0.0004
37. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000
38. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0003 0.0000
39. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0000
40. C 0.0002 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0164 0.0009
41. H 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0004 0.0000
42. H 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0003 0.0000
43. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0003
Atom 28 29 30 31 32 33 34 35 36
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0007 0.0001 0.0006 0.0002 0.0058 0.0003 0.0007 0.0015 0.0000
2. H 0.0003 0.0000 0.0001 0.0000 0.0015 0.0000 0.0001 0.0000 0.0000
3. H 0.0004 0.0000 0.0000 0.0000 0.0002 0.0000 0.0000 0.0002 0.0000
4. H 0.0021 0.0000 0.0001 0.0001 0.0079 0.0010 0.0007 0.0022 0.0000
5. N 0.0345 0.0007 0.0022 0.0018 0.0014 0.0035 0.0012 0.0011 0.0001
6. N 0.3477 0.0022 0.0075 0.0114 0.0056 0.0117 0.0064 0.0025 0.0012
7. C 0.0039 0.0004 0.0019 0.0002 0.0013 0.0003 0.0009 0.0001 0.0001
8. O 0.0078 0.0015 0.0071 0.0003 0.0025 0.0004 0.0013 0.0001 0.0003
9. C 0.0100 0.0002 0.0012 0.0007 0.0004 0.0007 0.0004 0.0002 0.0000
10. H 0.0003 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
11. H 0.0001 0.0000 0.0000 0.0001 0.0000 0.0001 0.0000 0.0000 0.0000
12. H 0.0005 0.0000 0.0001 0.0000 0.0002 0.0000 0.0000 0.0000 0.0000
13. C 0.0030 0.0022 0.0021 0.0100 0.0006 0.0217 0.0004 0.0043 0.0003
14. H 0.0005 0.0000 0.0001 0.0002 0.0000 0.0001 0.0000 0.0001 0.0000
15. C 0.0002 0.0000 0.0000 0.0008 0.0000 0.0005 0.0000 0.0003 0.0000
16. C 0.0002 0.0003 0.0002 0.0008 0.0001 0.0026 0.0001 0.0021 0.0000
17. C 0.0002 0.0003 0.0002 0.0012 0.0000 0.0013 0.0001 0.0003 0.0000
18. C 0.0000 0.0000 0.0000 0.0001 0.0000 0.0003 0.0000 0.0002 0.0000
19. H 0.0000 0.0000 0.0000 0.0002 0.0000 0.0004 0.0000 0.0021 0.0000
20. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0003 0.0000 0.0001 0.0000
21. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
22. C 0.0001 0.0002 0.0002 0.0005 0.0000 0.0013 0.0000 0.0003 0.0000
23. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
24. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
25. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
26. C 1.4986 0.0055 0.0163 1.1030 0.0161 0.0587 0.0113 0.0183 0.0017
27. H 0.0057 0.0031 0.0098 0.0037 0.0010 0.0023 0.0003 0.0071 0.0004
28. C 0.0000 0.8781 0.9780 0.0224 0.0483 0.0453 0.0157 0.0095 0.0175
29. H 0.8781 0.0000 0.0037 0.0079 0.0110 0.0010 0.0011 0.0008 0.0001
30. C 0.9780 0.0037 0.0000 0.0012 1.7254 0.0018 1.0413 0.0039 0.0105
31. C 0.0224 0.0079 0.0012 0.0000 0.0013 1.6829 0.0006 0.9774 0.0001
32. O 0.0483 0.0110 1.7254 0.0013 0.0000 0.0023 0.1638 0.0019 0.0122
33. O 0.0453 0.0010 0.0018 1.6829 0.0023 0.0000 0.0013 0.1466 0.0002
34. O 0.0157 0.0011 1.0413 0.0006 0.1638 0.0013 0.0000 0.0005 0.8793
35. O 0.0095 0.0008 0.0039 0.9774 0.0019 0.1466 0.0005 0.0000 0.0001
36. C 0.0175 0.0001 0.0105 0.0001 0.0122 0.0002 0.8793 0.0001 0.0000
37. H 0.0003 0.0000 0.0026 0.0000 0.0045 0.0000 0.0153 0.0000 0.9325
38. H 0.0003 0.0000 0.0026 0.0000 0.0046 0.0000 0.0145 0.0000 0.9291
39. H 0.0001 0.0000 0.0074 0.0000 0.0021 0.0000 0.0058 0.0000 0.9354
40. C 0.0003 0.0002 0.0003 0.0099 0.0009 0.0144 0.0001 0.8878 0.0000
41. H 0.0003 0.0000 0.0000 0.0019 0.0000 0.0041 0.0000 0.0169 0.0000
42. H 0.0003 0.0000 0.0001 0.0020 0.0000 0.0045 0.0000 0.0175 0.0000
43. H 0.0000 0.0000 0.0000 0.0081 0.0002 0.0026 0.0000 0.0058 0.0000
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Atom 37 38 39 40 41 42 43
---- ------ ------ ------ ------ ------ ------ ------
1. C 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000
2. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
3. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
4. H 0.0000 0.0000 0.0000 0.0001 0.0001 0.0000 0.0000
5. N 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000
6. N 0.0000 0.0001 0.0001 0.0001 0.0001 0.0001 0.0000
7. C 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
8. O 0.0000 0.0003 0.0000 0.0000 0.0000 0.0000 0.0000
9. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
10. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
11. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
12. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
13. C 0.0000 0.0000 0.0000 0.0001 0.0002 0.0001 0.0000
14. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
15. C 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000
16. C 0.0000 0.0000 0.0000 0.0003 0.0001 0.0004 0.0000
17. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000
18. C 0.0000 0.0000 0.0000 0.0002 0.0000 0.0003 0.0000
19. H 0.0000 0.0000 0.0000 0.0002 0.0001 0.0001 0.0000
20. C 0.0000 0.0000 0.0000 0.0001 0.0000 0.0001 0.0000
21. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
22. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
23. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
24. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
25. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
26. C 0.0001 0.0003 0.0002 0.0164 0.0004 0.0003 0.0001
27. H 0.0000 0.0000 0.0000 0.0009 0.0000 0.0000 0.0003
28. C 0.0003 0.0003 0.0001 0.0003 0.0003 0.0003 0.0000
29. H 0.0000 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000
30. C 0.0026 0.0026 0.0074 0.0003 0.0000 0.0001 0.0000
31. C 0.0000 0.0000 0.0000 0.0099 0.0019 0.0020 0.0081
32. O 0.0045 0.0046 0.0021 0.0009 0.0000 0.0000 0.0002
33. O 0.0000 0.0000 0.0000 0.0144 0.0041 0.0045 0.0026
34. O 0.0153 0.0145 0.0058 0.0001 0.0000 0.0000 0.0000
35. O 0.0000 0.0000 0.0000 0.8878 0.0169 0.0175 0.0058
36. C 0.9325 0.9291 0.9354 0.0000 0.0000 0.0000 0.0000
37. H 0.0000 0.0002 0.0003 0.0000 0.0000 0.0000 0.0000
38. H 0.0002 0.0000 0.0003 0.0000 0.0000 0.0000 0.0000
39. H 0.0003 0.0003 0.0000 0.0000 0.0000 0.0000 0.0000
40. C 0.0000 0.0000 0.0000 0.0000 0.9305 0.9319 0.9357
41. H 0.0000 0.0000 0.0000 0.9305 0.0000 0.0002 0.0003
42. H 0.0000 0.0000 0.0000 0.9319 0.0002 0.0000 0.0003
43. H 0.0000 0.0000 0.0000 0.9357 0.0003 0.0003 0.0000
Wiberg bond index, Totals by atom:
Atom 1
---- ------
1. C 3.7532
2. H 0.9456
3. H 0.9414
4. H 0.9273
5. N 3.6382
6. N 3.2131
7. C 3.8934
8. O 2.0014
9. C 3.8294
10. H 0.9483
11. H 0.9306
12. H 0.9369
13. C 3.9005
14. H 0.9346
15. C 3.9929
16. C 3.9421
17. C 3.9461
18. C 3.9464
19. H 0.9428
20. C 3.9455
21. H 0.9444
22. C 3.9460
23. H 0.9424
24. H 0.9419
25. H 0.9427
26. C 3.9359
27. H 0.9365
28. C 3.9330
29. H 0.9207
30. C 3.8287
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31. C 3.8509
32. O 2.0234
33. O 2.0147
34. O 2.1630
35. O 2.1117
36. C 3.7213
37. H 0.9561
38. H 0.9526
39. H 0.9518
40. C 3.7308
41. H 0.9554
42. H 0.9584
43. H 0.9536
---------------------o-------------------------o-------------------------------------o--------------------o-------------
3 tsx nbo: Wiberg bond index matrix in the NAO basis:
Atom 1 2 3 4 5 6 7 8 9
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0000 0.9315 0.9309 0.9103 0.9054 0.0257 0.0044 0.0071 0.0008
2. H 0.9315 0.0000 0.0007 0.0005 0.0011 0.0060 0.0012 0.0012 0.0004
3. H 0.9309 0.0007 0.0000 0.0003 0.0029 0.0005 0.0005 0.0001 0.0000
4. H 0.9103 0.0005 0.0003 0.0000 0.0033 0.0005 0.0005 0.0044 0.0004
5. N 0.9054 0.0011 0.0029 0.0033 0.0000 1.0700 0.0099 0.0040 0.0103
6. N 0.0257 0.0060 0.0005 0.0005 1.0700 0.0000 1.1423 0.1155 0.0097
7. C 0.0044 0.0012 0.0005 0.0005 0.0099 1.1423 0.0000 1.6183 1.0000
8. O 0.0071 0.0012 0.0001 0.0044 0.0040 0.1155 1.6183 0.0000 0.0417
9. C 0.0008 0.0004 0.0000 0.0004 0.0103 0.0097 1.0000 0.0417 0.0000
10. H 0.0001 0.0000 0.0000 0.0000 0.0001 0.0022 0.0050 0.0105 0.9086
11. H 0.0000 0.0000 0.0000 0.0000 0.0004 0.0054 0.0027 0.0020 0.9267
12. H 0.0000 0.0000 0.0000 0.0000 0.0001 0.0017 0.0038 0.0101 0.9344
13. C 0.0171 0.0007 0.0109 0.0092 1.4849 0.0954 0.0178 0.0090 0.0004
14. H 0.0107 0.0003 0.0001 0.0001 0.0015 0.0023 0.0003 0.0000 0.0001
15. C 0.0013 0.0018 0.0004 0.0001 0.0100 0.0091 0.0004 0.0002 0.0003
16. C 0.0012 0.0000 0.0013 0.0005 0.0284 0.4538 0.0046 0.0109 0.0012
17. C 0.0011 0.0001 0.0007 0.0002 0.0234 0.0617 0.0026 0.0026 0.0004
18. C 0.0008 0.0001 0.0001 0.0000 0.0008 0.0002 0.0000 0.0000 0.0000
19. H 0.0005 0.0001 0.0001 0.0001 0.0001 0.0001 0.0000 0.0000 0.0000
20. C 0.0005 0.0001 0.0001 0.0000 0.0003 0.0003 0.0000 0.0000 0.0000
21. H 0.0000 0.0000 0.0000 0.0000 0.0001 0.0001 0.0000 0.0000 0.0000
22. C 0.0004 0.0001 0.0003 0.0001 0.0055 0.0015 0.0003 0.0003 0.0000
23. H 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000
24. H 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000
25. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
26. C 0.0008 0.0001 0.0004 0.0001 0.0138 0.0026 0.0005 0.0005 0.0000
27. H 0.0001 0.0000 0.0000 0.0000 0.0002 0.0005 0.0000 0.0000 0.0000
28. C 0.0019 0.0021 0.0007 0.0003 0.0130 0.0034 0.0006 0.0005 0.0000
29. H 0.0001 0.0000 0.0000 0.0000 0.0007 0.0034 0.0008 0.0004 0.0002
30. C 0.0002 0.0000 0.0000 0.0000 0.0013 0.0077 0.0005 0.0003 0.0021
31. C 0.0002 0.0000 0.0001 0.0000 0.0032 0.0115 0.0003 0.0008 0.0001
32. O 0.0001 0.0000 0.0000 0.0000 0.0006 0.0023 0.0003 0.0001 0.0015
33. O 0.0001 0.0000 0.0000 0.0000 0.0021 0.0087 0.0003 0.0006 0.0000
34. O 0.0001 0.0000 0.0000 0.0000 0.0006 0.0057 0.0002 0.0002 0.0004
35. O 0.0000 0.0000 0.0000 0.0000 0.0005 0.0015 0.0001 0.0001 0.0000
36. C 0.0000 0.0000 0.0000 0.0000 0.0002 0.0008 0.0000 0.0000 0.0000
37. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
38. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
39. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000
40. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
41. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
42. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
43. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Atom 10 11 12 13 14 15 16 17 18
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0001 0.0000 0.0000 0.0171 0.0107 0.0013 0.0012 0.0011 0.0008
2. H 0.0000 0.0000 0.0000 0.0007 0.0003 0.0018 0.0000 0.0001 0.0001
3. H 0.0000 0.0000 0.0000 0.0109 0.0001 0.0004 0.0013 0.0007 0.0001
4. H 0.0000 0.0000 0.0000 0.0092 0.0001 0.0001 0.0005 0.0002 0.0000
5. N 0.0001 0.0004 0.0001 1.4849 0.0015 0.0100 0.0284 0.0234 0.0008
6. N 0.0022 0.0054 0.0017 0.0954 0.0023 0.0091 0.4538 0.0617 0.0002
7. C 0.0050 0.0027 0.0038 0.0178 0.0003 0.0004 0.0046 0.0026 0.0000
8. O 0.0105 0.0020 0.0101 0.0090 0.0000 0.0002 0.0109 0.0026 0.0000
9. C 0.9086 0.9267 0.9344 0.0004 0.0001 0.0003 0.0012 0.0004 0.0000
10. H 0.0000 0.0008 0.0007 0.0002 0.0000 0.0000 0.0001 0.0000 0.0000
11. H 0.0008 0.0000 0.0006 0.0001 0.0000 0.0000 0.0001 0.0000 0.0000
12. H 0.0007 0.0006 0.0000 0.0003 0.0000 0.0000 0.0003 0.0002 0.0000
13. C 0.0002 0.0001 0.0003 0.0000 0.8889 1.0488 0.0038 0.1534 0.0066
14. H 0.0000 0.0000 0.0000 0.8889 0.0000 0.0032 0.0005 0.0010 0.0001
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15. C 0.0000 0.0000 0.0000 1.0488 0.0032 0.0000 0.0003 0.0006 0.0136
16. C 0.0001 0.0001 0.0003 0.0038 0.0005 0.0003 0.0000 1.4003 0.0000
17. C 0.0000 0.0000 0.0002 0.1534 0.0010 0.0006 1.4003 0.0000 0.0001
18. C 0.0000 0.0000 0.0000 0.0066 0.0001 0.0136 0.0000 0.0001 0.0000
19. H 0.0000 0.0000 0.0000 0.0008 0.0001 0.0029 0.0000 0.0000 0.0041
20. C 0.0000 0.0000 0.0000 0.0070 0.0001 0.0121 0.0000 0.0002 0.0122
21. H 0.0000 0.0000 0.0000 0.0009 0.0000 0.0036 0.0002 0.0005 0.0002
22. C 0.0000 0.0000 0.0000 0.0031 0.0021 0.1046 0.0000 0.0021 1.4285
23. H 0.0000 0.0000 0.0000 0.0002 0.0001 0.0065 0.0000 0.0001 0.9187
24. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0066 0.0000 0.0000 0.0068
25. H 0.0000 0.0000 0.0000 0.0003 0.0000 0.0001 0.0000 0.0000 0.0034
26. C 0.0000 0.0000 0.0000 0.0133 0.0036 1.3879 0.0002 0.0028 0.1080
27. H 0.0000 0.0000 0.0000 0.0002 0.0000 0.0000 0.0054 0.9095 0.0000
28. C 0.0000 0.0000 0.0000 0.0138 0.0067 1.3789 0.0001 0.0051 1.4477
29. H 0.0000 0.0000 0.0003 0.0033 0.0000 0.0000 0.8928 0.0066 0.0000
30. C 0.0005 0.0002 0.0005 0.0011 0.0002 0.0000 0.9607 0.0143 0.0000
31. C 0.0000 0.0000 0.0000 0.0102 0.0005 0.0003 0.0274 1.1365 0.0000
32. O 0.0023 0.0006 0.0003 0.0003 0.0005 0.0000 0.0417 0.0084 0.0000
33. O 0.0000 0.0000 0.0000 0.0096 0.0003 0.0001 0.0279 0.0654 0.0000
34. O 0.0003 0.0000 0.0001 0.0004 0.0001 0.0000 0.0135 0.0050 0.0000
35. O 0.0000 0.0000 0.0000 0.0032 0.0025 0.0001 0.0052 0.0185 0.0000
36. C 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0141 0.0010 0.0000
37. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0003 0.0000 0.0000
38. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0001 0.0000
39. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0001 0.0000
40. C 0.0000 0.0000 0.0000 0.0001 0.0001 0.0000 0.0002 0.0130 0.0000
41. H 0.0000 0.0000 0.0000 0.0001 0.0001 0.0000 0.0001 0.0004 0.0000
42. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0004 0.0000
43. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000
Atom 19 20 21 22 23 24 25 26 27
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0005 0.0005 0.0000 0.0004 0.0000 0.0000 0.0000 0.0008 0.0001
2. H 0.0001 0.0001 0.0000 0.0001 0.0000 0.0000 0.0000 0.0001 0.0000
3. H 0.0001 0.0001 0.0000 0.0003 0.0000 0.0000 0.0000 0.0004 0.0000
4. H 0.0001 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0001 0.0000
5. N 0.0001 0.0003 0.0001 0.0055 0.0001 0.0001 0.0000 0.0138 0.0002
6. N 0.0001 0.0003 0.0001 0.0015 0.0000 0.0000 0.0000 0.0026 0.0005
7. C 0.0000 0.0000 0.0000 0.0003 0.0000 0.0000 0.0000 0.0005 0.0000
8. O 0.0000 0.0000 0.0000 0.0003 0.0000 0.0000 0.0000 0.0005 0.0000
9. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
10. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
11. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
12. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
13. C 0.0008 0.0070 0.0009 0.0031 0.0002 0.0001 0.0003 0.0133 0.0002
14. H 0.0001 0.0001 0.0000 0.0021 0.0001 0.0000 0.0000 0.0036 0.0000
15. C 0.0029 0.0121 0.0036 0.1046 0.0065 0.0066 0.0001 1.3879 0.0000
16. C 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000 0.0000 0.0002 0.0054
17. C 0.0000 0.0002 0.0005 0.0021 0.0001 0.0000 0.0000 0.0028 0.9095
18. C 0.0041 0.0122 0.0002 1.4285 0.9187 0.0068 0.0034 0.1080 0.0000
19. H 0.0000 0.0002 0.0002 0.0067 0.0015 0.0003 0.0002 0.0069 0.0000
20. C 0.0002 0.0000 0.0044 1.4347 0.0068 0.9178 0.0035 1.4429 0.0000
21. H 0.0002 0.0044 0.0000 0.0062 0.0003 0.0015 0.0001 0.8935 0.0000
22. C 0.0067 1.4347 0.0062 0.0000 0.0036 0.0034 0.9202 0.0139 0.0000
23. H 0.0015 0.0068 0.0003 0.0036 0.0000 0.0002 0.0015 0.0002 0.0000
24. H 0.0003 0.9178 0.0015 0.0034 0.0002 0.0000 0.0015 0.0037 0.0000
25. H 0.0002 0.0035 0.0001 0.9202 0.0015 0.0015 0.0000 0.0068 0.0000
26. C 0.0069 1.4429 0.8935 0.0139 0.0002 0.0037 0.0068 0.0000 0.0001
27. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000
28. C 0.9172 0.1082 0.0063 0.0130 0.0035 0.0002 0.0067 0.0173 0.0000
29. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0021
30. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0075
31. C 0.0000 0.0001 0.0015 0.0002 0.0000 0.0000 0.0000 0.0015 0.0038
32. O 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0009
33. O 0.0000 0.0001 0.0093 0.0003 0.0000 0.0001 0.0000 0.0055 0.0013
34. O 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002
35. O 0.0000 0.0000 0.0006 0.0000 0.0000 0.0000 0.0000 0.0003 0.0060
36. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002
37. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
38. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
39. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
40. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0006
41. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
42. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
43. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002
Atom 28 29 30 31 32 33 34 35 36
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0019 0.0001 0.0002 0.0002 0.0001 0.0001 0.0001 0.0000 0.0000
2. H 0.0021 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
3. H 0.0007 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
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4. H 0.0003 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
5. N 0.0130 0.0007 0.0013 0.0032 0.0006 0.0021 0.0006 0.0005 0.0002
6. N 0.0034 0.0034 0.0077 0.0115 0.0023 0.0087 0.0057 0.0015 0.0008
7. C 0.0006 0.0008 0.0005 0.0003 0.0003 0.0003 0.0002 0.0001 0.0000
8. O 0.0005 0.0004 0.0003 0.0008 0.0001 0.0006 0.0002 0.0001 0.0000
9. C 0.0000 0.0002 0.0021 0.0001 0.0015 0.0000 0.0004 0.0000 0.0000
10. H 0.0000 0.0000 0.0005 0.0000 0.0023 0.0000 0.0003 0.0000 0.0000
11. H 0.0000 0.0000 0.0002 0.0000 0.0006 0.0000 0.0000 0.0000 0.0000
12. H 0.0000 0.0003 0.0005 0.0000 0.0003 0.0000 0.0001 0.0000 0.0000
13. C 0.0138 0.0033 0.0011 0.0102 0.0003 0.0096 0.0004 0.0032 0.0001
14. H 0.0067 0.0000 0.0002 0.0005 0.0005 0.0003 0.0001 0.0025 0.0000
15. C 1.3789 0.0000 0.0000 0.0003 0.0000 0.0001 0.0000 0.0001 0.0000
16. C 0.0001 0.8928 0.9607 0.0274 0.0417 0.0279 0.0135 0.0052 0.0141
17. C 0.0051 0.0066 0.0143 1.1365 0.0084 0.0654 0.0050 0.0185 0.0010
18. C 1.4477 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
19. H 0.9172 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
20. C 0.1082 0.0000 0.0000 0.0001 0.0000 0.0001 0.0000 0.0000 0.0000
21. H 0.0063 0.0000 0.0000 0.0015 0.0000 0.0093 0.0000 0.0006 0.0000
22. C 0.0130 0.0000 0.0000 0.0002 0.0000 0.0003 0.0000 0.0000 0.0000
23. H 0.0035 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
24. H 0.0002 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000
25. H 0.0067 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
26. C 0.0173 0.0001 0.0000 0.0015 0.0000 0.0055 0.0000 0.0003 0.0000
27. H 0.0000 0.0021 0.0075 0.0038 0.0009 0.0013 0.0002 0.0060 0.0002
28. C 0.0000 0.0001 0.0000 0.0003 0.0000 0.0006 0.0000 0.0001 0.0000
29. H 0.0001 0.0000 0.0036 0.0058 0.0087 0.0008 0.0008 0.0008 0.0001
30. C 0.0000 0.0036 0.0000 0.0015 1.7214 0.0014 0.9854 0.0095 0.0102
31. C 0.0003 0.0058 0.0015 0.0000 0.0010 1.5903 0.0004 0.9430 0.0001
32. O 0.0000 0.0087 1.7214 0.0010 0.0000 0.0008 0.1135 0.0033 0.0081
33. O 0.0006 0.0008 0.0014 1.5903 0.0008 0.0000 0.0004 0.0946 0.0001
34. O 0.0000 0.0008 0.9854 0.0004 0.1135 0.0004 0.0000 0.0010 0.8543
35. O 0.0001 0.0008 0.0095 0.9430 0.0033 0.0946 0.0010 0.0000 0.0001
36. C 0.0000 0.0001 0.0102 0.0001 0.0081 0.0001 0.8543 0.0001 0.0000
37. H 0.0000 0.0000 0.0019 0.0000 0.0020 0.0000 0.0126 0.0002 0.9413
38. H 0.0000 0.0000 0.0018 0.0000 0.0023 0.0000 0.0128 0.0000 0.9424
39. H 0.0000 0.0000 0.0062 0.0000 0.0013 0.0000 0.0048 0.0000 0.9438
40. C 0.0000 0.0001 0.0004 0.0099 0.0005 0.0092 0.0001 0.8605 0.0000
41. H 0.0000 0.0000 0.0000 0.0015 0.0000 0.0017 0.0000 0.0135 0.0000
42. H 0.0000 0.0000 0.0002 0.0015 0.0001 0.0019 0.0000 0.0136 0.0000
43. H 0.0000 0.0000 0.0001 0.0065 0.0001 0.0016 0.0000 0.0048 0.0000
Atom 37 38 39 40 41 42 43
---- ------ ------ ------ ------ ------ ------ ------
1. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
2. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
3. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
4. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
5. N 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
6. N 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000
7. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
8. O 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
9. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
10. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
11. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
12. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
13. C 0.0000 0.0000 0.0000 0.0001 0.0001 0.0000 0.0000
14. H 0.0000 0.0000 0.0000 0.0001 0.0001 0.0000 0.0000
15. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
16. C 0.0003 0.0002 0.0001 0.0002 0.0001 0.0001 0.0000
17. C 0.0000 0.0001 0.0001 0.0130 0.0004 0.0004 0.0001
18. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
19. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
20. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
21. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
22. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
23. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
24. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
25. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
26. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
27. H 0.0000 0.0000 0.0000 0.0006 0.0000 0.0000 0.0002
28. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
29. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000
30. C 0.0019 0.0018 0.0062 0.0004 0.0000 0.0002 0.0001
31. C 0.0000 0.0000 0.0000 0.0099 0.0015 0.0015 0.0065
32. O 0.0020 0.0023 0.0013 0.0005 0.0000 0.0001 0.0001
33. O 0.0000 0.0000 0.0000 0.0092 0.0017 0.0019 0.0016
34. O 0.0126 0.0128 0.0048 0.0001 0.0000 0.0000 0.0000
35. O 0.0002 0.0000 0.0000 0.8605 0.0135 0.0136 0.0048
36. C 0.9413 0.9424 0.9438 0.0000 0.0000 0.0000 0.0000
37. H 0.0000 0.0002 0.0002 0.0000 0.0000 0.0000 0.0000
38. H 0.0002 0.0000 0.0002 0.0000 0.0000 0.0000 0.0000
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39. H 0.0002 0.0002 0.0000 0.0000 0.0000 0.0000 0.0000
40. C 0.0000 0.0000 0.0000 0.0000 0.9418 0.9434 0.9446
41. H 0.0000 0.0000 0.0000 0.9418 0.0000 0.0002 0.0002
42. H 0.0000 0.0000 0.0000 0.9434 0.0002 0.0000 0.0002
43. H 0.0000 0.0000 0.0000 0.9446 0.0002 0.0002 0.0000
Wiberg bond index, Totals by atom:
Atom 1
---- ------
1. C 3.7533
2. H 0.9481
3. H 0.9512
4. H 0.9311
5. N 3.5993
6. N 3.0525
7. C 3.8183
8. O 1.8416
9. C 3.8400
10. H 0.9315
11. H 0.9398
12. H 0.9535
13. C 3.8155
14. H 0.9263
15. C 3.9937
16. C 3.8976
17. C 3.8387
18. C 3.9522
19. H 0.9422
20. C 3.9517
21. H 0.9297
22. C 3.9513
23. H 0.9434
24. H 0.9423
25. H 0.9444
26. C 3.9275
27. H 0.9389
28. C 3.9486
29. H 0.9318
30. C 3.7409
31. C 3.7599
32. O 1.9230
33. O 1.8353
34. O 2.0129
35. O 1.9838
36. C 3.7170
37. H 0.9588
38. H 0.9602
39. H 0.9570
40. C 3.7245
41. H 0.9599
42. H 0.9618
43. H 0.9585
-------------------------------o----------------------------------------------o---------------------------------------------
3 tsn nbo: Wiberg bond index matrix in the NAO basis:
Atom 1 2 3 4 5 6 7 8 9
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0000 0.9047 0.8973 0.9239 0.9179 0.0321 0.0043 0.0137 0.0007
2. H 0.9047 0.0000 0.0007 0.0004 0.0027 0.0024 0.0002 0.0006 0.0001
3. H 0.8973 0.0007 0.0000 0.0011 0.0017 0.0028 0.0009 0.0128 0.0008
4. H 0.9239 0.0004 0.0011 0.0000 0.0018 0.0086 0.0008 0.0004 0.0002
5. N 0.9179 0.0027 0.0017 0.0018 0.0000 1.1236 0.0096 0.0079 0.0134
6. N 0.0321 0.0024 0.0028 0.0086 1.1236 0.0000 1.1736 0.1526 0.0122
7. C 0.0043 0.0002 0.0009 0.0008 0.0096 1.1736 0.0000 1.6637 0.9945
8. O 0.0137 0.0006 0.0128 0.0004 0.0079 0.1526 1.6637 0.0000 0.0554
9. C 0.0007 0.0001 0.0008 0.0002 0.0134 0.0122 0.9945 0.0554 0.0000
10. H 0.0000 0.0000 0.0000 0.0000 0.0006 0.0073 0.0030 0.0035 0.9172
11. H 0.0002 0.0000 0.0000 0.0001 0.0002 0.0063 0.0045 0.0129 0.9088
12. H 0.0001 0.0000 0.0000 0.0000 0.0003 0.0008 0.0037 0.0144 0.9221
13. C 0.0187 0.0111 0.0072 0.0014 1.4007 0.1150 0.0202 0.0174 0.0006
14. H 0.0137 0.0001 0.0002 0.0002 0.0026 0.0035 0.0003 0.0001 0.0002
15. C 0.0013 0.0003 0.0004 0.0008 0.0125 0.0114 0.0006 0.0004 0.0004
16. C 0.0022 0.0010 0.0007 0.0032 0.0186 0.0108 0.0010 0.0022 0.0000
17. C 0.0006 0.0007 0.0003 0.0001 0.0235 0.0102 0.0012 0.0019 0.0001
18. C 0.0012 0.0000 0.0001 0.0001 0.0007 0.0003 0.0000 0.0001 0.0000
19. H 0.0009 0.0004 0.0001 0.0002 0.0001 0.0001 0.0000 0.0000 0.0000
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136
20. C 0.0007 0.0000 0.0001 0.0001 0.0005 0.0003 0.0001 0.0000 0.0000
21. H 0.0000 0.0000 0.0000 0.0000 0.0003 0.0001 0.0000 0.0000 0.0000
22. C 0.0003 0.0006 0.0003 0.0002 0.0127 0.0083 0.0009 0.0018 0.0000
23. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
24. H 0.0000 0.0000 0.0000 0.0000 0.0002 0.0001 0.0000 0.0000 0.0000
25. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
26. C 0.0011 0.0019 0.0004 0.0005 0.0401 0.4171 0.0040 0.0188 0.0017
27. H 0.0001 0.0000 0.0000 0.0000 0.0006 0.0025 0.0002 0.0002 0.0003
28. C 0.0006 0.0015 0.0006 0.0000 0.0357 0.0506 0.0022 0.0032 0.0003
29. H 0.0000 0.0000 0.0000 0.0000 0.0003 0.0012 0.0000 0.0001 0.0000
30. C 0.0003 0.0004 0.0000 0.0000 0.0031 0.0123 0.0002 0.0015 0.0001
31. C 0.0003 0.0001 0.0000 0.0000 0.0016 0.0064 0.0011 0.0014 0.0008
32. O 0.0021 0.0030 0.0003 0.0000 0.0050 0.0086 0.0002 0.0009 0.0000
33. O 0.0004 0.0002 0.0001 0.0001 0.0022 0.0129 0.0016 0.0024 0.0004
34. O 0.0002 0.0008 0.0000 0.0000 0.0016 0.0048 0.0001 0.0005 0.0000
35. O 0.0027 0.0029 0.0001 0.0009 0.0007 0.0016 0.0012 0.0002 0.0012
36. C 0.0000 0.0000 0.0000 0.0000 0.0001 0.0003 0.0000 0.0000 0.0000
37. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000
38. H 0.0000 0.0000 0.0000 0.0000 0.0001 0.0002 0.0000 0.0000 0.0000
39. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
40. C 0.0002 0.0002 0.0000 0.0000 0.0001 0.0007 0.0001 0.0000 0.0001
41. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000
42. H 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
43. H 0.0000 0.0001 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000
Atom 10 11 12 13 14 15 16 17 18
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0000 0.0002 0.0001 0.0187 0.0137 0.0013 0.0022 0.0006 0.0012
2. H 0.0000 0.0000 0.0000 0.0111 0.0001 0.0003 0.0010 0.0007 0.0000
3. H 0.0000 0.0000 0.0000 0.0072 0.0002 0.0004 0.0007 0.0003 0.0001
4. H 0.0000 0.0001 0.0000 0.0014 0.0002 0.0008 0.0032 0.0001 0.0001
5. N 0.0006 0.0002 0.0003 1.4007 0.0026 0.0125 0.0186 0.0235 0.0007
6. N 0.0073 0.0063 0.0008 0.1150 0.0035 0.0114 0.0108 0.0102 0.0003
7. C 0.0030 0.0045 0.0037 0.0202 0.0003 0.0006 0.0010 0.0012 0.0000
8. O 0.0035 0.0129 0.0144 0.0174 0.0001 0.0004 0.0022 0.0019 0.0001
9. C 0.9172 0.9088 0.9221 0.0006 0.0002 0.0004 0.0000 0.0001 0.0000
10. H 0.0000 0.0009 0.0007 0.0003 0.0000 0.0001 0.0000 0.0000 0.0000
11. H 0.0009 0.0000 0.0008 0.0007 0.0000 0.0000 0.0001 0.0001 0.0000
12. H 0.0007 0.0008 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
13. C 0.0003 0.0007 0.0001 0.0000 0.8968 1.1100 0.0107 0.0141 0.0094
14. H 0.0000 0.0000 0.0000 0.8968 0.0000 0.0030 0.0073 0.0017 0.0001
15. C 0.0001 0.0000 0.0000 1.1100 0.0030 0.0000 1.3511 1.3558 0.0112
16. C 0.0000 0.0001 0.0000 0.0107 0.0073 1.3511 0.0000 0.0136 1.4535
17. C 0.0000 0.0001 0.0000 0.0141 0.0017 1.3558 0.0136 0.0000 0.1037
18. C 0.0000 0.0000 0.0000 0.0094 0.0001 0.0112 1.4535 0.1037 0.0000
19. H 0.0000 0.0000 0.0000 0.0013 0.0001 0.0031 0.9021 0.0080 0.0041
20. C 0.0000 0.0000 0.0000 0.0094 0.0003 0.0111 0.1036 1.4551 0.0109
21. H 0.0000 0.0000 0.0000 0.0017 0.0005 0.0029 0.0086 0.9139 0.0003
22. C 0.0000 0.0001 0.0000 0.0025 0.0007 0.0963 0.0118 0.0117 1.4239
23. H 0.0000 0.0000 0.0000 0.0002 0.0003 0.0082 0.0034 0.0003 0.9125
24. H 0.0000 0.0000 0.0000 0.0002 0.0000 0.0082 0.0003 0.0034 0.0083
25. H 0.0000 0.0000 0.0000 0.0004 0.0000 0.0002 0.0083 0.0083 0.0033
26. C 0.0004 0.0002 0.0003 0.0027 0.0009 0.0004 0.0001 0.0001 0.0000
27. H 0.0000 0.0001 0.0007 0.0022 0.0000 0.0000 0.0003 0.0003 0.0000
28. C 0.0000 0.0001 0.0001 0.1983 0.0009 0.0008 0.0132 0.0129 0.0001
29. H 0.0000 0.0000 0.0000 0.0005 0.0001 0.0001 0.0000 0.0000 0.0000
30. C 0.0000 0.0000 0.0000 0.0124 0.0004 0.0009 0.0010 0.0012 0.0001
31. C 0.0001 0.0007 0.0001 0.0029 0.0001 0.0000 0.0003 0.0003 0.0000
32. O 0.0000 0.0001 0.0000 0.0174 0.0005 0.0008 0.0041 0.0016 0.0004
33. O 0.0000 0.0002 0.0000 0.0011 0.0001 0.0001 0.0002 0.0002 0.0000
34. O 0.0000 0.0000 0.0000 0.0086 0.0001 0.0004 0.0010 0.0002 0.0002
35. O 0.0002 0.0010 0.0000 0.0004 0.0000 0.0000 0.0001 0.0000 0.0000
36. C 0.0000 0.0000 0.0000 0.0002 0.0000 0.0002 0.0004 0.0001 0.0002
37. H 0.0000 0.0000 0.0000 0.0003 0.0000 0.0000 0.0001 0.0000 0.0000
38. H 0.0000 0.0000 0.0000 0.0002 0.0000 0.0000 0.0006 0.0001 0.0006
39. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
40. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
41. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
42. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
43. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
Atom 19 20 21 22 23 24 25 26 27
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0009 0.0007 0.0000 0.0003 0.0000 0.0000 0.0000 0.0011 0.0001
2. H 0.0004 0.0000 0.0000 0.0006 0.0000 0.0000 0.0000 0.0019 0.0000
3. H 0.0001 0.0001 0.0000 0.0003 0.0000 0.0000 0.0000 0.0004 0.0000
4. H 0.0002 0.0001 0.0000 0.0002 0.0000 0.0000 0.0000 0.0005 0.0000
5. N 0.0001 0.0005 0.0003 0.0127 0.0000 0.0002 0.0000 0.0401 0.0006
6. N 0.0001 0.0003 0.0001 0.0083 0.0000 0.0001 0.0000 0.4171 0.0025
7. C 0.0000 0.0001 0.0000 0.0009 0.0000 0.0000 0.0000 0.0040 0.0002
8. O 0.0000 0.0000 0.0000 0.0018 0.0000 0.0000 0.0000 0.0188 0.0002
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9. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0017 0.0003
10. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0004 0.0000
11. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0002 0.0001
12. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0003 0.0007
13. C 0.0013 0.0094 0.0017 0.0025 0.0002 0.0002 0.0004 0.0027 0.0022
14. H 0.0001 0.0003 0.0005 0.0007 0.0003 0.0000 0.0000 0.0009 0.0000
15. C 0.0031 0.0111 0.0029 0.0963 0.0082 0.0082 0.0002 0.0004 0.0000
16. C 0.9021 0.1036 0.0086 0.0118 0.0034 0.0003 0.0083 0.0001 0.0003
17. C 0.0080 1.4551 0.9139 0.0117 0.0003 0.0034 0.0083 0.0001 0.0003
18. C 0.0041 0.0109 0.0003 1.4239 0.9125 0.0083 0.0033 0.0000 0.0000
19. H 0.0000 0.0003 0.0004 0.0080 0.0020 0.0004 0.0003 0.0000 0.0000
20. C 0.0003 0.0000 0.0038 1.4239 0.0084 0.9126 0.0033 0.0000 0.0000
21. H 0.0004 0.0038 0.0000 0.0085 0.0004 0.0022 0.0004 0.0000 0.0000
22. C 0.0080 1.4239 0.0085 0.0000 0.0034 0.0034 0.9141 0.0001 0.0002
23. H 0.0020 0.0084 0.0004 0.0034 0.0000 0.0004 0.0020 0.0000 0.0000
24. H 0.0004 0.9126 0.0022 0.0034 0.0004 0.0000 0.0020 0.0000 0.0000
25. H 0.0003 0.0033 0.0004 0.9141 0.0020 0.0020 0.0000 0.0000 0.0000
26. C 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.8850
27. H 0.0000 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000 0.8850 0.0000
28. C 0.0002 0.0002 0.0000 0.0097 0.0000 0.0000 0.0000 1.4217 0.0052
29. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0058 0.0027
30. C 0.0006 0.0001 0.0000 0.0005 0.0000 0.0000 0.0000 0.0235 0.0079
31. C 0.0000 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000 0.9692 0.0037
32. O 0.0035 0.0004 0.0000 0.0014 0.0001 0.0000 0.0000 0.0280 0.0009
33. O 0.0000 0.0000 0.0000 0.0002 0.0000 0.0000 0.0000 0.0596 0.0058
34. O 0.0005 0.0001 0.0000 0.0001 0.0000 0.0000 0.0000 0.0186 0.0001
35. O 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0130 0.0064
36. C 0.0000 0.0001 0.0000 0.0001 0.0000 0.0000 0.0000 0.0010 0.0003
37. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0004 0.0000
38. H 0.0001 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000 0.0005 0.0000
39. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000
40. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0187 0.0005
41. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0002 0.0001
42. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0003 0.0001
43. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0001
Atom 28 29 30 31 32 33 34 35 36
---- ------ ------ ------ ------ ------ ------ ------ ------ ------
1. C 0.0006 0.0000 0.0003 0.0003 0.0021 0.0004 0.0002 0.0027 0.0000
2. H 0.0015 0.0000 0.0004 0.0001 0.0030 0.0002 0.0008 0.0029 0.0000
3. H 0.0006 0.0000 0.0000 0.0000 0.0003 0.0001 0.0000 0.0001 0.0000
4. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0009 0.0000
5. N 0.0357 0.0003 0.0031 0.0016 0.0050 0.0022 0.0016 0.0007 0.0001
6. N 0.0506 0.0012 0.0123 0.0064 0.0086 0.0129 0.0048 0.0016 0.0003
7. C 0.0022 0.0000 0.0002 0.0011 0.0002 0.0016 0.0001 0.0012 0.0000
8. O 0.0032 0.0001 0.0015 0.0014 0.0009 0.0024 0.0005 0.0002 0.0000
9. C 0.0003 0.0000 0.0001 0.0008 0.0000 0.0004 0.0000 0.0012 0.0000
10. H 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0002 0.0000
11. H 0.0001 0.0000 0.0000 0.0007 0.0001 0.0002 0.0000 0.0010 0.0000
12. H 0.0001 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
13. C 0.1983 0.0005 0.0124 0.0029 0.0174 0.0011 0.0086 0.0004 0.0002
14. H 0.0009 0.0001 0.0004 0.0001 0.0005 0.0001 0.0001 0.0000 0.0000
15. C 0.0008 0.0001 0.0009 0.0000 0.0008 0.0001 0.0004 0.0000 0.0002
16. C 0.0132 0.0000 0.0010 0.0003 0.0041 0.0002 0.0010 0.0001 0.0004
17. C 0.0129 0.0000 0.0012 0.0003 0.0016 0.0002 0.0002 0.0000 0.0001
18. C 0.0001 0.0000 0.0001 0.0000 0.0004 0.0000 0.0002 0.0000 0.0002
19. H 0.0002 0.0000 0.0006 0.0000 0.0035 0.0000 0.0005 0.0000 0.0000
20. C 0.0002 0.0000 0.0001 0.0000 0.0004 0.0000 0.0001 0.0000 0.0001
21. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
22. C 0.0097 0.0000 0.0005 0.0002 0.0014 0.0002 0.0001 0.0000 0.0001
23. H 0.0000 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000
24. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
25. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
26. C 1.4217 0.0058 0.0235 0.9692 0.0280 0.0596 0.0186 0.0130 0.0010
27. H 0.0052 0.0027 0.0079 0.0037 0.0009 0.0058 0.0001 0.0064 0.0003
28. C 0.0000 0.9003 1.1168 0.0163 0.0669 0.0228 0.0165 0.0059 0.0157
29. H 0.9003 0.0000 0.0037 0.0087 0.0102 0.0013 0.0007 0.0005 0.0003
30. C 1.1168 0.0037 0.0000 0.0023 1.6298 0.0018 1.0040 0.0008 0.0098
31. C 0.0163 0.0087 0.0023 0.0000 0.0111 1.7451 0.0025 1.0379 0.0001
32. O 0.0669 0.0102 1.6298 0.0111 0.0000 0.0042 0.1447 0.0025 0.0130
33. O 0.0228 0.0013 0.0018 1.7451 0.0042 0.0000 0.0016 0.1657 0.0001
34. O 0.0165 0.0007 1.0040 0.0025 0.1447 0.0016 0.0000 0.0005 0.8905
35. O 0.0059 0.0005 0.0008 1.0379 0.0025 0.1657 0.0005 0.0000 0.0001
36. C 0.0157 0.0003 0.0098 0.0001 0.0130 0.0001 0.8905 0.0001 0.0000
37. H 0.0005 0.0000 0.0020 0.0000 0.0044 0.0000 0.0164 0.0000 0.9305
38. H 0.0003 0.0000 0.0024 0.0000 0.0037 0.0001 0.0168 0.0000 0.9326
39. H 0.0000 0.0001 0.0080 0.0000 0.0022 0.0000 0.0060 0.0000 0.9361
40. C 0.0008 0.0005 0.0002 0.0107 0.0011 0.0123 0.0001 0.8736 0.0000
41. H 0.0001 0.0000 0.0000 0.0028 0.0010 0.0039 0.0001 0.0139 0.0000
42. H 0.0001 0.0000 0.0000 0.0022 0.0000 0.0051 0.0000 0.0149 0.0000
43. H 0.0001 0.0000 0.0000 0.0074 0.0000 0.0021 0.0000 0.0055 0.0000
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Atom 37 38 39 40 41 42 43
---- ------ ------ ------ ------ ------ ------ ------
1. C 0.0000 0.0000 0.0000 0.0002 0.0000 0.0001 0.0000
2. H 0.0000 0.0000 0.0000 0.0002 0.0000 0.0001 0.0001
3. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
4. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
5. N 0.0000 0.0001 0.0000 0.0001 0.0000 0.0000 0.0000
6. N 0.0001 0.0002 0.0000 0.0007 0.0001 0.0000 0.0001
7. C 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000
8. O 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
9. C 0.0000 0.0000 0.0000 0.0001 0.0000 0.0000 0.0000
10. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
11. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
12. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
13. C 0.0003 0.0002 0.0000 0.0000 0.0001 0.0000 0.0000
14. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
15. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
16. C 0.0001 0.0006 0.0000 0.0000 0.0000 0.0000 0.0000
17. C 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
18. C 0.0000 0.0006 0.0000 0.0000 0.0000 0.0000 0.0000
19. H 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
20. C 0.0000 0.0001 0.0000 0.0000 0.0000 0.0000 0.0000
21. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
22. C 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
23. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
24. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
25. H 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000 0.0000
26. C 0.0004 0.0005 0.0001 0.0187 0.0002 0.0003 0.0001
27. H 0.0000 0.0000 0.0000 0.0005 0.0001 0.0001 0.0001
28. C 0.0005 0.0003 0.0000 0.0008 0.0001 0.0001 0.0001
29. H 0.0000 0.0000 0.0001 0.0005 0.0000 0.0000 0.0000
30. C 0.0020 0.0024 0.0080 0.0002 0.0000 0.0000 0.0000
31. C 0.0000 0.0000 0.0000 0.0107 0.0028 0.0022 0.0074
32. O 0.0044 0.0037 0.0022 0.0011 0.0010 0.0000 0.0000
33. O 0.0000 0.0001 0.0000 0.0123 0.0039 0.0051 0.0021
34. O 0.0164 0.0168 0.0060 0.0001 0.0001 0.0000 0.0000
35. O 0.0000 0.0000 0.0000 0.8736 0.0139 0.0149 0.0055
36. C 0.9305 0.9326 0.9361 0.0000 0.0000 0.0000 0.0000
37. H 0.0000 0.0002 0.0003 0.0000 0.0000 0.0000 0.0000
38. H 0.0002 0.0000 0.0003 0.0000 0.0000 0.0000 0.0000
39. H 0.0003 0.0003 0.0000 0.0000 0.0000 0.0000 0.0000
40. C 0.0000 0.0000 0.0000 0.0000 0.9280 0.9309 0.9358
41. H 0.0000 0.0000 0.0000 0.9280 0.0000 0.0002 0.0003
42. H 0.0000 0.0000 0.0000 0.9309 0.0002 0.0000 0.0003
43. H 0.0000 0.0000 0.0000 0.9358 0.0003 0.0003 0.0000
Wiberg bond index, Totals by atom:
Atom 1
---- ------
1. C 3.7426
2. H 0.9372
3. H 0.9292
4. H 0.9451
5. N 3.6433
6. N 3.2022
7. C 3.8943
8. O 1.9914
9. C 3.8319
10. H 0.9346
11. H 0.9380
12. H 0.9442
13. C 3.8974
14. H 0.9346
15. C 3.9932
16. C 3.9354
17. C 3.9455
18. C 3.9457
19. H 0.9369
20. C 3.9454
21. H 0.9439
22. C 3.9459
23. H 0.9417
24. H 0.9419
25. H 0.9427
26. C 3.9366
27. H 0.9266
28. C 3.9214
29. H 0.9371
30. C 3.8480
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139
31. C 3.8365
32. O 1.9741
33. O 2.0537
34. O 2.1384
35. O 2.1544
36. C 3.7318
37. H 0.9553
38. H 0.9590
39. H 0.9532
40. C 3.7150
41. H 0.9511
42. H 0.9545
43. H 0.9521
---------------------o---------------------------------------------o---------------------------------------
Optimized Molecule =AI:
-------------------------------------- --------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------
E(RB+HF-LYP) = -572.961695591
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.936895 1.532190 0.269932
2 1 0 0.015338 1.699221 0.824434
3 1 0 1.806944 1.697290 0.902747
4 1 0 0.976335 2.173203 -0.615163
5 7 0 1.007310 0.117240 -0.168518
6 7 0 2.195745 -0.404962 -0.598303
7 6 0 3.315392 -0.114903 0.137302
8 8 0 3.387864 0.472771 1.225441
9 6 0 4.572485 -0.659370 -0.526024
10 1 0 4.355193 -1.168043 -1.467522
11 1 0 5.267823 0.168120 -0.705878
12 1 0 5.068694 -1.353116 0.161341
13 6 0 -0.053126 -0.647121 -0.272035
14 1 0 0.200148 -1.676512 -0.506191
15 6 0 -1.465076 -0.309655 -0.140481
16 6 0 -2.044994 0.930941 -0.477974
17 6 0 -2.318257 -1.346644 0.293663
18 6 0 -3.417277 1.129708 -0.346318
19 1 0 -1.433292 1.729221 -0.881916
20 6 0 -3.686295 -1.139513 0.432875
21 1 0 -1.890890 -2.316661 0.534044
22 6 0 -4.241988 0.103133 0.118243
23 1 0 -3.845506 2.090026 -0.619679
24 1 0 -4.320571 -1.949264 0.782165
25 1 0 -5.311076 0.265804 0.220740
------------------------------------------------------------------------
Rotational constants (GHZ): 2.6347339 0.3340530 0.3147293
Thermochemical data:
Zero-point correction= 0.205706 (Hartree/Particle)
Thermal correction to Energy= 0.218058
Thermal correction to Enthalpy= 0.219002
Thermal correction to Gibbs Free Energy= 0.165757
Sum of electronic and zero-point Energies= -572.755989
Sum of electronic and thermal Energies= -572.743637
Sum of electronic and thermal Enthalpies= -572.742693
Sum of electronic and thermal Free Energies= -572.795938
Optimized Molecule = E1:
---------------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
-----------------------------------------------
E(RB+HF-LYP) = -170.834988653
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 1.323585 0.979223 0.000000
Page 290
Annexure 4
140
2 1 0 2.030954 0.155981 0.000000
3 1 0 1.727485 1.986348 0.000000
4 6 0 0.000000 0.776857 0.000000
5 1 0 -0.701211 1.607517 0.000000
6 6 0 -0.581105 -0.531073 0.000000
7 7 0 -1.073159 -1.585698 0.000000
---------------------------------------------------------------------
Rotational constants (GHZ): 50.2368037 4.9394672 4.4972783
Thermochemical data:
Zero-point correction= 0.051021 (Hartree/Particle)
Thermal correction to Energy= 0.055156
Thermal correction to Enthalpy= 0.056100
Thermal correction to Gibbs Free Energy= 0.025143
Sum of electronic and zero-point Energies= -170.783967
Sum of electronic and thermal Energies= -170.779833
Sum of electronic and thermal Enthalpies= -170.778889
Sum of electronic and thermal Free Energies= -170.809845
Optimized Molecule = E2: ------------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------
E(RB+HF-LYP) = -306.466612335
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 2.174514 -0.764248 -0.000122
2 1 0 1.671026 -1.725656 -0.000375
3 1 0 3.260892 -0.771163 -0.000212
4 6 0 1.490291 0.382451 0.000116
5 1 0 1.988501 1.347531 0.000254
6 6 0 0.010336 0.485109 0.000079
7 8 0 -0.588403 1.542773 -0.000121
8 8 0 -0.605434 -0.720382 0.000252
9 6 0 -2.039590 -0.671968 -0.000106
10 1 0 -2.367601 -1.711992 -0.001373
11 1 0 -2.407989 -0.154031 0.889677
12 1 0 -2.407437 -0.151881 -0.888829
---------------------------------------------------------------------
Rotational constants (GHZ): 6.8994605 2.7891059 2.0113890
Themochemical data Of molecule E3 : From frequency analysis:
Zero-point correction= 0.095853 (Hartree/Particle)
Thermal correction to Energy= 0.102488
Thermal correction to Enthalpy= 0.103432
Thermal correction to Gibbs Free Energy= 0.065386
Sum of electronic and zero-point Energies= -306.370759
Sum of electronic and thermal Energies= -306.364125
Sum of electronic and thermal Enthalpies= -306.363180
Sum of electronic and thermal Free Energies= -306.401226
Optimized Molecule = E3: --------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------
E(RB+HF-LYP) = -534.333723675
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -0.667238 -1.681062 -0.056931
2 1 0 -1.190410 -2.630291 -0.139420
3 6 0 0.666764 -1.681209 0.056599
4 1 0 1.189730 -2.630574 0.138869
5 6 0 1.579167 -0.505473 0.143225
6 6 0 -1.579453 -0.505167 -0.143102
7 8 0 2.548386 -0.480180 0.872887
8 8 0 -2.549482 -0.480015 -0.871699
9 8 0 1.246926 0.484078 -0.708668
10 8 0 -1.246091 0.484770 0.707933
11 6 0 2.086867 1.648858 -0.646966
Page 291
Annexure 4
141
12 1 0 2.012478 2.120892 0.336471
13 1 0 3.129378 1.379922 -0.834866
14 1 0 1.715061 2.317436 -1.423656
15 6 0 -2.086050 1.649558 0.646727
16 1 0 -2.012878 2.121143 -0.337018
17 1 0 -3.128340 1.380749 0.836039
18 1 0 -1.713259 2.318476 1.422651
---------------------------------------------------------------------
Rotational constants (GHZ): 2.0369030 0.9608030 0.7646490
------------------------------------------------------------------------------
Thermochemical data : From frequency analysis:
Zero-point correction= 0.139188 (Hartree/Particle)
Thermal correction to Energy= 0.150210
Thermal correction to Enthalpy= 0.151154
Thermal correction to Gibbs Free Energy= 0.100484
Sum of electronic and zero-point Energies= -534.194536
Sum of electronic and thermal Energies= -534.183513
Sum of electronic and thermal Enthalpies= -534.182569
Sum of electronic and thermal Free Energies= -534.233240
Optimized Molecule = 1PRX: --------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------
E(RB+HF-LYP) = -743.850821509
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.420939 -1.276465 1.733252
2 1 0 -0.540452 -1.790650 1.678349
3 1 0 1.176994 -1.979888 2.089243
4 1 0 0.343254 -0.455386 2.462963
5 7 0 0.810537 -0.845295 0.379723
6 7 0 2.075779 -0.196433 0.413581
7 6 0 3.156326 -0.706519 -0.288996
8 8 0 4.145661 -0.013442 -0.479146
9 6 0 3.047636 -2.149335 -0.741814
10 1 0 2.211709 -2.280637 -1.435588
11 1 0 3.984740 -2.418432 -1.231197
12 1 0 2.869731 -2.820235 0.105035
13 6 0 -0.065660 0.185227 -0.232468
14 1 0 0.239113 0.233979 -1.286314
15 6 0 -1.543003 -0.145166 -0.175930
16 6 0 -2.497036 0.710780 0.384251
17 6 0 -1.973540 -1.355270 -0.743913
18 6 0 -3.850825 0.363206 0.384301
19 1 0 -2.201657 1.665556 0.807710
20 6 0 -3.321316 -1.705646 -0.737416
21 1 0 -1.239349 -2.024123 -1.185280
22 6 0 -4.266195 -0.845245 -0.171396
23 1 0 -4.578006 1.043899 0.818124
24 1 0 -3.635974 -2.647338 -1.178953
25 1 0 -5.318833 -1.114327 -0.170446
26 6 0 1.948716 1.262408 0.594269
27 1 0 2.547068 1.766906 -0.167661
28 1 0 2.307397 1.584822 1.576271
29 6 0 0.422708 1.512197 0.436415
30 1 0 -0.040682 1.615066 1.423730
31 6 0 0.109375 2.713647 -0.333634
32 7 0 -0.146185 3.662498 -0.952496
---------------------------------------------------------------------
Rotational constants (GHZ): 0.7696638 0.3293365 0.2583469
Thermochemical data:
Zero-point correction= 0.263537 (Hartree/Particle)
Thermal correction to Energy= 0.279375
Thermal correction to Enthalpy= 0.280319
Thermal correction to Gibbs Free Energy= 0.219268
Sum of electronic and zero-point Energies= -743.587284
Sum of electronic and thermal Energies= -743.571447
Sum of electronic and thermal Enthalpies= -743.570503
Sum of electronic and thermal Free Energies= -743.631554
Page 292
Annexure 4
142
Optimized Molecule = 1PRN:
--------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------
E(RB+HF-LYP) = -743.847859882
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.533718 -0.232825 1.902559
2 1 0 -0.443557 -0.661694 2.131785
3 1 0 1.285063 -0.713201 2.533944
4 1 0 0.513041 0.839857 2.135784
5 7 0 0.868740 -0.536131 0.498097
6 7 0 2.121168 0.038894 0.150935
7 6 0 3.179871 -0.756412 -0.256606
8 8 0 4.141363 -0.256561 -0.824756
9 6 0 3.088769 -2.230475 0.086400
10 1 0 2.233109 -2.697151 -0.411235
11 1 0 4.014389 -2.707953 -0.238271
12 1 0 2.955044 -2.381215 1.162491
13 6 0 -0.033384 0.042076 -0.523976
14 1 0 0.290010 -0.426918 -1.464390
15 6 0 -1.503183 -0.281268 -0.342141
16 6 0 -2.521782 0.643735 -0.596818
17 6 0 -1.859560 -1.596208 -0.000052
18 6 0 -3.864081 0.269309 -0.494794
19 1 0 -2.284355 1.665593 -0.872222
20 6 0 -3.197845 -1.967652 0.107254
21 1 0 -1.076327 -2.326433 0.182746
22 6 0 -4.207084 -1.033603 -0.138984
23 1 0 -4.639315 1.004605 -0.691423
24 1 0 -3.452627 -2.988495 0.379003
25 1 0 -5.251471 -1.321575 -0.056471
26 6 0 1.973429 1.395678 -0.414685
27 1 0 2.339004 2.162204 0.273950
28 1 0 2.559922 1.455890 -1.333964
29 6 0 0.442342 1.532649 -0.674652
30 1 0 0.252492 1.883414 -1.694367
31 6 0 -0.176147 2.498881 0.240281
32 7 0 -0.640724 3.291844 0.950678
--------------------------------------------------------------------------------------------
Rotational constants (GHZ): 0.8185380 0.3300061 0.2640480
Thermochemical data :
Zero-point correction= 0.263807 (Hartree/Particle)
Thermal correction to Energy= 0.279475
Thermal correction to Enthalpy= 0.280419
Thermal correction to Gibbs Free Energy= 0.220176
Sum of electronic and zero-point Energies= -743.584053
Sum of electronic and thermal Energies= -743.568385
Sum of electronic and thermal Enthalpies= -743.567440
Sum of electronic and thermal Free Energies= -743.627684
Optimized Molecule = 1PSX:
-----------------------------------
# opt b3lyp/6-31g(d)
------------------------------
E(RB+HF-LYP) = -743.850821576
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -1.948637 1.262436 0.594049
2 1 0 -2.547198 1.767070 -0.167633
3 1 0 -2.307158 1.584624 1.576190
4 6 0 -0.422637 1.512267 0.436057
5 1 0 0.040710 1.615140 1.423398
6 6 0 -0.109270 2.713737 -0.333882
7 7 0 0.145861 3.663025 -0.952247
8 6 0 -0.420764 -1.276309 1.732961
9 1 0 0.540096 -1.791478 1.677887
10 1 0 -0.341941 -0.455037 2.462324
11 1 0 -1.177446 -1.978794 2.089413
12 7 0 -0.810441 -0.845212 0.379373
Page 293
Annexure 4
143
13 7 0 -2.075619 -0.196334 0.413052
14 6 0 -3.156471 -0.706680 -0.288683
15 8 0 -4.146116 -0.013834 -0.478244
16 6 0 -3.047793 -2.149471 -0.741601
17 1 0 -2.212645 -2.280423 -1.436390
18 1 0 -2.868615 -2.820399 0.104953
19 1 0 -3.985367 -2.418841 -1.229923
20 6 0 0.065756 0.185270 -0.232772
21 1 0 -0.238871 0.233970 -1.286663
22 6 0 1.543090 -0.145137 -0.176022
23 6 0 1.973620 -1.355215 -0.744008
24 6 0 2.497094 0.710713 0.384374
25 6 0 3.321389 -1.705696 -0.737368
26 1 0 1.239459 -2.024000 -1.185533
27 6 0 3.850845 0.363045 0.384580
28 1 0 2.201728 1.665476 0.807882
29 6 0 4.266227 -0.845413 -0.171145
30 1 0 3.636001 -2.647387 -1.178935
31 1 0 4.578018 1.043651 0.818548
32 1 0 5.318856 -1.114526 -0.170055
--------------------------------------------------------------------------------------------------------------
Rotational constants (GHZ): 0.7696456 0.3293286 0.2583264
Thermochemical data:
Zero-point correction= 0.263537 (Hartree/Particle)
Thermal correction to Energy= 0.279374
Thermal correction to Enthalpy= 0.280318
Thermal correction to Gibbs Free Energy= 0.219270
Sum of electronic and zero-point Energies= -743.587284
Sum of electronic and thermal Energies= -743.571447
Sum of electronic and thermal Enthalpies= -743.570503
Sum of electronic and thermal Free Energies= -743.631552
Optimized Molecule = 1PSN:
--------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------
E(RB+HF-LYP) = -743.847144860
----------------------------------------------------------------------
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -0.533995 0.105914 1.962768
2 1 0 -0.464514 1.203500 1.993837
3 1 0 -1.310549 -0.210859 2.662860
4 1 0 0.418355 -0.321042 2.283460
5 7 0 -0.874878 -0.441474 0.641216
6 7 0 -2.131860 0.051043 0.200422
7 6 0 -3.176051 -0.824276 -0.060917
8 8 0 -4.144984 -0.453398 -0.709312
9 6 0 -3.059871 -2.209837 0.543308
10 1 0 -2.170795 -2.728659 0.173009
11 1 0 -2.967980 -2.158940 1.633289
12 1 0 -3.959459 -2.767507 0.278822
13 6 0 0.020109 -0.081146 -0.485569
14 1 0 -0.302307 -0.741852 -1.298254
15 6 0 1.500078 -0.338862 -0.281917
16 6 0 2.052890 -1.461241 -0.917791
17 6 0 2.343058 0.458946 0.507770
18 6 0 3.402198 -1.781900 -0.776180
19 1 0 1.415366 -2.093228 -1.531803
20 6 0 3.694316 0.139703 0.649298
21 1 0 1.959570 1.339677 1.008199
22 6 0 4.229137 -0.979162 0.009955
23 1 0 3.804932 -2.655756 -1.280925
24 1 0 4.329626 0.774154 1.261075
25 1 0 5.282280 -1.221975 0.122074
26 6 0 -1.998869 1.281873 -0.602866
27 1 0 -2.314429 2.164374 -0.039415
28 1 0 -2.638236 1.191625 -1.483046
29 6 0 -0.482530 1.340803 -0.962908
30 1 0 -0.339561 1.417961 -2.045774
31 6 0 0.165724 2.508971 -0.363239
32 7 0 0.646797 3.458573 0.102192
--------------------------------------------------------------------------------------------------------------
Rotational constants (GHZ): 0.8062442 0.3239702 0.2663277
Page 294
Annexure 4
144
Thermochemical data:
Zero-point correction= 0.263898 (Hartree/Particle)
Thermal correction to Energy= 0.279583
Thermal correction to Enthalpy= 0.280527
Thermal correction to Gibbs Free Energy= 0.220045
Sum of electronic and zero-point Energies= -743.583247
Sum of electronic and thermal Energies= -743.567562
Sum of electronic and thermal Enthalpies= -743.566618
Sum of electronic and thermal Free Energies= -743.627100
Optimized Molecule = 1TSX:
---------------------------------------------------------
# opt=(calcfc,qst3) freq b3lyp/6-31g(d) geom=connectivity
---------------------------------------------------------
E(RB+HF-LYP) = -743.783076397 A.U. after 1 cycles
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -1.859959 1.452710 1.002810
2 1 0 -2.512893 2.091820 0.419934
3 1 0 -2.331550 0.982276 1.860385
4 6 0 -0.503236 1.777232 1.096153
5 1 0 0.094171 1.416622 1.927592
6 6 0 0.078163 2.788227 0.287836
7 7 0 0.569293 3.587375 -0.408227
8 6 0 -0.793299 -1.990511 0.753394
9 1 0 -0.768050 -1.692923 1.808609
10 1 0 -1.681687 -2.582327 0.544701
11 1 0 0.097655 -2.566345 0.504666
12 7 0 -0.853437 -0.799800 -0.109242
13 7 0 -2.023265 -0.110600 -0.203197
14 6 0 -3.193754 -0.794203 -0.458770
15 8 0 -3.257386 -1.968747 -0.815918
16 6 0 -4.438329 0.066742 -0.308518
17 1 0 -4.643973 0.276486 0.748294
18 1 0 -4.329368 1.026348 -0.823552
19 1 0 -5.284206 -0.480530 -0.727297
20 6 0 0.206957 -0.067263 -0.450159
21 1 0 -0.028355 0.687199 -1.189798
22 6 0 1.625543 -0.347222 -0.241818
23 6 0 2.183623 -1.018825 0.865936
24 6 0 2.503290 0.170324 -1.217199
25 6 0 3.560480 -1.199042 0.963680
26 1 0 1.552476 -1.370584 1.672886
27 6 0 3.878469 -0.015962 -1.116651
28 1 0 2.094053 0.723802 -2.057177
29 6 0 4.412525 -0.708793 -0.029024
30 1 0 3.971141 -1.714930 1.827066
31 1 0 4.532708 0.386734 -1.884288
32 1 0 5.485993 -0.852978 0.053972
------------------------------------------------------------------------------------------------
Rotational constants (GHZ): 0.7563549 0.3012513 0.2436734
Thermochemical data:
Zero-point correction= 0.259404 (Hartree/Particle)
Thermal correction to Energy= 0.275876
Thermal correction to Enthalpy= 0.276821
Thermal correction to Gibbs Free Energy= 0.214196
Sum of electronic and zero-point Energies= -743.523672
Sum of electronic and thermal Energies= -743.507200
Sum of electronic and thermal Enthalpies= -743.506256
Sum of electronic and thermal Free Energies= -743.568880
Optimized Molecule = 1TRN:
# opt=qst3 freq b3lyp/6-31g(d) geom=connectivity
------------------------------------------------
E(RB+HF-LYP) = -743.778109626 A.U. after 1 cycles
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
Page 295
Annexure 4
145
1 6 0 0.758569 -0.508089 1.665942
2 1 0 -0.133535 -1.045080 1.988081
3 1 0 1.642730 -0.978232 2.093026
4 1 0 0.709220 0.535837 1.988093
5 7 0 0.868134 -0.566033 0.194744
6 7 0 2.045817 -0.230316 -0.378811
7 6 0 3.243107 -0.818483 -0.029373
8 8 0 4.297175 -0.237011 -0.254950
9 6 0 3.248563 -2.247631 0.517219
10 1 0 2.271028 -2.736750 0.501746
11 1 0 3.949093 -2.827754 -0.090326
12 1 0 3.640103 -2.247767 1.540730
13 6 0 -0.186098 -0.484525 -0.614177
14 1 0 0.088957 -0.601599 -1.655466
15 6 0 -1.606385 -0.513499 -0.290920
16 6 0 -2.204551 0.066054 0.847817
17 6 0 -2.441972 -1.139667 -1.242352
18 6 0 -3.582539 -0.019056 1.035397
19 1 0 -1.614988 0.642332 1.548270
20 6 0 -3.814151 -1.230007 -1.041909
21 1 0 -1.998043 -1.567319 -2.137921
22 6 0 -4.389709 -0.674643 0.104358
23 1 0 -4.027696 0.447109 1.909550
24 1 0 -4.435690 -1.728024 -1.780607
25 1 0 -5.462758 -0.738354 0.261457
26 6 0 2.001851 1.727974 -0.910723
27 1 0 2.569622 2.030455 -0.037742
28 1 0 2.599972 1.557046 -1.797401
29 6 0 0.673965 2.105330 -1.045902
30 1 0 0.183016 2.100356 -2.013795
31 6 0 -0.057564 2.634075 0.046027
32 7 0 -0.659228 3.034469 0.965993
-------------------------------------------------------------------------------------------------------------------
Rotational constants (GHZ): 0.7905690 0.2967699 0.2534073
Thermochemical data:
Zero-point correction= 0.258798 (Hartree/Particle)
Thermal correction to Energy= 0.275408
Thermal correction to Enthalpy= 0.276352
Thermal correction to Gibbs Free Energy= 0.213964
Sum of electronic and zero-point Energies= -743.519312
Sum of electronic and thermal Energies= -743.502702
Sum of electronic and thermal Enthalpies= -743.501758
Sum of electronic and thermal Free Energies= -743.564146
Optimized Molecule = 1TRX:
-----------------------------------------------------------------------------
# opt=qst3 freq b3lyp/6-31g(d) geom=connectivity
---------------------------------------------------------------------------------
E(RB+HF-LYP) = -743.774818215 A.U. after 1 cycles
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.904862 -1.865909 0.952541
2 1 0 0.158130 -2.600536 0.649547
3 1 0 1.888473 -2.330904 0.956423
4 1 0 0.684346 -1.493373 1.959031
5 7 0 0.922699 -0.747954 -0.005927
6 7 0 2.051454 -0.009030 -0.109284
7 6 0 3.286862 -0.557051 -0.372187
8 8 0 4.304362 0.054987 -0.070202
9 6 0 3.374564 -1.871953 -1.150571
10 1 0 2.415689 -2.227366 -1.537067
11 1 0 4.060720 -1.711600 -1.987034
12 1 0 3.821631 -2.646566 -0.516995
13 6 0 -0.179838 -0.127788 -0.427090
14 1 0 0.038759 0.633970 -1.163479
15 6 0 -1.587255 -0.427792 -0.216493
16 6 0 -2.153399 -1.239058 0.792941
17 6 0 -2.469232 0.221799 -1.111720
18 6 0 -3.531803 -1.413898 0.871123
19 1 0 -1.534815 -1.714504 1.542317
20 6 0 -3.845094 0.042252 -1.026695
21 1 0 -2.059427 0.885966 -1.866274
22 6 0 -4.383983 -0.784412 -0.039341
Page 296
Annexure 4
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23 1 0 -3.943758 -2.040101 1.657582
24 1 0 -4.496483 0.554837 -1.728354
25 1 0 -5.458540 -0.927220 0.029904
26 6 0 1.858493 1.705474 0.999643
27 1 0 2.481709 2.254380 0.304611
28 1 0 2.386150 1.293786 1.852940
29 6 0 0.505968 1.986159 1.107733
30 1 0 -0.066537 1.652130 1.968288
31 6 0 -0.173501 2.824137 0.185955
32 7 0 -0.752839 3.474907 -0.592626
------------------------------------------------------------------------------------------------------
Rotational constants (GHZ): 0.7395686 0.3009429 0.2426497
Thermochemical data:
Zero-point correction= 0.258757 (Hartree/Particle)
Thermal correction to Energy= 0.275505
Thermal correction to Enthalpy= 0.276449
Thermal correction to Gibbs Free Energy= 0.212811
Sum of electronic and zero-point Energies= -743.516061
Sum of electronic and thermal Energies= -743.499313
Sum of electronic and thermal Enthalpies= -743.498369
Sum of electronic and thermal Free Energies= -743.562008
Optimized Molecule = 1TSN:
---------------------------------------------------------
# opt=(calcfc,qst3) freq b3lyp/6-31g(d) geom=connectivity
---------------------------------------------------------
E(RB+HF-LYP) = -743.778108189 A.U. after 1 cycles
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -0.761168 -0.499789 1.664819
2 1 0 -0.713567 0.546048 1.981010
3 1 0 -1.645709 -0.968564 2.092956
4 1 0 0.130883 -1.034021 1.991651
5 7 0 -0.868058 -0.565950 0.193786
6 7 0 -2.045364 -0.233213 -0.382581
7 6 0 -3.242351 -0.819216 -0.027029
8 8 0 -4.296786 -0.236975 -0.248288
9 6 0 -3.246353 -2.249170 0.517499
10 1 0 -3.659228 -2.253346 1.532490
11 1 0 -3.929129 -2.834687 -0.105156
12 1 0 -2.265006 -2.730605 0.520937
13 6 0 0.187066 -0.487417 -0.614240
14 1 0 -0.087260 -0.609426 -1.655231
15 6 0 1.607112 -0.514440 -0.290064
16 6 0 2.443573 -1.142367 -1.239617
17 6 0 2.204473 0.067980 0.847670
18 6 0 3.815694 -1.231500 -1.038329
19 1 0 1.614426 0.645542 1.546642
20 6 0 3.582409 -0.016019 1.036107
21 1 0 2.000344 -1.572344 -2.134415
22 6 0 4.390413 -0.673255 0.106959
23 1 0 4.026868 0.452321 1.909451
24 1 0 4.437841 -1.730845 -1.775617
25 1 0 5.463416 -0.736040 0.264735
26 6 0 -2.002452 1.723959 -0.912626
27 1 0 -2.569103 2.026515 -0.038941
28 1 0 -2.601585 1.553199 -1.798655
29 6 0 -0.675095 2.103123 -1.049227 30 1 0 -0.184890 2.098516 -2.017492
31 6 0 0.055872 2.634338 0.041854
32 7 0 0.656400 3.037188 0.961549
-------------------------------------------------------------------------------------------------------------------
Rotational constants (GHZ): 0.7907142 0.2968029 0.2533837
Thermochemical data:
--------------------------------------------------------------------------------------------
Zero-point correction= 0.258814 (Hartree/Particle)
Thermal correction to Energy= 0.275415
Thermal correction to Enthalpy= 0.276359
Thermal correction to Gibbs Free Energy= 0.214004
Sum of electronic and zero-point Energies= -743.519295
Page 297
Annexure 4
147
Sum of electronic and thermal Energies= -743.502693
Sum of electronic and thermal Enthalpies= -743.501749
Sum of electronic and thermal Free Energies= -743.564104
Optimized Molecule = 2PRX:
--------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------
E(RB+HF-LYP) = -879.485349749
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -1.707770 1.293682 0.145989
2 1 0 -1.769684 1.815456 1.109458
3 1 0 -2.224621 1.886721 -0.610057
4 6 0 -0.232722 1.030294 -0.208651
5 1 0 -0.127636 0.807823 -1.273318
6 6 0 0.678569 2.175958 0.176825
7 8 0 0.814313 2.592004 1.309370
8 8 0 1.316939 2.686699 -0.892761
9 6 0 2.215911 3.775508 -0.613390
10 1 0 2.635996 4.060579 -1.577879
11 1 0 1.675750 4.612472 -0.163471
12 1 0 3.004450 3.451028 0.070206
13 6 0 -1.507703 -1.857389 1.634469
14 1 0 -1.652336 -1.272321 2.558280
15 1 0 -2.404657 -2.439053 1.418991
16 1 0 -0.665866 -2.542154 1.773908
17 7 0 -1.208025 -1.016571 0.475247
18 7 0 -2.259317 -0.056327 0.228753
19 6 0 -3.395456 -0.513382 -0.403626
20 8 0 -3.620891 -1.706969 -0.554770
21 6 0 -4.394235 0.555752 -0.833135
22 1 0 -4.538282 1.332359 -0.074981
23 1 0 -4.071626 1.044617 -1.761220
24 1 0 -5.344873 0.055873 -1.024184
25 6 0 0.036036 -0.243545 0.630218
26 1 0 0.168748 0.088238 1.674041
27 6 0 1.263466 -1.026580 0.204732
28 6 0 1.205705 -1.953476 -0.843767
29 6 0 2.488419 -0.793335 0.842138
30 6 0 2.357142 -2.627656 -1.250711
31 1 0 0.247986 -2.152483 -1.314975
32 6 0 3.641209 -1.464351 0.430985
33 1 0 2.537416 -0.083480 1.665152
34 6 0 3.578091 -2.383456 -0.617554
35 1 0 2.299645 -3.349412 -2.061409
36 1 0 4.584992 -1.275588 0.935976
37 1 0 4.473110 -2.912414 -0.934357
---------------------------------------------------------------------
Rotational constants (GHZ): 0.4523391 0.3038184 0.2087712
Thremochemical data:
Zero-point correction= 0.308748 (Hartree/Particle)
Thermal correction to Energy= 0.326987
Thermal correction to Enthalpy= 0.327931
Thermal correction to Gibbs Free Energy= 0.261092
Sum of electronic and zero-point Energies= -879.167365
Sum of electronic and thermal Energies= -879.149126
Sum of electronic and thermal Enthalpies= -879.148182
Sum of electronic and thermal Free Energies= -879.215021
Optimized Molecule = 2PRN:
--------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------
E(RB+HF-LYP) = -879.480483836 A.U.
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 1.805232 0.086120 -1.578645
Page 298
Annexure 4
148
2 1 0 2.486359 0.935548 -1.526697
3 1 0 2.002201 -0.455025 -2.513989
4 6 0 0.321645 0.496213 -1.524720
5 1 0 -0.082631 0.703287 -2.517137
6 6 0 0.042934 1.744727 -0.701846
7 8 0 -0.712952 2.625260 -1.048008
8 8 0 0.739041 1.765492 0.454441
9 6 0 0.483469 2.894531 1.309706
10 1 0 1.106604 2.737852 2.190058
11 1 0 0.750783 3.826346 0.804405
12 1 0 -0.573469 2.926736 1.584578
13 6 0 0.737767 -2.813767 -0.018497
14 1 0 -0.252315 -3.171751 0.280095
15 1 0 0.998301 -3.254752 -0.996562
16 1 0 1.464100 -3.127205 0.732895
17 7 0 0.698212 -1.354208 -0.044604
18 7 0 1.967491 -0.793317 -0.424057
19 6 0 2.893706 -0.635280 0.589141
20 8 0 2.762522 -1.181292 1.675197
21 6 0 4.130490 0.184031 0.242250
22 1 0 4.536158 -0.056460 -0.745932
23 1 0 3.900460 1.256434 0.264074
24 1 0 4.885396 -0.022572 1.002243
25 6 0 -0.316918 -0.808922 -0.956725
26 1 0 -0.447005 -1.475466 -1.828986
27 6 0 -1.670206 -0.640800 -0.285912
28 6 0 -1.775841 -0.439821 1.096006
29 6 0 -2.834548 -0.660880 -1.063091
30 6 0 -3.027957 -0.253357 1.684308
31 1 0 -0.870325 -0.451787 1.694007
32 6 0 -4.084550 -0.468536 -0.475568
33 1 0 -2.763013 -0.829020 -2.136051
34 6 0 -4.184084 -0.263327 0.901988
35 1 0 -3.099856 -0.105876 2.758902
36 1 0 -4.979655 -0.485288 -1.091679
37 1 0 -5.157715 -0.119588 1.362989
---------------------------------------------------------------------
Rotational constants (GHZ): 0.6003963 0.3006283 0.2603712
Thermochemical data:
Zero-point correction= 0.308080 (Hartree/Particle)
Thermal correction to Energy= 0.326524
Thermal correction to Enthalpy= 0.327468
Thermal correction to Gibbs Free Energy= 0.260171
Sum of electronic and zero-point Energies= -879.172404
Sum of electronic and thermal Energies= -879.153960
Sum of electronic and thermal Enthalpies= -879.153016
Sum of electronic and thermal Free Energies= -879.220313
Optimized Molecule = 2PSX:
--------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------
E(RB+HF-LYP) = -879.476113184 A.U.
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.734065 -0.309717 -1.290027
2 1 0 1.668252 -0.237606 -1.843085
3 1 0 -0.055812 -0.643338 -1.972896
4 6 0 0.335961 1.020916 -0.641150
5 1 0 -0.244808 1.651126 -1.321401
6 6 0 1.494541 1.869618 -0.117068
7 8 0 1.342769 2.812347 0.628544
8 8 0 2.695304 1.480496 -0.591025
9 6 0 3.819751 2.243311 -0.113886
10 1 0 4.695341 1.799474 -0.587801
11 1 0 3.715592 3.293445 -0.397775
12 1 0 3.890456 2.170276 0.973831
13 6 0 -0.392226 -1.529669 1.935326
14 1 0 -1.184946 -2.122454 1.457090
15 1 0 0.360575 -2.196247 2.354733
16 1 0 -0.837878 -0.938874 2.741932
17 7 0 0.275516 -0.591521 1.035127
18 7 0 0.857764 -1.223648 -0.142642
19 6 0 1.962416 -2.030359 0.059797
Page 299
Annexure 4
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20 8 0 2.307786 -2.416844 1.168430
21 6 0 2.683855 -2.484206 -1.204287
22 1 0 3.417345 -1.729592 -1.514923
23 1 0 3.222552 -3.402316 -0.963815
24 1 0 2.007150 -2.666719 -2.044713
25 6 0 -0.529762 0.542640 0.549473
26 1 0 -0.516953 1.307122 1.331670
27 6 0 -1.985427 0.294824 0.156630
28 6 0 -2.936945 1.268489 0.490915
29 6 0 -2.416241 -0.842599 -0.543882
30 6 0 -4.275179 1.125363 0.123965
31 1 0 -2.622407 2.151518 1.043442
32 6 0 -3.756551 -0.992802 -0.904338
33 1 0 -1.707754 -1.626367 -0.793053
34 6 0 -4.689804 -0.008368 -0.576555
35 1 0 -4.993771 1.895608 0.391574
36 1 0 -4.071031 -1.884394 -1.440600
37 1 0 -5.732450 -0.127123 -0.858670
---------------------------------------------------------------------
Rotational constants (GHZ): 0.5748833 0.2759851 0.2188551
Thermochemical data:
Zero-point correction= 0.308253 (Hartree/Particle)
Thermal correction to Energy= 0.326824
Thermal correction to Enthalpy= 0.327768
Thermal correction to Gibbs Free Energy= 0.259451
Sum of electronic and zero-point Energies= -879.177097
Sum of electronic and thermal Energies= -879.158526
Sum of electronic and thermal Enthalpies= -879.157582
Sum of electronic and thermal Free Energies= -879.225899
Optimized Molecule = 2PSN:
--------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------
E(RB+HF-LYP) = -879.480483868 A.U.
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -1.805582 0.085536 -1.578771
2 1 0 -2.486706 0.934972 -1.527043
3 1 0 -2.002717 -0.456007 -2.513849
4 6 0 -0.321950 0.495565 -1.525322
5 1 0 0.082071 0.702396 -2.517892
6 6 0 -0.042827 1.744213 -0.702790
7 8 0 0.713214 2.624479 -1.049286
8 8 0 -0.738684 1.765382 0.453642
9 6 0 -0.482529 2.894437 1.308717
10 1 0 -1.106075 2.738450 2.188904
11 1 0 0.574341 2.925836 1.583953
12 1 0 -0.748924 3.826340 0.803102
13 6 0 -0.738671 -2.814744 -0.020377
14 1 0 0.251304 -3.173422 0.277750
15 1 0 -1.464955 -3.128421 0.730978
16 1 0 -0.999635 -3.254965 -0.998678
17 7 0 -0.698483 -1.355213 -0.045412
18 7 0 -1.967606 -0.793468 -0.423846
19 6 0 -2.892665 -0.634261 0.590286
20 8 0 -2.760828 -1.180093 1.676333
21 6 0 -4.129096 0.186009 0.244425
22 1 0 -4.536095 -0.054607 -0.743181
23 1 0 -4.883326 -0.019564 1.005369
24 1 0 -3.898072 1.258212 0.265459
25 6 0 0.316782 -0.809476 -0.957167
26 1 0 0.447412 -1.475942 -1.829390
27 6 0 1.669780 -0.640965 -0.285829
28 6 0 1.774826 -0.440403 1.096189
29 6 0 2.834413 -0.660298 -1.062599
30 6 0 3.026653 -0.253591 1.685002
31 1 0 0.869088 -0.452994 1.693846
32 6 0 4.084119 -0.467621 -0.474564
33 1 0 2.763338 -0.828103 -2.135643
34 6 0 4.183067 -0.262818 0.903098
35 1 0 3.098100 -0.106452 2.759674
36 1 0 4.979454 -0.483788 -1.090357
37 1 0 5.156470 -0.118827 1.364503
Page 300
Annexure 4
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---------------------------------------------------------------------
Rotational constants (GHZ): 0.6002948 0.3007219 0.2604694
Thermochemical data:
Zero-point correction= 0.308079 (Hartree/Particle)
Thermal correction to Energy= 0.326523
Thermal correction to Enthalpy= 0.327467
Thermal correction to Gibbs Free Energy= 0.260168
Sum of electronic and zero-point Energies= -879.172405
Sum of electronic and thermal Energies= -879.153961
Sum of electronic and thermal Enthalpies= -879.153017
Sum of electronic and thermal Free Energies= -879.220316
Optimized Molecule = 2TRX:
---------------------------------------------------------
# opt=(calcfc,qst3) freq b3lyp/6-31g(d) geom=connectivity
---------------------------------------------------------
SCF Done: E(RB+HF-LYP) = -879.417189331 A.U. after 1 cycles
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 1.840552 1.020903 1.156414
2 1 0 2.387916 1.756449 0.580323
3 1 0 2.408588 0.528606 1.939990
4 6 0 0.468474 1.186079 1.326347
5 1 0 -0.048618 0.693083 2.142923
6 6 0 -0.307979 2.249548 0.696829
7 8 0 -1.432652 2.590202 1.021226
8 8 0 0.355290 2.835787 -0.353112
9 6 0 -0.340318 3.922213 -0.973295
10 1 0 0.305511 4.261301 -1.785197
11 1 0 -1.308054 3.595654 -1.364849
12 1 0 -0.511382 4.733894 -0.259856
13 6 0 0.925013 -2.453860 0.610518
14 1 0 0.033369 -3.017687 0.337813
15 1 0 1.816653 -3.015429 0.340080
16 1 0 0.918786 -2.236543 1.685259
17 7 0 0.955499 -1.197140 -0.155193
18 7 0 2.102263 -0.467455 -0.182585
19 6 0 3.295102 -1.093142 -0.465913
20 8 0 3.408806 -2.235062 -0.910311
21 6 0 4.508101 -0.210119 -0.215857
22 1 0 4.341253 0.818582 -0.548211
23 1 0 4.746286 -0.181889 0.854841
24 1 0 5.359846 -0.638349 -0.747188
25 6 0 -0.127237 -0.469279 -0.429897
26 1 0 0.088923 0.357300 -1.095963
27 6 0 -1.533353 -0.845207 -0.273810
28 6 0 -2.069518 -1.549871 0.821753
29 6 0 -2.416581 -0.402981 -1.278074
30 6 0 -3.431377 -1.832027 0.883868
31 1 0 -1.431964 -1.842934 1.647549
32 6 0 -3.776548 -0.691927 -1.215920
33 1 0 -2.023027 0.163973 -2.117442
34 6 0 -4.288501 -1.413525 -0.136461
35 1 0 -3.827361 -2.369109 1.741135
36 1 0 -4.437046 -0.347904 -2.006647
37 1 0 -5.350564 -1.635091 -0.081545
-------------------------------------------------------------------------------------------------------------------
Rotational constants (GHZ): 0.4620143 0.2882331 0.2042163
Thermochemical data:
Zero-point correction= 0.303825 (Hartree/Particle)
Thermal correction to Energy= 0.323076
Thermal correction to Enthalpy= 0.324020
Thermal correction to Gibbs Free Energy= 0.254443
Sum of electronic and zero-point Energies= -879.113364
Sum of electronic and thermal Energies= -879.094114
Sum of electronic and thermal Enthalpies= -879.093169
Sum of electronic and thermal Free Energies= -879.162746
Optimized Molecule = 2TRN:
---------------------------------------------------------
# opt=(calcfc,qst3) freq b3lyp/6-31g(d) geom=connectivity
Page 301
Annexure 4
151
---------------------------------------------------------
SCF Done: E(RB+HF-LYP) = -879.418232803 A.U. after 1 cycles
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 1.923375 1.062116 -1.232339
2 1 0 2.385909 1.649825 -0.446602
3 1 0 2.578167 0.803375 -2.056937
4 6 0 0.567249 1.254661 -1.497074
5 1 0 0.157077 0.999794 -2.468110
6 6 0 -0.304465 2.102091 -0.699314
7 8 0 -1.410235 2.495669 -1.030217
8 8 0 0.240903 2.440824 0.524269
9 6 0 -0.523976 3.388525 1.276552
10 1 0 0.040094 3.562389 2.194938
11 1 0 -0.640699 4.323651 0.720926
12 1 0 -1.519941 2.999200 1.507621
13 6 0 0.847675 -0.718804 1.747679
14 1 0 -0.056918 -1.198712 2.119970
15 1 0 1.721454 -1.168924 2.213690
16 1 0 0.814169 0.359034 1.928414
17 7 0 0.958663 -0.964592 0.297883
18 7 0 2.134190 -0.694546 -0.328784
19 6 0 3.309637 -1.177499 0.203230
20 8 0 3.385886 -2.026245 1.089771
21 6 0 4.552597 -0.594583 -0.452093
22 1 0 4.474499 -0.593760 -1.543776
23 1 0 4.711507 0.441473 -0.129204
24 1 0 5.412400 -1.192426 -0.145560
25 6 0 -0.079801 -1.003601 -0.534803
26 1 0 0.201249 -1.316495 -1.532163
27 6 0 -1.504864 -1.050305 -0.210664
28 6 0 -2.131126 -0.315700 0.814970
29 6 0 -2.308144 -1.863187 -1.036041
30 6 0 -3.502937 -0.427571 1.027103
31 1 0 -1.555365 0.370942 1.422763
32 6 0 -3.677241 -1.975434 -0.817843
33 1 0 -1.843954 -2.418079 -1.847299
34 6 0 -4.279336 -1.261350 0.220496
35 1 0 -3.969812 0.153218 1.817453
36 1 0 -4.274837 -2.616277 -1.459846
37 1 0 -5.349259 -1.342396 0.390294
---------------------------------------------------------------------------------------------------
Rotational constants (GHZ): 0.5157548 0.2783919 0.2194104
Thermochemical data:
Zero-point correction= 0.304100 (Hartree/Particle)
Thermal correction to Energy= 0.323175
Thermal correction to Enthalpy= 0.324119
Thermal correction to Gibbs Free Energy= 0.255901
Sum of electronic and zero-point Energies= -879.114133
Sum of electronic and thermal Energies= -879.095058
Sum of electronic and thermal Enthalpies= -879.094114
Sum of electronic and thermal Free Energies= -879.162332
Optimized Molecule = 2TSX:
---------------------------------------------------------
# opt=(calcfc,qst3) freq b3lyp/6-31g(d) geom=connectivity
---------------------------------------------------------
E(RB+HF-LYP) = -879.417722914 A.U. after 1 cycles
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -2.045887 0.736895 1.039249
2 1 0 -2.758046 1.270087 0.421551
3 1 0 -2.485827 0.193086 1.871178
4 6 0 -0.778221 1.300335 1.224328
5 1 0 -0.178313 1.040056 2.089496
6 6 0 -0.317534 2.476443 0.507170
7 8 0 0.678465 3.135106 0.782034
8 8 0 -1.104208 2.783699 -0.573057
9 6 0 -0.711478 3.954454 -1.297680
Page 302
Annexure 4
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10 1 0 -1.422478 4.043011 -2.120882
11 1 0 -0.756237 4.841792 -0.659458
12 1 0 0.307417 3.853734 -1.682404
13 6 0 -0.397710 -2.336669 1.008176
14 1 0 0.666085 -2.438695 1.207220
15 1 0 -0.915610 -2.033608 1.923975
16 1 0 -0.827466 -3.265945 0.639169
17 7 0 -0.624823 -1.282322 -0.003251
18 7 0 -1.891127 -0.806205 -0.150460
19 6 0 -2.910434 -1.718374 -0.338526
20 8 0 -2.746844 -2.910555 -0.586100
21 6 0 -4.296232 -1.096741 -0.267932
22 1 0 -4.339510 -0.139625 -0.796049
23 1 0 -5.008233 -1.796452 -0.708611
24 1 0 -4.585493 -0.916888 0.774896
25 6 0 0.311572 -0.410190 -0.358015
26 1 0 -0.049899 0.358573 -1.029314
27 6 0 1.765081 -0.616063 -0.223247
28 6 0 2.361787 -1.851224 -0.540813
29 6 0 2.588441 0.468493 0.129226
30 6 0 3.745770 -2.004108 -0.479061
31 1 0 1.744282 -2.681780 -0.870578
32 6 0 3.970685 0.303399 0.195721
33 1 0 2.144946 1.429719 0.373079
34 6 0 4.553995 -0.929530 -0.104299
35 1 0 4.191380 -2.961562 -0.734388
36 1 0 4.593570 1.145524 0.484103
37 1 0 5.632763 -1.050048 -0.055783
---------------------------------------------------------------------
Rotational constants (GHZ): 0.4245758 0.3021655 0.1933336
Thermochemical data:
Zero-point correction= 0.303699 (Hartree/Particle)
Thermal correction to Energy= 0.323015
Thermal correction to Enthalpy= 0.323959
Thermal correction to Gibbs Free Energy= 0.254709
Sum of electronic and zero-point Energies= -879.114024
Sum of electronic and thermal Energies= -879.094708
Sum of electronic and thermal Enthalpies= -879.093764
Sum of electronic and thermal Free Energies= -879.163014
Optimized Molecule = 2TSN:
# opt=(calcfc,qst3) freq b3lyp/6-31g(d) geom=connectivity
---------------------------------------------------------
E(RB+HF-LYP) = -879.417861122 A.U. after 1 cycles
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -2.045596 1.198985 -0.975936
2 1 0 -2.511204 1.572827 -0.069543
3 1 0 -2.721688 1.090720 -1.817106
4 6 0 -0.726342 1.587111 -1.241722
5 1 0 -0.360397 1.594462 -2.262926
6 6 0 0.120178 2.306125 -0.309064
7 8 0 1.200526 2.813378 -0.581240
8 8 0 -0.401800 2.370168 0.961538
9 6 0 0.395209 3.095887 1.903340
10 1 0 -0.158325 3.066150 2.843780
11 1 0 1.378280 2.631361 2.024406
12 1 0 0.537404 4.130796 1.579402
13 6 0 -0.744626 -0.912010 1.530153
14 1 0 0.305859 -0.925838 1.809879
15 1 0 -1.193579 0.030619 1.851361
16 1 0 -1.283053 -1.754801 1.959042
17 7 0 -0.869933 -0.982715 0.056650
18 7 0 -2.075208 -0.684144 -0.498612
19 6 0 -3.196815 -1.319289 -0.002025
20 8 0 -3.173615 -2.290126 0.749543
21 6 0 -4.503323 -0.741940 -0.523647
22 1 0 -4.469355 -0.570654 -1.604015
23 1 0 -5.304568 -1.443710 -0.287076
24 1 0 -4.723648 0.217773 -0.040606
25 6 0 0.152487 -0.786864 -0.767270
26 1 0 -0.129609 -0.783142 -1.811165
27 6 0 1.576660 -0.945016 -0.429876
28 6 0 2.031268 -2.032963 0.340364
Page 303
Annexure 4
153
29 6 0 2.519690 -0.058276 -0.979389
30 6 0 3.393213 -2.214723 0.570629
31 1 0 1.319354 -2.756628 0.726492
32 6 0 3.879765 -0.244182 -0.738207
33 1 0 2.184500 0.801477 -1.548459
34 6 0 4.321262 -1.318740 0.035744
35 1 0 3.728846 -3.064062 1.159210
36 1 0 4.595088 0.459898 -1.153554
37 1 0 5.383016 -1.461219 0.217308
---------------------------------------------------------------------
Rotational constants (GHZ): 0.4973750 0.2861943 0.2151843
Thermochemical data:
Zero-point correction= 0.303878 (Hartree/Particle)
Thermal correction to Energy= 0.323113
Thermal correction to Enthalpy= 0.324057
Thermal correction to Gibbs Free Energy= 0.255111
Sum of electronic and zero-point Energies= -879.113983
Sum of electronic and thermal Energies= -879.094748
Sum of electronic and thermal Enthalpies= -879.093804
Sum of electronic and thermal Free Energies= -879.162750
Optimized Molecule = 2PRX-r:
E(RB+HF-LYP) = -879.485548768 A.U.
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.017275 -1.076486 -1.012095
2 1 0 0.060749 -2.131332 -0.728742
3 1 0 -0.476320 -1.012293 -1.986429
4 6 0 1.423967 -0.427661 -1.087867
5 1 0 1.793570 -0.361420 -2.114148
6 6 0 2.466623 -1.253572 -0.331593
7 8 0 3.289368 -1.950846 -0.877617
8 8 0 2.275685 -1.207552 1.004462
9 6 0 3.240964 -1.936310 1.781031
10 1 0 2.943414 -1.800136 2.821215
11 1 0 3.232496 -2.995752 1.511881
12 1 0 4.240359 -1.528655 1.610107
13 6 0 -0.821986 1.852998 -1.355447
14 1 0 -1.861963 2.063539 -1.097654
15 1 0 -0.303999 2.801592 -1.515279
16 1 0 -0.796810 1.282253 -2.296175
17 7 0 -0.180773 1.168135 -0.216966
18 7 0 1.189397 0.909681 -0.510792
19 6 0 2.217110 1.655485 0.013239
20 8 0 3.379794 1.312160 -0.176037
21 6 0 1.833369 2.902078 0.784362
22 1 0 1.077711 2.678746 1.542282
23 1 0 2.736994 3.301357 1.247503
24 1 0 1.410341 3.662411 0.117869
25 6 0 -0.697688 -0.206606 0.045017
26 1 0 -0.278140 -0.477942 1.021514
27 6 0 -2.207566 -0.283527 0.141210
28 6 0 -2.972156 -1.153237 -0.643585
29 6 0 -2.865166 0.520175 1.086680
30 6 0 -4.360399 -1.216988 -0.493021
31 1 0 -2.490499 -1.796660 -1.373673
32 6 0 -4.249284 0.464498 1.232468
33 1 0 -2.278904 1.197261 1.702639
34 6 0 -5.003202 -0.407150 0.441381
35 1 0 -4.936242 -1.901850 -1.109777
36 1 0 -4.740497 1.097220 1.967000
37 1 0 -6.082574 -0.455324 0.557017
---------------------------------------------------------------------
Rotational constants (GHZ): 0.6886476 0.2325717 0.2044275
Thermochemical data:
Zero-point correction= 0.308202 (Hartree/Particle)
Thermal correction to Energy= 0.326668
Thermal correction to Enthalpy= 0.327613
Thermal correction to Gibbs Free Energy= 0.260576
Sum of electronic and zero-point Energies= -879.177347
Sum of electronic and thermal Energies= -879.158880
Sum of electronic and thermal Enthalpies= -879.157936
Sum of electronic and thermal Free Energies= -879.224973
Page 304
Annexure 4
154
Optimized Molecule = 2PRN-r:
E(RB+HF-LYP) = -879.478423586 A.U.
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -0.010428 -0.948739 -1.026156
2 1 0 0.070217 -1.695359 -0.230714
3 1 0 0.176073 -1.440828 -1.984120
4 6 0 -1.401916 -0.275104 -0.987546
5 1 0 -1.735230 -0.020325 -1.998631
6 6 0 -2.473892 -1.209244 -0.426307
7 8 0 -3.322907 -1.740257 -1.108747
8 8 0 -2.346709 -1.397385 0.901979
9 6 0 -3.303705 -2.295303 1.492779
10 1 0 -3.060706 -2.321860 2.554916
11 1 0 -4.320098 -1.924245 1.338825
12 1 0 -3.217756 -3.291291 1.050505
13 6 0 0.321904 0.637237 1.652711
14 1 0 1.361522 0.765921 1.961017
15 1 0 -0.301723 1.311925 2.242520
16 1 0 0.009401 -0.399977 1.841291
17 7 0 0.196242 1.059573 0.248313
18 7 0 -1.152548 0.945827 -0.199067
19 6 0 -2.013131 2.008701 -0.016138
20 8 0 -1.700985 2.991786 0.638397
21 6 0 -3.394284 1.855538 -0.641089
22 1 0 -3.353013 1.572804 -1.698558
23 1 0 -3.987408 1.094501 -0.120747
24 1 0 -3.901680 2.816178 -0.543612
25 6 0 0.923809 0.249043 -0.755000
26 1 0 0.930550 0.865696 -1.666049
27 6 0 2.365042 -0.035522 -0.384161
28 6 0 2.883013 -1.330876 -0.286922
29 6 0 3.226244 1.052106 -0.167062
30 6 0 4.230099 -1.538215 0.023812
31 1 0 2.242852 -2.190789 -0.460323
32 6 0 4.566737 0.847179 0.150718
33 1 0 2.829349 2.061375 -0.239454
34 6 0 5.074226 -0.451826 0.246151
35 1 0 4.615737 -2.552037 0.091439
36 1 0 5.217556 1.700851 0.320127
37 1 0 6.121005 -0.613350 0.489074
---------------------------------------------------------------------
Rotational constants (GHZ): 0.6730467 0.2309691 0.1957762
Thermochemical data:
Zero-point correction= 0.307984 (Hartree/Particle)
Thermal correction to Energy= 0.326621
Thermal correction to Enthalpy= 0.327565
Thermal correction to Gibbs Free Energy= 0.259185
Sum of electronic and zero-point Energies= -879.170439
Sum of electronic and thermal Energies= -879.151803
Sum of electronic and thermal Enthalpies= -879.150859
Sum of electronic and thermal Free Energies= -879.219239
Optimized Molecule = 2PSX-r:
E(RB+HF-LYP) = -879.470597430 A.U.
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -0.233108 -1.506847 -0.231048
2 1 0 -0.752434 -2.350993 0.224745
3 1 0 0.286717 -1.877143 -1.116470
4 6 0 -1.236305 -0.381986 -0.600028
5 1 0 -1.327711 -0.283197 -1.685264
6 6 0 -2.651950 -0.649991 -0.060153
7 8 0 -3.317593 0.116334 0.595383
8 8 0 -3.085693 -1.858234 -0.479957
9 6 0 -4.427696 -2.202764 -0.088741
10 1 0 -4.612945 -3.187830 -0.517386
11 1 0 -4.511706 -2.233334 1.000435
12 1 0 -5.138810 -1.470831 -0.480396
Page 305
Annexure 4
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13 6 0 0.848918 1.369831 1.866258
14 1 0 1.592248 1.836895 1.205418
15 1 0 0.222562 2.142890 2.300943
16 1 0 1.379902 0.831365 2.658441
17 7 0 0.008200 0.375051 1.193838
18 7 0 -0.641468 0.822653 -0.034650
19 6 0 -1.219997 2.076624 -0.163113
20 8 0 -1.054997 2.988274 0.633861
21 6 0 -2.022522 2.292824 -1.442957
22 1 0 -3.034731 1.891619 -1.328807
23 1 0 -2.095075 3.371250 -1.592700
24 1 0 -1.561257 1.837856 -2.325830
25 6 0 0.750864 -0.841028 0.761198
26 1 0 0.858046 -1.455550 1.661211
27 6 0 2.145900 -0.630231 0.180132
28 6 0 2.367594 0.094997 -1.001994
29 6 0 3.254226 -1.172084 0.842490
30 6 0 3.658287 0.269140 -1.500397
31 1 0 1.525315 0.537214 -1.525120
32 6 0 4.547208 -1.008639 0.341264
33 1 0 3.103011 -1.734252 1.761989
34 6 0 4.753253 -0.285249 -0.832981
35 1 0 3.809458 0.838920 -2.413641
36 1 0 5.390823 -1.444437 0.870224
37 1 0 5.757701 -0.152935 -1.225992
---------------------------------------------------------------------
Rotational constants (GHZ): 0.6618743 0.2403891 0.2079820
Thermochemical data:
--------------------------------------------------------------------------------------
Zero-point correction= 0.308253 (Hartree/Particle)
Thermal correction to Energy= 0.326672
Thermal correction to Enthalpy= 0.327616
Thermal correction to Gibbs Free Energy= 0.259624
Sum of electronic and zero-point Energies= -879.162344
Sum of electronic and thermal Energies= -879.143925
Sum of electronic and thermal Enthalpies= -879.142981
Sum of electronic and thermal Free Energies= -879.210974
Optimized Molecule = 2PSN-r:
E(RB+HF-LYP) = -879.464367442 A.U.
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -0.055065 -1.148466 -0.878219
2 1 0 -0.242726 -1.721008 0.034773
3 1 0 -0.305167 -1.783487 -1.730262
4 6 0 1.407960 -0.655261 -0.942893
5 1 0 1.759695 -0.651813 -1.977948
6 6 0 2.348741 -1.652633 -0.236510
7 8 0 2.970990 -2.439912 -0.911613
8 8 0 2.443432 -1.727135 1.106680
9 6 0 1.780570 -0.862176 2.049849
10 1 0 1.654768 -1.466909 2.950125
11 1 0 2.414535 -0.000833 2.276139
12 1 0 0.811954 -0.504238 1.699941
13 6 0 -0.361855 2.449884 -0.228582
14 1 0 -1.427575 2.559930 -0.012787
15 1 0 0.220413 3.074773 0.443674
16 1 0 -0.172275 2.754874 -1.271075
17 7 0 -0.025781 1.036331 -0.005111
18 7 0 1.330748 0.723805 -0.437265
19 6 0 2.406751 1.448017 0.027115
20 8 0 2.294218 2.400277 0.792205
21 6 0 3.770496 1.014924 -0.497802
22 1 0 4.397063 1.908538 -0.531217
23 1 0 4.239154 0.305746 0.194589
24 1 0 3.741605 0.551947 -1.487786
25 6 0 -0.859741 0.156980 -0.852659
26 1 0 -0.900975 0.558135 -1.881602
27 6 0 -2.274672 0.002769 -0.332866
28 6 0 -2.543477 -0.115298 1.037586
29 6 0 -3.339013 -0.073088 -1.238973
30 6 0 -3.849086 -0.310107 1.487744
31 1 0 -1.726897 -0.033261 1.748270
32 6 0 -4.645029 -0.275971 -0.790388
33 1 0 -3.143830 0.027873 -2.304517
Page 306
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34 6 0 -4.903377 -0.395125 0.575595
35 1 0 -4.043729 -0.393207 2.553737
36 1 0 -5.459278 -0.333157 -1.507737
37 1 0 -5.919861 -0.547378 0.928150
---------------------------------------------------------------------
Rotational constants (GHZ): 0.7005564 0.2367675 0.2144106
--------------------------------------------------------------------------------------
----------------------------------------------------------------------------------------------------------------------------
Thermochemical data:
----------------------------------------------------------------------------------------------------------------------------------
Zero-point correction= 0.308392 (Hartree/Particle)
Thermal correction to Energy= 0.326642
Thermal correction to Enthalpy= 0.327587
Thermal correction to Gibbs Free Energy= 0.261551
Sum of electronic and zero-point Energies= -879.155976
Sum of electronic and thermal Energies= -879.137725
Sum of electronic and thermal Enthalpies= -879.136781
Sum of electronic and thermal Free Energies= -879.202816
Optimized Molecule = 2TRX-r:
# opt=(calcfc,qst3) freq b3lyp/6-31g(d) geom=connectivity
---------------------------------------------------------
E(RB+HF-LYP) = -879.399377589 A.U.
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.156303 -1.142620 -1.414367
2 1 0 -0.130748 -2.072813 -0.937619
3 1 0 -0.498849 -0.793867 -2.207968
4 6 0 1.466692 -0.719183 -1.371199
5 1 0 1.873007 -0.027428 -2.098674
6 6 0 2.506094 -1.450250 -0.607841
7 8 0 3.683118 -1.479483 -0.895311
8 8 0 1.981998 -2.130964 0.449268
9 6 0 2.937859 -2.877439 1.213754
10 1 0 2.367865 -3.357910 2.010585
11 1 0 3.432247 -3.628235 0.590766
12 1 0 3.698160 -2.212711 1.632861
13 6 0 -0.579941 2.269883 -0.724997
14 1 0 -1.630588 2.440118 -0.490878
15 1 0 -0.010635 3.171590 -0.508152
16 1 0 -0.464104 2.025661 -1.787412
17 7 0 -0.056154 1.166559 0.099161
18 7 0 1.269721 0.977157 0.158847
19 6 0 2.149527 2.022238 0.374916
20 8 0 3.287370 1.984766 -0.070112
21 6 0 1.735658 3.152239 1.326778
22 1 0 0.736929 3.035527 1.755662
23 1 0 2.468909 3.176490 2.138858
24 1 0 1.805496 4.114791 0.808003
25 6 0 -0.764753 0.031123 0.286358
26 1 0 -0.265848 -0.631031 0.984249
27 6 0 -2.227309 -0.119467 0.178670
28 6 0 -3.003625 0.284493 -0.924259
29 6 0 -2.878480 -0.783306 1.236172
30 6 0 -4.380190 0.067943 -0.945450
31 1 0 -2.530379 0.743391 -1.785550
32 6 0 -4.254083 -1.000340 1.213032
33 1 0 -2.293885 -1.122557 2.087463
34 6 0 -5.013079 -0.569030 0.123706
35 1 0 -4.957981 0.386601 -1.808744
36 1 0 -4.732606 -1.507438 2.046304
37 1 0 -6.085879 -0.738459 0.101805
---------------------------------------------------------------------
Rotational constants (GHZ): 0.5499596 0.2337741 0.1911104
Thermochemical data:
Zero-point correction= 0.303009 (Hartree/Particle)
Thermal correction to Energy= 0.322360
Thermal correction to Enthalpy= 0.323304
Thermal correction to Gibbs Free Energy= 0.253639
Sum of electronic and zero-point Energies= -879.096369
Sum of electronic and thermal Energies= -879.077017
Sum of electronic and thermal Enthalpies= -879.076073
Sum of electronic and thermal Free Energies= -879.145739
Page 307
Annexure 4
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Optimized Molecule = 2TRN-r:
# opt=(calcfc,qst3) freq b3lyp/6-31g(d) geom=connectivity
---------------------------------------------------------
E(RB+HF-LYP) = -879.415641940 A.U.
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -0.024965 0.973908 -1.559923
2 1 0 -0.386689 1.767581 -0.914964
3 1 0 -0.587246 0.835752 -2.478958
4 6 0 1.332396 0.680613 -1.560494
5 1 0 1.788812 0.150174 -2.386356
6 6 0 2.311110 1.337948 -0.680513
7 8 0 3.518314 1.312826 -0.850624
8 8 0 1.736986 2.024786 0.350031
9 6 0 2.660790 2.716299 1.202973
10 1 0 2.047613 3.227685 1.946417
11 1 0 3.342996 2.012544 1.688170
12 1 0 3.249182 3.438029 0.630248
13 6 0 -0.017113 -0.587023 1.699732
14 1 0 -1.041849 -0.663754 2.061495
15 1 0 0.630007 -1.261884 2.254625
16 1 0 0.339141 0.443789 1.779729
17 7 0 0.021997 -1.015545 0.286577
18 7 0 1.179957 -1.300944 -0.320707
19 6 0 2.181641 -1.987813 0.354007
20 8 0 2.035878 -2.598452 1.411633
21 6 0 3.490014 -1.997662 -0.412158
22 1 0 3.333735 -2.364148 -1.432478
23 1 0 3.905829 -0.986940 -0.491155
24 1 0 4.194405 -2.648912 0.108434
25 6 0 -0.943105 -0.667124 -0.604842
26 1 0 -0.865552 -1.268544 -1.504056
27 6 0 -2.320934 -0.260652 -0.241690
28 6 0 -2.626826 0.811436 0.615785
29 6 0 -3.384356 -0.949145 -0.851365
30 6 0 -3.951487 1.156338 0.878478
31 1 0 -1.827513 1.391730 1.064857
32 6 0 -4.708564 -0.602734 -0.589384
33 1 0 -3.166333 -1.770420 -1.529511
34 6 0 -4.997074 0.449516 0.281050
35 1 0 -4.166480 1.987746 1.544162
36 1 0 -5.513966 -1.154967 -1.065590
37 1 0 -6.028347 0.723257 0.485577
---------------------------------------------------------------------
Rotational constants (GHZ): 0.6187190 0.2326103 0.2019620
Thermochemical data:
Zero-point correction= 0.303905 (Hartree/Particle)
Thermal correction to Energy= 0.322960
Thermal correction to Enthalpy= 0.323904
Thermal correction to Gibbs Free Energy= 0.255719
Sum of electronic and zero-point Energies= -879.111737
Sum of electronic and thermal Energies= -879.092682
Sum of electronic and thermal Enthalpies= -879.091738
Sum of electronic and thermal Free Energies= -879.159923
Optimized Molecule = 2TSX-r:
# opt=(calcfc,qst3) freq b3lyp/6-31g(d) geom=connectivity
---------------------------------------------------------
E(RB+HF-LYP) = -879.413033843 A.U.
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.205359 -1.136447 1.342170
2 1 0 -0.042035 -2.106215 0.924329
3 1 0 -0.404826 -0.819783 2.184300
4 6 0 1.528410 -0.721532 1.276389
5 1 0 1.943466 -0.022338 1.991991
6 6 0 2.534008 -1.392433 0.439371
7 8 0 3.737301 -1.219276 0.524439
8 8 0 1.976739 -2.247451 -0.459747
Page 308
Annexure 4
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9 6 0 2.909245 -2.919635 -1.317271
10 1 0 2.305746 -3.555165 -1.966778
11 1 0 3.477576 -2.196701 -1.908620
12 1 0 3.607695 -3.523520 -0.731494
13 6 0 -0.633696 2.091837 0.974654
14 1 0 -1.635803 1.797992 1.279723
15 1 0 0.041026 2.062453 1.836884
16 1 0 -0.617861 3.095141 0.556641
17 7 0 -0.125000 1.131859 -0.033121
18 7 0 1.189233 1.058164 -0.287649
19 6 0 1.927625 2.237272 -0.301835
20 8 0 1.449676 3.369676 -0.336943
21 6 0 3.421395 2.001058 -0.410214
22 1 0 3.692779 1.934361 -1.471434
23 1 0 3.942504 2.862993 0.013248
24 1 0 3.744971 1.077000 0.073860
25 6 0 -0.744552 -0.064870 -0.196688
26 1 0 -0.230689 -0.674906 -0.934333
27 6 0 -2.227639 -0.198458 -0.152322
28 6 0 -3.058165 0.827578 -0.639524
29 6 0 -2.829969 -1.394144 0.271905
30 6 0 -4.443304 0.672293 -0.672082
31 1 0 -2.612229 1.742737 -1.017463
32 6 0 -4.214856 -1.549694 0.233534
33 1 0 -2.215488 -2.209279 0.638898
34 6 0 -5.028381 -0.515754 -0.232353
35 1 0 -5.063323 1.479185 -1.053042
36 1 0 -4.658221 -2.482109 0.572172
37 1 0 -6.107524 -0.638031 -0.259882
---------------------------------------------------------------------
Rotational constants (GHZ): 0.5540963 0.2435619 0.1855666
Thermochemical data:
Zero-point correction= 0.303625 (Hartree/Particle)
Thermal correction to Energy= 0.322798
Thermal correction to Enthalpy= 0.323742
Thermal correction to Gibbs Free Energy= 0.254607
Sum of electronic and zero-point Energies= -879.109409
Sum of electronic and thermal Energies= -879.090236
Sum of electronic and thermal Enthalpies= -879.089292
Sum of electronic and thermal Free Energies= -879.158427
Optimized Molecule = 2TSN-r:
# opt=(calcfc,qst3) freq b3lyp/6-31g(d) geom=connectivity
---------------------------------------------------------
E(RB+HF-LYP) = -879.415641766 A.U.
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.024823 0.974875 -1.559086
2 1 0 0.386128 1.768246 -0.913518
3 1 0 0.587399 0.837484 -2.478057
4 6 0 -1.332416 0.681043 -1.560210
5 1 0 -1.788374 0.150849 -2.386486
6 6 0 -2.311749 1.337774 -0.680423
7 8 0 -3.518799 1.313021 -0.851658
8 8 0 -1.738408 2.023619 0.351189
9 6 0 -2.662739 2.715447 1.203307
10 1 0 -2.050062 3.226612 1.947312
11 1 0 -3.250362 3.437380 0.630045
12 1 0 -3.345674 2.011974 1.687852
13 6 0 0.017599 -0.587242 1.699843
14 1 0 1.042224 -0.665019 2.061720
15 1 0 -0.337769 0.443848 1.780164
16 1 0 -0.630137 -1.261764 2.254439
17 7 0 -0.021689 -1.015302 0.286565
18 7 0 -1.179723 -1.300551 -0.320661
19 6 0 -2.181040 -1.988247 0.353683
20 8 0 -2.034924 -2.599515 1.410916
21 6 0 -3.489485 -1.998112 -0.412385
22 1 0 -3.333253 -2.365211 -1.432496
23 1 0 -4.194019 -2.648937 0.108538
24 1 0 -3.905075 -0.987364 -0.491911
25 6 0 0.943322 -0.666612 -0.604796
26 1 0 0.865736 -1.267707 -1.504227
27 6 0 2.321190 -0.260229 -0.241700
Page 309
Annexure 4
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28 6 0 3.384520 -0.948407 -0.851901
29 6 0 2.627214 0.811462 0.616218
30 6 0 4.708765 -0.602071 -0.590026
31 1 0 3.166388 -1.769381 -1.530376
32 6 0 3.951916 1.156297 0.878796
33 1 0 1.827981 1.391515 1.065735
34 6 0 4.997409 0.449794 0.280831
35 1 0 5.514092 -1.154058 -1.066646
36 1 0 4.167011 1.987400 1.544828
37 1 0 6.028713 0.723480 0.485277
---------------------------------------------------------------------
Rotational constants (GHZ): 0.6187303 0.2325717 0.2019369
Thermochemical data:
Zero-point correction= 0.303905 (Hartree/Particle)
Thermal correction to Energy= 0.322961
Thermal correction to Enthalpy= 0.323905
Thermal correction to Gibbs Free Energy= 0.255718
Sum of electronic and zero-point Energies= -879.111737
Sum of electronic and thermal Energies= -879.092681
Sum of electronic and thermal Enthalpies= -879.091737
Sum of electronic and thermal Free Energies= -879.159924
Optimized Molecule = 3PRX:
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------
E(RB+HF-LYP) = -1107.35493670
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.690627 -2.252835 -1.584633
2 1 0 1.706328 -2.563624 -1.332299
3 1 0 0.131457 -3.131335 -1.914041
4 1 0 0.731065 -1.536417 -2.419053
5 7 0 0.041163 -1.726586 -0.368164
6 7 0 -1.297490 -1.329386 -0.659658
7 6 0 -2.393451 -2.130575 -0.442808
8 8 0 -3.517821 -1.688631 -0.654167
9 6 0 -2.127511 -3.547307 0.022371
10 1 0 -1.352949 -3.574799 0.792886
11 1 0 -3.065885 -3.957301 0.399402
12 1 0 -1.787276 -4.172053 -0.812143
13 6 0 0.634811 -0.465333 0.151880
14 1 0 0.208988 -0.323789 1.151470
15 6 0 2.144137 -0.515207 0.274042
16 6 0 2.997650 0.342446 -0.428716
17 6 0 2.707815 -1.454094 1.152700
18 6 0 4.383058 0.262116 -0.260034
19 1 0 2.592150 1.090458 -1.103459
20 6 0 4.088291 -1.541015 1.314925
21 1 0 2.051260 -2.121485 1.704914
22 6 0 4.932257 -0.680552 0.607106
23 1 0 5.030241 0.939833 -0.810290
24 1 0 4.506476 -2.275241 1.998325
25 1 0 6.009350 -0.743019 0.736293
26 6 0 -1.456772 0.112723 -0.893639
27 1 0 -1.853151 0.321708 -1.889911
28 6 0 0.009066 0.630207 -0.750438
29 1 0 0.470339 0.629750 -1.740366
30 6 0 0.127461 2.028696 -0.169327
31 6 0 -2.422129 0.801369 0.081661
32 8 0 -0.055731 2.315073 0.993870
33 8 0 -3.067151 1.775245 -0.235387
34 8 0 0.479390 2.919849 -1.117618
35 8 0 -2.387088 0.270494 1.312438
36 6 0 0.578888 4.285786 -0.670653
37 1 0 -0.385606 4.627156 -0.287376
38 1 0 1.331934 4.375421 0.116273
39 1 0 0.869128 4.858816 -1.551253
40 6 0 -3.200252 0.943474 2.288857
41 1 0 -2.855193 1.972317 2.415851
42 1 0 -4.246578 0.942106 1.974546
43 1 0 -3.074253 0.377660 3.212129
-------------------------------------------------------------------------------------------------------------
Rotational constants (GHZ): 0.3473467 0.2250194 0.1624149
Page 310
Annexure 4
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Thermochemical data:
Zero-point correction= 0.351190 (Hartree/Particle)
Thermal correction to Energy= 0.374287
Thermal correction to Enthalpy= 0.375231
Thermal correction to Gibbs Free Energy= 0.297356
Sum of electronic and zero-point Energies= -1107.003747
Sum of electronic and thermal Energies= -1106.980650
Sum of electronic and thermal Enthalpies= -1106.979705
Sum of electronic and thermal Free Energies= -1107.057580
Optimized Molecule = 3PRN:
--------------------------------------
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------
E(RB+HF-LYP) = -1107.34887790 A.U.
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.401005 2.950561 -1.012724
2 1 0 1.465643 3.171003 -1.138331
3 1 0 -0.083300 2.952434 -2.003287
4 1 0 -0.043661 3.741131 -0.403440
5 7 0 0.285207 1.663820 -0.320668
6 7 0 -1.090352 1.291944 -0.149373
7 6 0 -1.676627 1.409941 1.102104
8 8 0 -2.765678 0.901923 1.333892
9 6 0 -0.943626 2.258127 2.120266
10 1 0 0.036989 1.826148 2.336972
11 1 0 -0.780785 3.279688 1.762373
12 1 0 -1.551980 2.286576 3.025436
13 6 0 0.947523 0.572540 -1.088511
14 1 0 1.010050 0.879509 -2.145291
15 6 0 2.361208 0.268385 -0.622921
16 6 0 2.783828 0.514238 0.688052
17 6 0 3.268772 -0.289975 -1.532808
18 6 0 4.085863 0.200513 1.081050
19 1 0 2.089044 0.963618 1.388127
20 6 0 4.567587 -0.610241 -1.139705
21 1 0 2.955943 -0.476607 -2.558328
22 6 0 4.980380 -0.364759 0.171234
23 1 0 4.402221 0.401516 2.101389
24 1 0 5.257427 -1.044930 -1.858015
25 1 0 5.993790 -0.607612 0.479297
26 6 0 -0.061411 -0.615570 -1.070777
27 1 0 0.038677 -1.201239 -1.986507
28 6 0 -1.391789 0.168268 -1.050712
29 1 0 -1.564245 0.577624 -2.054007
30 6 0 -2.634844 -0.652091 -0.696573
31 6 0 0.145815 -1.610744 0.066246
32 8 0 -2.613590 -1.732495 -0.151125
33 8 0 0.488572 -2.756776 -0.108787
34 8 0 -3.732111 -0.070921 -1.209080
35 8 0 -0.040090 -1.054039 1.280480
36 6 0 -4.975014 -0.685059 -0.830686
37 1 0 -4.998501 -1.732633 -1.141259
38 1 0 -5.097455 -0.620373 0.253379
39 1 0 -5.750714 -0.113299 -1.340829
40 6 0 0.040788 -1.969288 2.386910
41 1 0 -0.714437 -2.750650 2.275869
42 1 0 1.033708 -2.423031 2.435044
43 1 0 -0.155967 -1.369841 3.275975
---------------------------------------------------------------------
Rotational constants (GHZ): 0.4727611 0.1946195 0.1803116
Thermochemical data:
Zero-point correction= 0.350940 (Hartree/Particle)
Thermal correction to Energy= 0.373755
Thermal correction to Enthalpy= 0.374699
Thermal correction to Gibbs Free Energy= 0.298260
Sum of electronic and zero-point Energies= -1106.997938
Sum of electronic and thermal Energies= -1106.975123
Sum of electronic and thermal Enthalpies= -1106.974179
Sum of electronic and thermal Free Energies= -1107.050618
Page 311
Annexure 4
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Optimized Molecule = 3PSX:
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------
E(RB+HF-LYP) = -1107.34950816 A.U.
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -0.224772 0.794644 2.475172
2 1 0 0.334526 0.258289 3.247967
3 1 0 -0.311645 1.839501 2.780458
4 1 0 -1.225909 0.357315 2.373545
5 7 0 0.568766 0.760806 1.239823
6 7 0 -0.051398 1.454789 0.177665
7 6 0 0.203505 2.801652 0.011608
8 8 0 0.903532 3.425338 0.795059
9 6 0 -0.469954 3.461485 -1.182907
10 1 0 -1.559729 3.375788 -1.120245
11 1 0 -0.192080 4.515968 -1.172643
12 1 0 -0.144178 3.020498 -2.132807
13 6 0 0.898810 -0.552036 0.693168
14 1 0 0.786744 -1.291832 1.492674
15 6 0 2.328309 -0.626138 0.158263
16 6 0 3.197858 0.464927 0.247656
17 6 0 2.786692 -1.822670 -0.411727
18 6 0 4.504173 0.360674 -0.237600
19 1 0 2.842452 1.385746 0.699536
20 6 0 4.092798 -1.926320 -0.887993
21 1 0 2.118210 -2.679084 -0.484057
22 6 0 4.956385 -0.831209 -0.803990
23 1 0 5.170014 1.217040 -0.167759
24 1 0 4.435713 -2.861346 -1.323414
25 1 0 5.974571 -0.909414 -1.176114
26 6 0 -0.163913 -0.836239 -0.451365
27 1 0 0.349020 -1.168636 -1.352692
28 6 0 -0.798379 0.569320 -0.707612
29 1 0 -0.615925 0.840743 -1.752088
30 6 0 -2.320210 0.669248 -0.518111
31 6 0 -1.087018 -1.982821 -0.081344
32 8 0 -2.890760 1.388588 0.266741
33 8 0 -1.039713 -3.079809 -0.592553
34 8 0 -2.939137 -0.113179 -1.426724
35 8 0 -1.910613 -1.675017 0.945776
36 6 0 -4.377791 -0.090926 -1.387314
37 1 0 -4.736067 -0.427955 -0.411352
38 1 0 -4.747948 0.920388 -1.573546
39 1 0 -4.701974 -0.771627 -2.174420
40 6 0 -2.767187 -2.740169 1.396520
41 1 0 -3.404073 -3.088552 0.579683
42 1 0 -2.169606 -3.578232 1.763846
43 1 0 -3.365994 -2.311654 2.200072
--------------------------------------------------------------------------------------------
Rotational constants (GHZ): 0.3673058 0.2176085 0.1651214
Thermochemical data:
Zero-point correction= 0.350859 (Hartree/Particle)
Thermal correction to Energy= 0.374012
Thermal correction to Enthalpy= 0.374956
Thermal correction to Gibbs Free Energy= 0.296635
Sum of electronic and zero-point Energies= -1106.998649
Sum of electronic and thermal Energies= -1106.975496
Sum of electronic and thermal Enthalpies= -1106.974552
Sum of electronic and thermal Free Energies= -1107.052873
Optimized Molecule = 3PSN:
# opt b3lyp/6-31g(d) geom=connectivity
--------------------------------------
E(RB+HF-LYP) = -1107.33814817 A.U.
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -0.736292 -3.022167 0.169727
Page 312
Annexure 4
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2 1 0 -1.816337 -3.060488 0.005594
3 1 0 -0.238813 -3.674687 -0.545846
4 1 0 -0.516778 -3.357698 1.198273
5 7 0 -0.309721 -1.638319 -0.064838
6 7 0 1.098519 -1.462486 0.244265
7 6 0 2.025365 -2.171205 -0.489581
8 8 0 1.699513 -2.926847 -1.395933
9 6 0 3.481199 -2.078526 -0.048624
10 1 0 3.647330 -1.605782 0.922557
11 1 0 3.862613 -3.102366 -0.006643
12 1 0 4.058373 -1.544429 -0.809301
13 6 0 -1.015631 -0.705735 0.823869
14 1 0 -1.094928 -1.138853 1.840134
15 6 0 -2.424859 -0.378697 0.362401
16 6 0 -2.794246 -0.416630 -0.987942
17 6 0 -3.382588 -0.023547 1.320991
18 6 0 -4.099199 -0.098546 -1.365945
19 1 0 -2.050031 -0.689569 -1.726629
20 6 0 -4.683586 0.306674 0.940908
21 1 0 -3.110095 -0.010674 2.374893
22 6 0 -5.045469 0.267913 -0.406667
23 1 0 -4.375752 -0.134869 -2.416379
24 1 0 -5.414448 0.581800 1.696782
25 1 0 -6.060391 0.515836 -0.706302
26 6 0 1.311517 -0.288341 1.092654
27 1 0 1.436943 -0.578844 2.142047
28 6 0 -0.040545 0.483070 0.972189
29 1 0 -0.226517 1.031908 1.896762
30 6 0 -0.076480 1.484855 -0.179039
31 6 0 2.513637 0.609772 0.792192
32 8 0 -0.296947 1.251144 -1.342426
33 8 0 3.187295 1.099254 1.671296
34 8 0 0.185541 2.725823 0.300421
35 8 0 2.694326 0.828768 -0.518836
36 6 0 0.181663 3.773542 -0.684082
37 1 0 0.923406 3.573250 -1.461705
38 1 0 -0.804273 3.854631 -1.149063
39 1 0 0.426987 4.686247 -0.140498
40 6 0 3.778431 1.715784 -0.854226
41 1 0 3.618883 2.696855 -0.400418
42 1 0 4.727040 1.306503 -0.497656
43 1 0 3.769867 1.782438 -1.941701
--------------------------------------------------------------------------------------------
Rotational constants (GHZ): 0.4058668 0.2121265 0.1647509
Thermochemical data:
Zero-point correction= 0.350964 (Hartree/Particle)
Thermal correction to Energy= 0.373877
Thermal correction to Enthalpy= 0.374821
Thermal correction to Gibbs Free Energy= 0.297427
Sum of electronic and zero-point Energies= -1106.987184
Sum of electronic and thermal Energies= -1106.964272
Sum of electronic and thermal Enthalpies= -1106.963327
Sum of electronic and thermal Free Energies= -1107.040721
Optimized Molecule = 3TRX:
------------------------------------------------
# opt=qst3 freq b3lyp/6-31g(d) geom=connectivity
------------------------------------------------
SCF Done: E(RB+HF-LYP) = -1107.27563783 A.U. after 1 cycles
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z ---------------------------------------------------------------------
1 6 0 0.070740 -2.806274 -1.068847
2 1 0 0.998873 -3.252403 -0.711266
3 1 0 -0.720244 -3.554047 -1.064062
4 1 0 0.197259 -2.429386 -2.089026
5 7 0 -0.330634 -1.703410 -0.177678
6 7 0 -1.595236 -1.245772 -0.259458
7 6 0 -2.714813 -2.015203 -0.075738
8 8 0 -3.804610 -1.611160 -0.466767
9 6 0 -2.610557 -3.327337 0.705947
10 1 0 -1.659382 -3.459778 1.229210
11 1 0 -3.426401 -3.339200 1.433650
12 1 0 -2.773116 -4.175566 0.030609
Page 313
Annexure 4
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13 6 0 0.534010 -0.854158 0.372390
14 1 0 0.054592 -0.146139 1.038706
15 6 0 1.992518 -0.898944 0.380092
16 6 0 2.814116 -1.362555 -0.667783
17 6 0 2.617229 -0.368158 1.528801
18 6 0 4.200707 -1.334458 -0.546332
19 1 0 2.378472 -1.703771 -1.599128
20 6 0 4.003495 -0.347525 1.647723
21 1 0 1.999488 0.023891 2.331845
22 6 0 4.802042 -0.838323 0.612588
23 1 0 4.815271 -1.688756 -1.369133
24 1 0 4.460165 0.055578 2.547147
25 1 0 5.884579 -0.820255 0.700879
26 6 0 -1.623505 0.639963 -1.159670
27 1 0 -2.193699 0.227718 -1.983889
28 6 0 -0.301512 0.982356 -1.385371
29 1 0 0.176881 0.638330 -2.297397
30 6 0 0.448068 1.972621 -0.616869
31 6 0 -2.505100 1.405486 -0.204169
32 8 0 0.113396 2.520696 0.422850
33 8 0 -3.283241 2.239537 -0.613517
34 8 0 1.643274 2.234901 -1.224694
35 8 0 -2.346935 1.089472 1.090106
36 6 0 2.455595 3.213101 -0.568205
37 1 0 1.924245 4.164878 -0.478627
38 1 0 2.741565 2.874888 0.432151
39 1 0 3.340954 3.328836 -1.195627
40 6 0 -3.096124 1.907657 2.001394
41 1 0 -2.757879 2.945138 1.937082
42 1 0 -4.163811 1.856984 1.774634
43 1 0 -2.893244 1.500271 2.992661
---------------------------------------------------------------------------------------------------
Rotational constants (GHZ): 0.3554698 0.2081792 0.1559693
Thermochemical data:
Zero-point correction= 0.346039 (Hartree/Particle)
Thermal correction to Energy= 0.370162
Thermal correction to Enthalpy= 0.371107
Thermal correction to Gibbs Free Energy= 0.288940
Sum of electronic and zero-point Energies= -1106.929599
Sum of electronic and thermal Energies= -1106.905475
Sum of electronic and thermal Enthalpies= -1106.904531
Sum of electronic and thermal Free Energies= -1106.986697
Optimized Molecule = 3TRN:
-------------------------------------------
# opt=qst3 b3lyp/6-31g(d) geom=connectivity
-------------------------------------------
E(RB+HF-LYP) = -1107.27897788 A.U
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 0.011898 1.309059 1.655712
2 1 0 1.000205 1.539610 2.052501
3 1 0 -0.723253 1.986780 2.085602
4 1 0 -0.291340 0.283600 1.873035
5 7 0 0.016488 1.505510 0.190529
6 7 0 -1.158832 1.569475 -0.465496
7 6 0 -2.191493 2.404213 -0.095355
8 8 0 -3.340785 2.132170 -0.421241
9 6 0 -1.874727 3.733025 0.591301
10 1 0 -0.807589 3.964642 0.641116 11 1 0 -2.388935 4.521620 0.034505
12 1 0 -2.294226 3.730612 1.603616
13 6 0 1.054607 1.189792 -0.584458
14 1 0 0.905714 1.486645 -1.614592
15 6 0 2.402287 0.786713 -0.197328
16 6 0 2.730492 -0.025384 0.907421
17 6 0 3.447147 1.212761 -1.043785
18 6 0 4.057208 -0.355267 1.172230
19 1 0 1.948634 -0.436535 1.533453
20 6 0 4.770781 0.883238 -0.772970
21 1 0 3.209627 1.815922 -1.916288
22 6 0 5.082375 0.102818 0.342499
23 1 0 4.289463 -0.987460 2.024663
Page 314
Annexure 4
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24 1 0 5.558740 1.231203 -1.434768
25 1 0 6.114843 -0.160138 0.554309
26 6 0 -0.354678 -0.890675 -1.493092
27 1 0 0.024893 -0.724414 -2.495892
28 6 0 -1.580427 -0.318990 -1.174961
29 1 0 -2.139483 0.107541 -1.999795
30 6 0 -2.496721 -0.779472 -0.068102
31 6 0 0.410338 -1.919806 -0.792592
32 8 0 -2.362510 -0.626467 1.127208
33 8 0 1.357316 -2.512129 -1.283209
34 8 0 -3.558905 -1.400615 -0.619903
35 8 0 -0.023452 -2.179198 0.478567
36 6 0 -4.566010 -1.832181 0.308609
37 1 0 -4.153898 -2.558010 1.014937
38 1 0 -4.960127 -0.975981 0.861974
39 1 0 -5.346532 -2.289501 -0.300227
40 6 0 0.622318 -3.282751 1.123566
41 1 0 0.477762 -4.204705 0.552752
42 1 0 1.696490 -3.104270 1.226536
43 1 0 0.149732 -3.364704 2.103785
-------------------------------------------------------------------------------------------------------
Rotational constants (GHZ): 0.3943503 0.1989845 0.1538646
Thermochemical data:
Zero-point correction= 0.346571 (Hartree/Particle)
Thermal correction to Energy= 0.370310
Thermal correction to Enthalpy= 0.371255
Thermal correction to Gibbs Free Energy= 0.291883
Sum of electronic and zero-point Energies= -1106.932407
Sum of electronic and thermal Energies= -1106.908667
Sum of electronic and thermal Enthalpies= -1106.907723
Sum of electronic and thermal Free Energies= -1106.987094
Optimized Molecule = 3TSX:
-------------------------------------------
# opt=qst3 b3lyp/6-31g(d) geom=connectivity
-------------------------------------------
E(RB+HF-LYP) = -1107.27991082 A.U.
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -1.207663 2.404934 1.137585
2 1 0 -2.184560 2.001103 1.392735
3 1 0 -0.554546 2.378431 2.014437
4 1 0 -1.277603 3.427695 0.773578
5 7 0 -0.578718 1.566096 0.090790
6 7 0 0.767054 1.643546 -0.077175
7 6 0 1.316321 2.908829 -0.202675
8 8 0 0.649171 3.924239 -0.385969
9 6 0 2.833007 2.952146 -0.181443
10 1 0 3.235878 2.432301 -1.055071
11 1 0 3.137870 3.999418 -0.200367
12 1 0 3.251034 2.471424 0.710358
13 6 0 -1.119451 0.432427 -0.330531
14 1 0 -0.497401 -0.121133 -1.023999
15 6 0 -2.555326 0.106187 -0.226495
16 6 0 1.570900 0.141099 0.861640
17 6 0 0.565059 -0.777247 1.212205
18 6 0 -4.880890 0.736762 -0.560280
19 1 0 -3.216744 2.058565 -0.884427
20 6 0 -4.328533 -1.508227 0.135890
21 1 0 -2.239688 -1.942222 0.399446
22 6 0 -5.286330 -0.549928 -0.201070
23 1 0 -5.617138 1.485556 -0.838892
24 1 0 -4.636415 -2.510958 0.418748
25 1 0 -6.342373 -0.805366 -0.190145
26 6 0 -2.970851 -1.192049 0.116195
27 1 0 0.055020 -0.639238 2.159702
28 6 0 -3.526824 1.064957 -0.573647
29 1 0 1.943089 0.744158 1.686580
30 6 0 2.687684 -0.255109 -0.088733
31 6 0 0.350152 -2.096339 0.642838
32 8 0 2.768984 -0.036048 -1.273682
33 8 0 -0.355819 -2.965073 1.140492
34 8 0 3.651252 -0.878449 0.627481
35 8 0 0.994852 -2.290867 -0.546620
36 6 0 4.776554 -1.340872 -0.136950
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Annexure 4
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37 1 0 4.451761 -2.057739 -0.895496
38 1 0 5.278753 -0.504270 -0.630480
39 1 0 5.442293 -1.817791 0.582987
40 6 0 0.837479 -3.589448 -1.129740
41 1 0 1.210653 -4.366126 -0.456282
42 1 0 -0.214398 -3.793176 -1.349742
43 1 0 1.420908 -3.567283 -2.051311
---------------------------------------------------------------------
Rotational constants (GHZ): 0.3553515 0.2021413 0.1403536
Thermochemical data:
Zero-point correction= 0.346570 (Hartree/Particle)
Thermal correction to Energy= 0.370353
Thermal correction to Enthalpy= 0.371297
Thermal correction to Gibbs Free Energy= 0.290988
Sum of electronic and zero-point Energies= -1106.933341
Sum of electronic and thermal Energies= -1106.909558
Sum of electronic and thermal Enthalpies= -1106.908614
Sum of electronic and thermal Free Energies= -1106.988923
Optimized Molecule = 3TSN:
-------------------------------------------
# opt=qst3 b3lyp/6-31g(d) geom=connectivity
-------------------------------------------
E(RB+HF-LYP) = -1107.28800331 A.U.
Standard orientation:
---------------------------------------------------------------------
Center Atomic Atomic Coordinates (Angstroms)
Number Number Type X Y Z
---------------------------------------------------------------------
1 6 0 -0.334911 -1.417000 1.583618
2 1 0 -0.475726 -0.384164 1.905948
3 1 0 -1.163984 -2.042472 1.904228
4 1 0 0.602023 -1.823119 1.964570
5 7 0 -0.303346 -1.469345 0.106675
6 7 0 -1.457406 -1.359154 -0.600323
7 6 0 -2.529387 -2.161980 -0.261637
8 8 0 -2.465722 -3.123742 0.499381
9 6 0 -3.820818 -1.791834 -0.971062
10 1 0 -4.471359 -2.668402 -0.973524
11 1 0 -4.329962 -0.987141 -0.428301
12 1 0 -3.652305 -1.455900 -1.998233
13 6 0 0.782073 -1.224432 -0.620467
14 1 0 0.646798 -1.456992 -1.668807
15 6 0 2.156725 -1.042278 -0.153596
16 6 0 2.530425 -0.339989 1.009688
17 6 0 3.172722 -1.584013 -0.966016
18 6 0 3.874200 -0.223761 1.358911
19 1 0 1.779714 0.158436 1.609916
20 6 0 4.512688 -1.470087 -0.608914
21 1 0 2.900010 -2.108960 -1.877988
22 6 0 4.867983 -0.794328 0.560492
23 1 0 4.145939 0.323723 2.257202
24 1 0 5.278995 -1.905985 -1.243515
25 1 0 5.913368 -0.702473 0.841655
26 6 0 -1.561298 0.528878 -1.238216
27 1 0 -2.093265 0.272156 -2.148380
28 6 0 -0.242994 0.965787 -1.418867
29 1 0 0.204392 0.879673 -2.402592
30 6 0 0.436238 1.836355 -0.474205
31 6 0 -2.479642 1.248449 -0.273906
32 8 0 0.098904 2.075624 0.681366
33 8 0 -3.128815 2.206109 -0.635949
34 8 0 1.553570 2.382629 -1.030071
35 8 0 -2.544267 0.729247 0.965416
36 6 0 2.278641 3.289410 -0.193019
37 1 0 1.632298 4.099745 0.155370
38 1 0 2.696336 2.771923 0.675445
39 1 0 3.082415 3.683951 -0.816690
40 6 0 -3.310458 1.503508 1.905132
41 1 0 -2.836154 2.476512 2.054743
42 1 0 -4.332049 1.647582 1.545577
43 1 0 -3.304698 0.926343 2.830158
---------------------------------------------------------------------------------------------
Rotational constants (GHZ): 0.3926247 0.2050931 0.1608645
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Annexure 4
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Thermochemical data:
Zero-point correction= 0.347055 (Hartree/Particle)
Thermal correction to Energy= 0.370685
Thermal correction to Enthalpy= 0.371629
Thermal correction to Gibbs Free Energy= 0.292566
Sum of electronic and zero-point Energies= -1106.940948
Sum of electronic and thermal Energies= -1106.917319
Sum of electronic and thermal Enthalpies= -1106.916374
Sum of electronic and thermal Free Energies= -1106.995437
IRC polt
--------------------------------------------------------------------------------------------------------------------------------------------------------------------
1TRX - IRC 1TRN - IRC
1TSX - IRC 1TSN - IRC
2TRX –IRC 2TRN –IRC
2TSX –IRC 2TSN –IRC
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2TRX-r –IRC 2TRN-r –IRC
2TSX-r –IRC 2TSN-r –IRC
3TRX –IRC 3TRN –IRC
3TSX –IRC 3TSN –IRC