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Research ArticleElectronic Structure Spectroscopic (IR Raman UV-Vis NMR)Optoelectronic and NLO Properties Investigations of RubescinE (C31H36O7) Molecule in Gas Phase and Chloroform SolutionUsing Ab Initio and DFT Methods
Richard Arnaud Yossa Kamsi 12 GehWilson Ejuh 234 Fidegravele Tchoffo1
Pierre Mkounga5 and Jean-Marie Bienvenu Ndjaka 12
1University of Yaounde I Faculty of Science Department of Physics PO Box 812 Yaounde Cameroon2CETIC (Centre drsquoExcellence Africain en Technologies de lrsquoInformation et de la Communication)Universite de Yaounde I BP 8390 Yaounde Cameroon3University of Bamenda National Higher Polytechnic Institute Department of Electrical and Electronic EngineeringP O Box 39 Bambili Cameroon4University of Dschang IUT Bandjoun Department of General and Scientific Studies PO Box 134 Bandjoun Cameroon5University of Yaounde I Faculty of Science Department of Chemistry PO Box 812 Yaounde Cameroon
Correspondence should be addressed to Richard Arnaud Yossa Kamsi richardkamsiyahoofr
Received 12 October 2018 Accepted 28 November 2018 Published 2 January 2019
Academic Editor Jorg Fink
Copyright copy 2019 Richard Arnaud Yossa Kamsi et al This is an open access article distributed under the Creative CommonsAttribution License which permits unrestricted use distribution and reproduction in any medium provided the original work isproperly cited
Quantum chemical methods were used to study the electronic structure and some physicochemical properties of Rubescin Emolecule Good agreement with experiment was found for 3JH-H coupling constant IR 1H NMR and 13C NMR The excitationenergy and oscillator strength calculated by TD-DFT also complement with experiment Large values were obtained for dipolemoment polarizability first static hyperpolarizability electric susceptibility refractive index and dielectric constant meaning thatRubescin E has strong optical and phonon application and can be a good candidate as NLOs material The 3D analysis of the titlemolecule leads us to the conclusion that electron can easily be transferred from furan to tetrahydrofuran ringThe global reactivitydescriptors were evaluated Mulliken ESP and NBO charges comparisons were carried out and described
1 Introduction
Many molecules from plant research were found nowadaysto have application in the field of medicine where thereare use for the treatment of many diseases among whichwe found malaria caused by plasmodium falciparum Thenew limonoid name Rubescin E (C31H36O7) extracted fromthe roots of Trichilia Rubescens collected from Cameroonhas been evaluated against erythrocytic stages of strain3D7 plasmodium falciparum and also exhibited significantantiplasmodial in vitro activity with IC50 value of 113120583M [1]The FT-IR performed on Rubescin E molecule revealed the
presence of 120572 120573-unsaturated carbonyl moiety at 1720 cmminus1and 1664 cmminus1 These values can be obtained theoreticallyby performing the vibrational frequencies calculation on thetitle molecule and used to explain the different motion ofatoms or group of atoms in a molecular system The 1D(1H 13C NMR) and 2D NMR spectra were run on a BrukerAV spectrometer [1] in order to predict the structure ofthe title molecule and were done in this work in order totake out similarities between experiment done previously andtheoretical calculation performed here
In this work quantum chemical calculation was per-formed in order to take out the electronic structure (energy
HindawiAdvances in Condensed Matter PhysicsVolume 2019 Article ID 4246810 22 pageshttpsdoiorg10115520194246810
2 Advances in Condensed Matter Physics
gap charge distributions NLO properties vibrational fre-quencies NMR and UV-vis calculation) and some physico-chemical properties (3JH-H chemical coupling-coupling con-stant the global reactivity descriptors and some geometricalparameters such as bonds lengths and bonds angles) ofRubescin E molecule To the best of our knowledge notheoretical studywas performed yet on the titlemolecule thatis what motivated us to investigate the electronic structurethe spectroscopic and some physicochemical propertiesof Rubescin E molecule Except for NMR UV-vis 3JH-Hchemical coupling-coupling constant and the vibrationalfrequencies obtained for the two 120572 120573-unsaturated carbonylmoiety most of our results were not compared and weare optimistic that it can be used as threshold for futureexperimental or theoretical research Hartree Fock andDFT (using B3LYP and B3PW91 functionals) methods wereused for these purposes These properties were calculatedby employing the triple split valence basis set along withpolarization functions with and without diffuse functions asimplemented in Gaussian 09 Rev A02 in both gas phase andin a solution of chloroformThe methods and basis sets usedare among the most widely used [2ndash5] and provide excellentresults which are generally very close to experiments [6ndash8]
2 Computational Methods
Theoretical calculations were performed on Rubescin Eusing HF and DFT methods at the B3LYP and B3PW91levels as implemented in Gaussian 09W code [9] All thesecalculations were done in gas phase and in a solution ofchloroform No geometry restriction was applied duringthe optimization procedure The solvent effects were treatedwithin the conductor-like polarizable continuum model(CPCM) For the geometry optimization the 6-311G(dp) and6-311++G(dp) basis set were used in both gas and solventConvergence criteria in which both the maximum force anddisplacement are smaller than the cut-off of 0000015 and0000060 and RMS force and displacement less than thecut-off values of 0000010 and 0000040 were used in thecalculations in order to increase the accuracy of our resultsThe chemical 3JH-H proton-proton coupling constant func-tion of angle between two C-H vectors was calculated fromthe optimization output using the original Karplus equation[10] The optimized form of our molecule was then used todetermine the global reactivity descriptors electronic andNLOs properties The net charges were also evaluated usingMPA ESP and NBOs methods at the three levels mentionedabove and all this was done in both gas phase and chloroformwith the 6-311++G(dp) basis set In order to confirm thestability of our molecule the vibrational frequencies (IR andRaman) were evaluated at the 6-311G(dp) and no imaginaryfrequencies were found leading us to the results that ourmolecule was stable at the levels and basis set consideredThetime dependent density functional theory (TD-DFT) fieldwas used in gas phase with the 6-311++G(dp) basis in orderto understand the electronic transition of our molecule andthe obtained results were compared to experimentTheGIAO(gauge independent atomic orbital) method was used on theoptimized form of our molecule in a solution of chloroform
to determine the 1H and 13C NMR spectra parameters at thethree levels and with the 6-311++G(dp) basis set In orderto compare the calculated values of 1H and 13C chemicalshift with experimental results the reference and widelyusedmolecule TMS (tetramethylsilane) for this purpose wereexploited at the same level at the same phase and with thesame basis set
3 Results and Discussion
31 Optimized Structure The optimized geometry ofRubescin E obtained using the B3LYP6-311++G(dp)method in chloroform is shown in Figure 1 The value ofthe total electronic energy of the molecule obtained at theB3LYP shows that Figure 1 is the most stable structure of themolecule The total electronic energy calculated within thetwo methods in gas and in a solution of chloroform with the6-311++G(dp) is given in Table 1
32 Structural Properties A part of the optimized geometri-cal parameters (bond length bond angle) and total electronicenergy of the title molecule both in gas and in a solution ofchloroform are given in Table 1 using the three levels andwith the 6-311++G(dp) basis set The total description of themolecular geometry of Rubescin Emolecule in gas phase andin a solution of chloroform using ab initio (RHF) and DFT(B3LYP and B3PW91) methods with the 6-311++G(dp) basisset can be obtained from Supplementary Material S1
The atom numbering scheme adopted for this purposeis the same as in Figure 1 The energy differences betweenthe two used phases increase when we move from B3PW91to B3LYP and to RHF and are found to be approximatively048 eV 049 eV and 057 eV respectively The optimizedbond length and bond angle of Rubescin E are also listedin Table 1 with some specific experimental values [12ndash14]found in the literature for some groups of compounds suchas furan ethylene oxide and tetrahydrofuran present in ourmolecule It can be observed fromTable 1 that the values of thebond length obtained at B3LYP are slightly higher than thoseobtained at the B3PW91 level These differences are foundbetween 00034 A and 00107 A for C-C 00061 A and 00095A for C-O and 00007 A and 00013 A for C=C in gas phaseThe value of C=O bond length is better at the DFT methodssince its values are closer to 210 A found in literature [11] Itcan also been observed that the calculated bonds length usingHartree Fock and DFT methods are very close to the valuesfound in literature for the specific groups of compoundspresent in our molecule These observed differences variedfrom 00012 A at the B3LYP level to 00363 A at the RHF levelfrom 00002 A at the B3PW91 level to 00288 A at the B3LYPlevel and from 00019 A at the B3LYP level to 00259 A at theRHF level for C-C C-O and C=C bonds both in gas phaseand in chloroform solution respectively
The bonds angles of the studied molecule are slightlydifferent when we move from one phase to another at eachlevel with larger values obtained at the RHF level From ourresults it can be seen that the C-C-C bond angle varies from963773∘ to 1293418∘ from 966032∘ to 1288385∘ and from964146∘ to 1287371∘ at the gas phase respectively at the RHF
Advances in Condensed Matter Physics 3
Table 1 Optimized geometric parameters in gas phase and in chloroform solution of Rubescin E at the RHF B3LYP and B3PW91 level withthe 6-311++G (dp) basis sets
Levels RHF B3LYP B3PW91Theory a[11] b[12] c[13]Basis set Gaz CDCl3 Gaz CDCl3 Gaz CDCl3
B3LYP and B3PW91 level of the theory In CDCl3 the C-C-C bond angles are similar to those obtained at the gasphase The smallest value of C-C-C bond angle was C20-C8-C29 bond angle and the largest C51-C14-C57 bond angle Forthe C-C-O angle the smallest value was 1044386∘ obtainedat the RHF and the largest value was 123472∘ obtained at theB3LYP level both in the gas phaseTheC-O-C bond angle wasfound between 1071084∘ and 1234264∘ obtained at the RHFlevel These bonds angles compared to some known valuesfound in literature [12 14] for specific compound present inour structure show good similaritiesThe little differences arefound between 00268∘ and 15507∘ for C-C-C bond between00595∘ and 30614∘ for C-C-O bond and between 00202∘and 0781∘ for C-O-C bond These observed differences aredue to the fact that these groups of compounds were notisolated
33 Calculated 3119869119867-119867 Coupling Constant The chemical 3JH-Hproton-proton coupling constant was calculated using theoriginal Karplus [10] equation in gas and solvent and itsresults compared to experimental values [1] obtained byextracting Rubescin E in a solution of chloroform From ourresults we found that the calculated parameters both in gasand in chloroform are all similar at all the levels used Theseobtained results are also very close to experiment As pre-dicted in literature [10] we observed from Table 2 that whenthe angles between the two C-H vectors are close enough to00 or 1800 the value of 3JH-H coupling constant is greater (with31198691800 gt 311986900) and is very small when the angle is close to 900
34 Electronic Properties341 Mulliken ESP and Natural Charge Distribution TheMulliken atomic charges of our molecule calculated at all
6 Advances in Condensed Matter Physics
Figure 1 Ground state geometry of Rubescin E at B3LYP6-311++G(dp) in chloroform solution
the levels in gas phase and chloroform show positive chargefor all the hydrogen atoms The net charge on all theatoms varies from -1109653e to 1980512e from -1164916eto 1904034e and from -0891775e to 1524787e respectivelyin gas phase at the RHF B3PW91 and B3LYP levels In asolution of chloroform the charges varied from -1064962e to1826589e from -1206706e to 1904292e and from -0945041eto 1550492e with some oxygen atoms charges being positiveand can be explained by the fact that the oxygen is related toextremely negative carbon atoms The most positive chargeatoms are C63 C5 C8 and the most negative charge atoms areC71 C62 C67
The electrostatic charges were evaluated in this workusing the CHelpG scheme of Breneman model We foundfrom our results that the most positive charges atom is C4followed by C62 and C2 and the most negative charge atom isC12 followed by C5 and C7 The observation made at all levelsand basis set in gas phase and in a solution of chloroform isthat the most positive charge atoms are directly related to themost negative charge atoms
The natural atomic charges obtained using the naturalbonding orbitalmethodwere also used to evaluate the atomiccharge of Rubescin E Positive and negative charges werefound for all hydrogen and oxygen atoms respectively Inthis case all carbon atoms directly linked to hydrogen atomswere found to have negative charges except for those linked tooxygen atomsThemost negative charge atom was calculatedusing HF method and was observed for O65 (-069456e) andO60 (-068330e) respectively in chloroform and gas phaseThemost positive charge atomwas found to beC62 in both gas(097067e 080601e and 081407e respectively at the RHF
B3PW91 and B3LYP levels) and solvent (098887e 081804eand 082650e respectively at the RHF B3PW91 and B3LYPlevels) this is due to the fact that C62 is related to negativecharge atoms (O65 O60 and C63) Mulliken electrostatic andnatural atomic charge distributions are graphically shown inFigure 2 From Figure 2 one can observe that for almost allthe methods used for charge description the most positiveand negative charge atoms were calculated at the RHF levelin both gas and chloroform and this is due to the fact thatthe effect of electron correlation is not well described in HFmethod
342 Global Reactivity Descriptors In order to understandthe relationships between structure stability and reactivity ofRubescin Emolecule the global reactivity descriptors param-eters such as chemical hardness (H) chemical potential (120583119888119901)chemical softness (s) electronegativity (119883) and electrophilic-ity index (120596) were calculated The finite difference equationgiven by (1) was used to calculate the ionization potentialand electron affinity which are generally used to calculate theabove cited parameters
119868119875 = 119864119902=119873+1 minus 119864119902=119873119864119860 = 119864119902=119873 minus 119864119902=119873minus1
(1)
The IP and EA calculated from (1) were then used to calculate119867 120583119888119901 s119883 and120596 using equations found in the literature [15ndash17] All these parameters calculated using the twomethods ingas phase are presented in Table 3 A high value of 120583119888119901 and 120596characterizes a good electrophile while a small value standsfor good nucleophile
Advances in Condensed Matter Physics 7
Table2Ex
perim
entaland
calculated3J H
-Hproton
-protoncoup
lingconstant
ofRu
bescin
Ein
gasp
hase
andin
chloroform
solutio
n
PARA
MET
ERS
RHF
B3LY
PB3
PW91
EXP[1]
Gaz
CDCl3
Gaz
CDCl3
Gaz
CDCl3
Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)H10-C9-C12-H13
455506
620
438143
649
4813
93579
459537
614
4832
85576
4616
62610
40
H10-C9-C20-H21
1695
395
1265
1698
194
1267
168824
1261
168658
1259
1685
1258
1682201
1256
120
H27-C26-C40-H41
-110
718
1065
-120311
1059
-101794
1070
-1089
1066
-104324
1069
-112
981064
65
H28-C26-C40-H41
1053029
296
103995
283
1063433
307
1053319
296
1061668
305
10496
4292
13H33-C32-C34-H35
-02873
11-012
311
-05893
11-0366
11-0566
11-033
3111
100
H47-C46-C48-H49
-613
614
382
-611286
385
-619
356
374
-618
438
375
-615
482
379
-614
875
380
42
H47-C46-C48-H50
5874
37417
587503
417
580428
427
578579
430
5853
4420
58304
4424
42
H49-C48-C51-H52
-425704
669
-421786
675
-439616
646
-433642
656
-445718
636
-439227
647
42
H50-C48-C51-H52
-164
093
1221
-163817
1218
-16522
1232
-164
673
1227
-165874
1237
-165259
1232
11H54-C53-C55-H56
-03838
11-02856
11-032
7511
-02429
11-039
2111
-03074
11H66-C64-C67-H68
-177906
1299
-177979
1299
17846
741299
1787874
131784147
1299
178548
1299
H66-C64-C67-H69
-569125
443
-569428
443
-603746
395
-599
903
4-6040
07395
-601923
397
70H66-C64-C67-H70
606324
391
604696
394
566811
447
56944
9442
566504
447
567234
446
70
8 Advances in Condensed Matter Physics
05
minus15
minus10
minus05
0
05
10
15
20
25
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Gas
minus15
minus10
minus05
0
05
10
15
20
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Mul
liken
char
ges
Mul
liken
char
ges
Chloroform
minus10
minus05
0
05
10
15
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
ESP
char
ges
ESP
char
ges
Chloroform
minus10
minus05
0
05
10
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Chloroform
minus10
minus05
0
10
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Nat
ural
atom
ic ch
arge
s
Nat
ural
atom
ic ch
arge
s
Gas
minus10
minus05
0
05
10
15
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Gas
Figure 2 Charge distribution on Rubescin E calculated at the RHF B3PW91 and B3LYP levels in both gas phase and chloroform solutionand with the 6-311++G(dp) basis set
Advances in Condensed Matter Physics 9
Table 3 Global reactivity descriptors of Rubescin E at the RHF B3LYP and B3PW91 levels in gas phase and in chloroform solution using the6-311++G(dp) basis set
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
Figure 3 Molecular orbital and the HOMO and LUMO energy of Rubescin E in gas phase
The calculated vertical IP values in gas phase are biggerthan their corresponding values in solvent From Table 3we also found that putting the molecule in solvent increasesits electron affinity From the calculated IP and EA valuesone can conclude that solvent effect increases the capacityof molecule of gaining an electron compared to donating itIt also reduces the harness of our molecule and increasesthe softness Hence the presence of solvent increases thereactivity of the molecule Rubescin
343 Frontier Molecular Orbitals The frontier molecularorbitals of Rubescin E were evaluated using the ab initio andDFT methods The 6-311G(dp) and 6-311++G(dp) basis setswere used for this purpose in gas phase and in chloroformsolutionThe results show that the energy gap of ourmoleculedecreases when diffuse functions are added onto all theatoms We also found that whenever the basis set andmethods used the energy gap is greater than 4 showing thatour molecule is hard and can be used as insulator in manyelectronic devices In Figure 3 the 3Dplots of theHOMOandLUMO orbitals computed at the RHF B3PW91 and B3LYPlevels with the 6-311G(dp) basis set are illustrated in gasphase We observed that the HOMO of Rubescin E is locatedover the furan ring at the three levels and also at the C-Cof cyclohexane ring and C-O of oxiran ring By contrast the
LUMO orbital is located over the cyclohex-2-enone ring C-C and C-O bond of tetrahydrofuran ring We can thereforeconclude that electron can easily be transferred from furanring to tetrahydrofuran ring
The total density of states (DOS) spectrum of RubescinE at the gas phase and in chloroform is given in Figure 4for each level at the 6-311++G(dp) basis set These DOSsspectra presented in Figure 4 were obtained from Gauss-Sum 30 program [18] which was used in order to show thecontributions of different group tomolecular orbital (HOMOand LUMO) From Figure 4 we observe that the HOMO-LUMO energy gap is smaller when we move from RHF toB3PW91 and from B3PW91 to B3LYP level respectively forboth gas and chloroform phases with larger values obtainedin chloroform
344 UV-Vis SpectraAnalysis Timedependent density func-tional theory (TD-DFT) was used in gas phase at the twolevels B3PW91 and B3LYP with the 6-311++G(dp) basis setin order to determine the first six excited states to investigatethe UV-vis absorption spectra of themoleculeThe excitationenergy (E) wavelength (120582) and oscillator strength (f) alongwith their major contributions are given in Table 4 and theirresults are compared to experiment
10 Advances in Condensed Matter Physics
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3LYP Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
Energy (eV)
B3LYP Gas
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Gas
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Chloroform
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Gas
4293 eV
9797 eV9516 eV
4315 eV 4333 eV
4314 eV
Figure 4 Total density of state (DOS) spectrum of Rubescin E at the RHF B3PW91 and B3LYP levels in both gas and chloroform phase andwith the 6-311++G(dp) basis set
Two intense electronic transitions were predicted at44934 eV (27592 nm) and 34415 eV (36027 nm) withoscillator strengths of 00043 and 00014 respectively at theB3PW91 level and 45123 eV (27477 nm) and 34603 eV(35831 nm) with oscillator strengths of 00041 and 00014respectively at the B3LYP levelWe observed from the spectra
that the maximum absorption wavelength corresponds tothe electronic transition from HOMO to LUMO+1 with100 contribution followed by the electronic transition fromHOMO to LUMO with 99 contribution at the two levelsThe experimental absorption spectra of the title moleculepredict two bands at 254 nm and 365 nm The error between
Advances in Condensed Matter Physics 11
Table 4Theoretical absorption wavelength (120582) excitation energy (E) and oscillator strengths of Rubescin E at the B3PW91 and B3LYP levelsin gas with the 6-311++G(dp) basis set
Excited states Exp [1] B3PW91 B3LYP120582 (nm) 120582 (nm) E (eV) f Major contributions 120582 (nm) E (eV) f Major contributions
1 365 36027 34415 00014 H-1 997888rarr L (93) 35831 34603 00014 H-1 997888rarr L (93)2 31218 39715 00000 H 997888rarr L (99) 31369 39524 00000 H 997888rarr L (99)3 254 27592 44934 00043 H-4 997888rarr L (24) 27477 45123 00041 H-4 997888rarr L (28)4 27266 45473 00006 H-4 997888rarr L (50) 27227 45538 00004 H-4 997888rarr L (44)5 26956 45994 00001 H-4 997888rarr L (19) 26847 46182 00001 H-4 997888rarr L (20)6 26121 47465 00000 H 997888rarr L+1 (100) 26316 47113 00000 H 997888rarr L+1 (100)
200 250 300 350 400 450 5000
50
100
150
200
250
300
350
wavelength (nm)
Epsi
lon
B3LYP
200 250 300 350 400 450 5000
50100150200250300350400
Wavelength (nm)
Epsi
lon
B3PW91
UV vis spectrumOscillator strength
UV vis spectrumOscillator strength
Figure 5 Theoretical absorption spectra of Rubescin E at the B3PW91 and B3LYP levels in gas with the 6-311++G(dp) basis set
the theoretical and experimental results range from - 473 nmto 2192 nm at the B3PW91 and from - 669 nm to 2077 nm atthe B3LYP levelThese errors are due to the fact that only onemolecule was considered for simulationThe theoretical UV-vis absorption spectra of Rubescin E in gas phase are shownin Figure 5
345 Dipole Moment (120583119863119872) Average Polarizability (120572) FirstStatic Hyperpolarizability (120573) and Anisotropy of PolarizationIn this work the dipole moment 120583119863119872 average polarizability120572 first static hyperpolarizability 120573 and anisotropy of polar-izability Δ120572 of Rubescin E were evaluated in both gas phaseand chloroform solution in order to define the nonlinearityof Rubescin E The finite-field approach was used for thispurpose Equations (2) (3) (4) and (5) were used to calculatethe polarizability dipole moment anisotropy of polarizabil-ity and first static hyperpolarizability respectively using thex 119910 119911 components obtained from Gaussian 09 W outputThe calculated parameters were presented in Table 5 at thethree levels with the 6-311++G(dp) basis set
The calculated values of polarizability and first static hyper-polarizability obtained from Gaussian output are in atomicunit These values were then converted into electrostatic unit(esu) for comparison purpose (for 120572 1 au = 01482 x 10minus24esu for 120573 1 au = 86393 x 10minus33 esu) [19ndash22] From a givingmolecule when these values (120583119863119872 and 120573) are greater thanthose of urea the molecule is said to have good active NLOproperties We observed from our results that the values of120572 120573 and 120583119863119872 are higher in solvent than their correspondingvalue in gas phase 120573 and 120583119863119872 of Rubescin E calculated at the6-311++G(dp) basis set using different methods were greaterthan those of urea These values calculated using the HF6-311D(dp)method (120583119863119872 = 52175Dand120573 = 17603169x10minus33esu) were also higher than those of urea (120583119863119872 = 38851D and120573 = 372811990910minus33esu) obtained using the same method and
12 Advances in Condensed Matter Physics
Table 5 Electric dipole moment polarizability anisotropy of polarization first-order hyperpolarizability and molar refractivity of RubescinE at the RHF B3LYP and B3PW91 levels with the 6-311G (d p) and 6-311++G (d p) basis sets
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
Table 6 Calculated values of polarization density (P) average electric field (E) electric susceptibility (120594) refractive index (120578) dielectricconstant (E) magnitude of the displacement (D) and molar refractivity (MR) of Rubescin E molecule obtained at the RHF B3LYP andB3PW91 levels with the 6-311++G(dp) basis set
Parameters RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
basis set [21] Hence Rubescin E can be considered to havegood active NLO properties and this is due to the delocalize electron on the furan ring
346 Optoelectronic Properties In order to recognize theoptoelectronic nature of Rubescin E for different devicesapplications some parameters such as electric field (E) elec-tric polarization (P) electric susceptibility (120594) permittivity(E) refractive index (120578) and electric displacement (D) werecalculated using equations given in the literature [23ndash25]We observed from Table 6 that the results of the calculatedparameters are slightly different when we move from onelevel to another and also when the medium changes Thevalue of electric field is greater in a solution of chloroformthan its corresponding value in gas phase This is because the
polarizability increases in presence of a solvent The valuesof electric susceptibility dielectric constant and refractiveindex are greater at B3LYP level compared to their corre-sponding value at the RHF All the calculated parametersof optoelectronic properties obtained at the B3LYP level aresimilar to those obtained at the B3PW91 level None of theseparameters have been determined before either theoreticallyor experimentally
One of the central goals of this study is to understandthe underlying structurendashproperty relationships whichmightform the basis for a ldquomolecular engineeringrdquo approachto electronics optoelectronics and photonics The molarrefractivity of our molecule known to be an importantparameter in quantitative structurendashproperty relationshipanalysis was calculated for this purpose The value of the
Advances in Condensed Matter Physics 13
Table 7 Experimental and calculated 1HNMR chemical shifts 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
molar refractivity was calculated at the three levels in bothgas and chloroform using the 6-311++G(dp) basis set TheLorenz-Lorentz equation was used for this calculation [2627] and its results are listed in Table 6
The high values of molar refractivity polarizabilityanisotropy of polarizability and first static hyperpolarizabil-ity of Rubescin E molecule show that the molecule has goodquantitative structurendashproperty relationship analysis andmight therefore form the basis for a ldquomolecular engineeringrdquoapproach to electronics optoelectronics and photonics
35 NMR Study of Rubescin E After the optimization ofthe Rubescin E molecule the 1H and 13C chemical shiftswere calculated at the RHF B3LYP and B3PW91 levels of thetheory using the 6-311++G(dp) basis set In order to comparethe calculated values of 1H and 13C chemical shifts withexperimental results we also need to calculate the absoluteshielding value of 1Hand 13C for the tetramethylsilane (TMS)using the same methods above The GIAO (Gauge InvariantAtomic Orbitals) approach known to provide satisfactorychemical shifts for different nuclei with larger molecules [28]was used for this purpose and the following equation
120575119894 (119901119901119898) = 119894119904119900119905119903119900119901119894119888 (119879119872119878119894) minus 119894119904119900119905119903119900119901119894119888 (119894) (6)
where 119894 is the atom type and was used to convert the chemicalshielding to chemical shifts
The experimental and calculated chemical shifts of 1Halong with their corresponding error are listed in Table 7From our results we observed that all the methods provideresults which are very close to experiment since the errorsbetween the experimental and calculated results are smaller
In order to compare experimental and theoretical resultsa linear correlation of 1H-NMR chemical shifts was estab-lished as shown in Figure 6 The regression line was plottedusing the following equations 120575119888119886119897 = 098880120575119890119909119901 minus 017198120575119888119886119897 = 097379120575119890119909119901 + 018796 and 120575119888119886119897 = 097069120575119890119909119901 +019387 respectively at the RHF B3PW91 and B3LYP levelsof the theory The theoretical results obtained from usingthe 6-311++G(dp) basis set show good correlation withexperiment since and the calculated R-square values arefound to be close to 1 at each level as shown by Figure 6
The calculated and experimental 13C chemical shifts ofour molecule are given in Table 8 and their comparison canbe found in Figure 7 The linear regression line plotted inFigure 7 shows that theoretical results are in good agreementwith experiment This is confirmed by the linear correlationcoefficient calculated here as R-square at the RHF B3PW91and B3LYP levels using the 6-311++G(dp) basis set
The following regression line plotted for each level usingthe general equation 120575119888119886119897 = 119886120575119890119909119901 + 119887 where a and b are givenin Figure 7 shows that the calculated 13C chemical shiftscorrelate very well with experiment The linear correlationcoefficient calculated as R-square found in Figure 7 alsoconfirms this
36 Vibrational Frequencies Analysis The vibrational fre-quencies of our molecule were computed by using B3LYP6-311G(dp) method in both gas phase and chloroform Theexperimental IR vibrational frequencies obtained for the twocarbonyl moiety present in our structure along with thecalculated scaled and unscaled vibrational frequencies IRand Raman frequencies with their approximate descriptions
14 Advances in Condensed Matter Physics
Table 8 Experimental and calculated 13C NMR chemical shift 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
y = +100x -0254 max dev150 r=0960 y = +0987x +0127 max dev104 r=0979
y = +0980x +0141 max dev103 r=0981
y = +100x -0254 max dev150 y = +0987x +0127 max dev104
y = +0980x +0141 max dev103
Figure 6 Comparison of experimental and theoretical 1H chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set in chloroform
Advances in Condensed Matter Physics 15
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3LYP6-311++G(dp)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3PW916-311++G(dp)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
minus250
255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
RHF6-311++G(dp)
y = +107x -517 max dev836 r=0994 y = +105x +238 max dev648 r=0998
y = +105x +354 max dev541 r=0998
y = +107x -517 max dev836 y = +105x +238 max dev648
y = +105x +354 max dev541
Figure 7 Comparison of experimental and theoretical 13C chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set
are given in Table 9 The rest of the vibrational parameterof Rubescin E molecule which is not described in Table 9can be obtained from Supplementary Material S2 The scalefactor was determined as the mean value of the scale factorthat matches correctly for the C=O stretching and the givenexperimental valueThe obtained scale factor was 09706 Noimaginary frequencies were found showing that structure ofthe molecule Rubescin E is stable in both gas and solventFigure 8 gives the representation of the scaled IR intensity andRaman scattering activity
The C=O double bond gives rise to a very intenseabsorption band in IR spectrum The position and intensityof this band range from 1870 cmminus1 to 1540 cmminus1 dependingon the physical state electronic andmass effects of neighbor-ing substituents intra- and intermolecular interactions andconjugations [29] The C=O double bond absorption spectra
were observed experimentally at 1720 cmminus1 and 1664 cmminus1[1] In this study the vibrational mode of C=O was found at172620 cmminus1 and 169057 cmminus1 gas phase and at 170101 cmminus1and 166759 cmminus1 in chloroform There is good agreementbetween the vibrational modes with experimental values
4 Conclusion
In this study the geometry optimization of Rubescin E hasbeen carried out using ab initio HF and density functionaltheoryDFT (B3LYP and B3PW91)methods in both gas phaseand chloroform solution with the 6-311++G(dp) basis setThe optimized parameters were compared to those of someexisting groups of compound present in our molecule sincenone of this have been done before for the title molecule andgood agreement was found In order to confirm the geometry
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
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2 Advances in Condensed Matter Physics
gap charge distributions NLO properties vibrational fre-quencies NMR and UV-vis calculation) and some physico-chemical properties (3JH-H chemical coupling-coupling con-stant the global reactivity descriptors and some geometricalparameters such as bonds lengths and bonds angles) ofRubescin E molecule To the best of our knowledge notheoretical studywas performed yet on the titlemolecule thatis what motivated us to investigate the electronic structurethe spectroscopic and some physicochemical propertiesof Rubescin E molecule Except for NMR UV-vis 3JH-Hchemical coupling-coupling constant and the vibrationalfrequencies obtained for the two 120572 120573-unsaturated carbonylmoiety most of our results were not compared and weare optimistic that it can be used as threshold for futureexperimental or theoretical research Hartree Fock andDFT (using B3LYP and B3PW91 functionals) methods wereused for these purposes These properties were calculatedby employing the triple split valence basis set along withpolarization functions with and without diffuse functions asimplemented in Gaussian 09 Rev A02 in both gas phase andin a solution of chloroformThe methods and basis sets usedare among the most widely used [2ndash5] and provide excellentresults which are generally very close to experiments [6ndash8]
2 Computational Methods
Theoretical calculations were performed on Rubescin Eusing HF and DFT methods at the B3LYP and B3PW91levels as implemented in Gaussian 09W code [9] All thesecalculations were done in gas phase and in a solution ofchloroform No geometry restriction was applied duringthe optimization procedure The solvent effects were treatedwithin the conductor-like polarizable continuum model(CPCM) For the geometry optimization the 6-311G(dp) and6-311++G(dp) basis set were used in both gas and solventConvergence criteria in which both the maximum force anddisplacement are smaller than the cut-off of 0000015 and0000060 and RMS force and displacement less than thecut-off values of 0000010 and 0000040 were used in thecalculations in order to increase the accuracy of our resultsThe chemical 3JH-H proton-proton coupling constant func-tion of angle between two C-H vectors was calculated fromthe optimization output using the original Karplus equation[10] The optimized form of our molecule was then used todetermine the global reactivity descriptors electronic andNLOs properties The net charges were also evaluated usingMPA ESP and NBOs methods at the three levels mentionedabove and all this was done in both gas phase and chloroformwith the 6-311++G(dp) basis set In order to confirm thestability of our molecule the vibrational frequencies (IR andRaman) were evaluated at the 6-311G(dp) and no imaginaryfrequencies were found leading us to the results that ourmolecule was stable at the levels and basis set consideredThetime dependent density functional theory (TD-DFT) fieldwas used in gas phase with the 6-311++G(dp) basis in orderto understand the electronic transition of our molecule andthe obtained results were compared to experimentTheGIAO(gauge independent atomic orbital) method was used on theoptimized form of our molecule in a solution of chloroform
to determine the 1H and 13C NMR spectra parameters at thethree levels and with the 6-311++G(dp) basis set In orderto compare the calculated values of 1H and 13C chemicalshift with experimental results the reference and widelyusedmolecule TMS (tetramethylsilane) for this purpose wereexploited at the same level at the same phase and with thesame basis set
3 Results and Discussion
31 Optimized Structure The optimized geometry ofRubescin E obtained using the B3LYP6-311++G(dp)method in chloroform is shown in Figure 1 The value ofthe total electronic energy of the molecule obtained at theB3LYP shows that Figure 1 is the most stable structure of themolecule The total electronic energy calculated within thetwo methods in gas and in a solution of chloroform with the6-311++G(dp) is given in Table 1
32 Structural Properties A part of the optimized geometri-cal parameters (bond length bond angle) and total electronicenergy of the title molecule both in gas and in a solution ofchloroform are given in Table 1 using the three levels andwith the 6-311++G(dp) basis set The total description of themolecular geometry of Rubescin Emolecule in gas phase andin a solution of chloroform using ab initio (RHF) and DFT(B3LYP and B3PW91) methods with the 6-311++G(dp) basisset can be obtained from Supplementary Material S1
The atom numbering scheme adopted for this purposeis the same as in Figure 1 The energy differences betweenthe two used phases increase when we move from B3PW91to B3LYP and to RHF and are found to be approximatively048 eV 049 eV and 057 eV respectively The optimizedbond length and bond angle of Rubescin E are also listedin Table 1 with some specific experimental values [12ndash14]found in the literature for some groups of compounds suchas furan ethylene oxide and tetrahydrofuran present in ourmolecule It can be observed fromTable 1 that the values of thebond length obtained at B3LYP are slightly higher than thoseobtained at the B3PW91 level These differences are foundbetween 00034 A and 00107 A for C-C 00061 A and 00095A for C-O and 00007 A and 00013 A for C=C in gas phaseThe value of C=O bond length is better at the DFT methodssince its values are closer to 210 A found in literature [11] Itcan also been observed that the calculated bonds length usingHartree Fock and DFT methods are very close to the valuesfound in literature for the specific groups of compoundspresent in our molecule These observed differences variedfrom 00012 A at the B3LYP level to 00363 A at the RHF levelfrom 00002 A at the B3PW91 level to 00288 A at the B3LYPlevel and from 00019 A at the B3LYP level to 00259 A at theRHF level for C-C C-O and C=C bonds both in gas phaseand in chloroform solution respectively
The bonds angles of the studied molecule are slightlydifferent when we move from one phase to another at eachlevel with larger values obtained at the RHF level From ourresults it can be seen that the C-C-C bond angle varies from963773∘ to 1293418∘ from 966032∘ to 1288385∘ and from964146∘ to 1287371∘ at the gas phase respectively at the RHF
Advances in Condensed Matter Physics 3
Table 1 Optimized geometric parameters in gas phase and in chloroform solution of Rubescin E at the RHF B3LYP and B3PW91 level withthe 6-311++G (dp) basis sets
Levels RHF B3LYP B3PW91Theory a[11] b[12] c[13]Basis set Gaz CDCl3 Gaz CDCl3 Gaz CDCl3
B3LYP and B3PW91 level of the theory In CDCl3 the C-C-C bond angles are similar to those obtained at the gasphase The smallest value of C-C-C bond angle was C20-C8-C29 bond angle and the largest C51-C14-C57 bond angle Forthe C-C-O angle the smallest value was 1044386∘ obtainedat the RHF and the largest value was 123472∘ obtained at theB3LYP level both in the gas phaseTheC-O-C bond angle wasfound between 1071084∘ and 1234264∘ obtained at the RHFlevel These bonds angles compared to some known valuesfound in literature [12 14] for specific compound present inour structure show good similaritiesThe little differences arefound between 00268∘ and 15507∘ for C-C-C bond between00595∘ and 30614∘ for C-C-O bond and between 00202∘and 0781∘ for C-O-C bond These observed differences aredue to the fact that these groups of compounds were notisolated
33 Calculated 3119869119867-119867 Coupling Constant The chemical 3JH-Hproton-proton coupling constant was calculated using theoriginal Karplus [10] equation in gas and solvent and itsresults compared to experimental values [1] obtained byextracting Rubescin E in a solution of chloroform From ourresults we found that the calculated parameters both in gasand in chloroform are all similar at all the levels used Theseobtained results are also very close to experiment As pre-dicted in literature [10] we observed from Table 2 that whenthe angles between the two C-H vectors are close enough to00 or 1800 the value of 3JH-H coupling constant is greater (with31198691800 gt 311986900) and is very small when the angle is close to 900
34 Electronic Properties341 Mulliken ESP and Natural Charge Distribution TheMulliken atomic charges of our molecule calculated at all
6 Advances in Condensed Matter Physics
Figure 1 Ground state geometry of Rubescin E at B3LYP6-311++G(dp) in chloroform solution
the levels in gas phase and chloroform show positive chargefor all the hydrogen atoms The net charge on all theatoms varies from -1109653e to 1980512e from -1164916eto 1904034e and from -0891775e to 1524787e respectivelyin gas phase at the RHF B3PW91 and B3LYP levels In asolution of chloroform the charges varied from -1064962e to1826589e from -1206706e to 1904292e and from -0945041eto 1550492e with some oxygen atoms charges being positiveand can be explained by the fact that the oxygen is related toextremely negative carbon atoms The most positive chargeatoms are C63 C5 C8 and the most negative charge atoms areC71 C62 C67
The electrostatic charges were evaluated in this workusing the CHelpG scheme of Breneman model We foundfrom our results that the most positive charges atom is C4followed by C62 and C2 and the most negative charge atom isC12 followed by C5 and C7 The observation made at all levelsand basis set in gas phase and in a solution of chloroform isthat the most positive charge atoms are directly related to themost negative charge atoms
The natural atomic charges obtained using the naturalbonding orbitalmethodwere also used to evaluate the atomiccharge of Rubescin E Positive and negative charges werefound for all hydrogen and oxygen atoms respectively Inthis case all carbon atoms directly linked to hydrogen atomswere found to have negative charges except for those linked tooxygen atomsThemost negative charge atom was calculatedusing HF method and was observed for O65 (-069456e) andO60 (-068330e) respectively in chloroform and gas phaseThemost positive charge atomwas found to beC62 in both gas(097067e 080601e and 081407e respectively at the RHF
B3PW91 and B3LYP levels) and solvent (098887e 081804eand 082650e respectively at the RHF B3PW91 and B3LYPlevels) this is due to the fact that C62 is related to negativecharge atoms (O65 O60 and C63) Mulliken electrostatic andnatural atomic charge distributions are graphically shown inFigure 2 From Figure 2 one can observe that for almost allthe methods used for charge description the most positiveand negative charge atoms were calculated at the RHF levelin both gas and chloroform and this is due to the fact thatthe effect of electron correlation is not well described in HFmethod
342 Global Reactivity Descriptors In order to understandthe relationships between structure stability and reactivity ofRubescin Emolecule the global reactivity descriptors param-eters such as chemical hardness (H) chemical potential (120583119888119901)chemical softness (s) electronegativity (119883) and electrophilic-ity index (120596) were calculated The finite difference equationgiven by (1) was used to calculate the ionization potentialand electron affinity which are generally used to calculate theabove cited parameters
119868119875 = 119864119902=119873+1 minus 119864119902=119873119864119860 = 119864119902=119873 minus 119864119902=119873minus1
(1)
The IP and EA calculated from (1) were then used to calculate119867 120583119888119901 s119883 and120596 using equations found in the literature [15ndash17] All these parameters calculated using the twomethods ingas phase are presented in Table 3 A high value of 120583119888119901 and 120596characterizes a good electrophile while a small value standsfor good nucleophile
Advances in Condensed Matter Physics 7
Table2Ex
perim
entaland
calculated3J H
-Hproton
-protoncoup
lingconstant
ofRu
bescin
Ein
gasp
hase
andin
chloroform
solutio
n
PARA
MET
ERS
RHF
B3LY
PB3
PW91
EXP[1]
Gaz
CDCl3
Gaz
CDCl3
Gaz
CDCl3
Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)H10-C9-C12-H13
455506
620
438143
649
4813
93579
459537
614
4832
85576
4616
62610
40
H10-C9-C20-H21
1695
395
1265
1698
194
1267
168824
1261
168658
1259
1685
1258
1682201
1256
120
H27-C26-C40-H41
-110
718
1065
-120311
1059
-101794
1070
-1089
1066
-104324
1069
-112
981064
65
H28-C26-C40-H41
1053029
296
103995
283
1063433
307
1053319
296
1061668
305
10496
4292
13H33-C32-C34-H35
-02873
11-012
311
-05893
11-0366
11-0566
11-033
3111
100
H47-C46-C48-H49
-613
614
382
-611286
385
-619
356
374
-618
438
375
-615
482
379
-614
875
380
42
H47-C46-C48-H50
5874
37417
587503
417
580428
427
578579
430
5853
4420
58304
4424
42
H49-C48-C51-H52
-425704
669
-421786
675
-439616
646
-433642
656
-445718
636
-439227
647
42
H50-C48-C51-H52
-164
093
1221
-163817
1218
-16522
1232
-164
673
1227
-165874
1237
-165259
1232
11H54-C53-C55-H56
-03838
11-02856
11-032
7511
-02429
11-039
2111
-03074
11H66-C64-C67-H68
-177906
1299
-177979
1299
17846
741299
1787874
131784147
1299
178548
1299
H66-C64-C67-H69
-569125
443
-569428
443
-603746
395
-599
903
4-6040
07395
-601923
397
70H66-C64-C67-H70
606324
391
604696
394
566811
447
56944
9442
566504
447
567234
446
70
8 Advances in Condensed Matter Physics
05
minus15
minus10
minus05
0
05
10
15
20
25
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Gas
minus15
minus10
minus05
0
05
10
15
20
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Mul
liken
char
ges
Mul
liken
char
ges
Chloroform
minus10
minus05
0
05
10
15
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
ESP
char
ges
ESP
char
ges
Chloroform
minus10
minus05
0
05
10
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Chloroform
minus10
minus05
0
10
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Nat
ural
atom
ic ch
arge
s
Nat
ural
atom
ic ch
arge
s
Gas
minus10
minus05
0
05
10
15
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Gas
Figure 2 Charge distribution on Rubescin E calculated at the RHF B3PW91 and B3LYP levels in both gas phase and chloroform solutionand with the 6-311++G(dp) basis set
Advances in Condensed Matter Physics 9
Table 3 Global reactivity descriptors of Rubescin E at the RHF B3LYP and B3PW91 levels in gas phase and in chloroform solution using the6-311++G(dp) basis set
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
Figure 3 Molecular orbital and the HOMO and LUMO energy of Rubescin E in gas phase
The calculated vertical IP values in gas phase are biggerthan their corresponding values in solvent From Table 3we also found that putting the molecule in solvent increasesits electron affinity From the calculated IP and EA valuesone can conclude that solvent effect increases the capacityof molecule of gaining an electron compared to donating itIt also reduces the harness of our molecule and increasesthe softness Hence the presence of solvent increases thereactivity of the molecule Rubescin
343 Frontier Molecular Orbitals The frontier molecularorbitals of Rubescin E were evaluated using the ab initio andDFT methods The 6-311G(dp) and 6-311++G(dp) basis setswere used for this purpose in gas phase and in chloroformsolutionThe results show that the energy gap of ourmoleculedecreases when diffuse functions are added onto all theatoms We also found that whenever the basis set andmethods used the energy gap is greater than 4 showing thatour molecule is hard and can be used as insulator in manyelectronic devices In Figure 3 the 3Dplots of theHOMOandLUMO orbitals computed at the RHF B3PW91 and B3LYPlevels with the 6-311G(dp) basis set are illustrated in gasphase We observed that the HOMO of Rubescin E is locatedover the furan ring at the three levels and also at the C-Cof cyclohexane ring and C-O of oxiran ring By contrast the
LUMO orbital is located over the cyclohex-2-enone ring C-C and C-O bond of tetrahydrofuran ring We can thereforeconclude that electron can easily be transferred from furanring to tetrahydrofuran ring
The total density of states (DOS) spectrum of RubescinE at the gas phase and in chloroform is given in Figure 4for each level at the 6-311++G(dp) basis set These DOSsspectra presented in Figure 4 were obtained from Gauss-Sum 30 program [18] which was used in order to show thecontributions of different group tomolecular orbital (HOMOand LUMO) From Figure 4 we observe that the HOMO-LUMO energy gap is smaller when we move from RHF toB3PW91 and from B3PW91 to B3LYP level respectively forboth gas and chloroform phases with larger values obtainedin chloroform
344 UV-Vis SpectraAnalysis Timedependent density func-tional theory (TD-DFT) was used in gas phase at the twolevels B3PW91 and B3LYP with the 6-311++G(dp) basis setin order to determine the first six excited states to investigatethe UV-vis absorption spectra of themoleculeThe excitationenergy (E) wavelength (120582) and oscillator strength (f) alongwith their major contributions are given in Table 4 and theirresults are compared to experiment
10 Advances in Condensed Matter Physics
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3LYP Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
Energy (eV)
B3LYP Gas
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Gas
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Chloroform
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Gas
4293 eV
9797 eV9516 eV
4315 eV 4333 eV
4314 eV
Figure 4 Total density of state (DOS) spectrum of Rubescin E at the RHF B3PW91 and B3LYP levels in both gas and chloroform phase andwith the 6-311++G(dp) basis set
Two intense electronic transitions were predicted at44934 eV (27592 nm) and 34415 eV (36027 nm) withoscillator strengths of 00043 and 00014 respectively at theB3PW91 level and 45123 eV (27477 nm) and 34603 eV(35831 nm) with oscillator strengths of 00041 and 00014respectively at the B3LYP levelWe observed from the spectra
that the maximum absorption wavelength corresponds tothe electronic transition from HOMO to LUMO+1 with100 contribution followed by the electronic transition fromHOMO to LUMO with 99 contribution at the two levelsThe experimental absorption spectra of the title moleculepredict two bands at 254 nm and 365 nm The error between
Advances in Condensed Matter Physics 11
Table 4Theoretical absorption wavelength (120582) excitation energy (E) and oscillator strengths of Rubescin E at the B3PW91 and B3LYP levelsin gas with the 6-311++G(dp) basis set
Excited states Exp [1] B3PW91 B3LYP120582 (nm) 120582 (nm) E (eV) f Major contributions 120582 (nm) E (eV) f Major contributions
1 365 36027 34415 00014 H-1 997888rarr L (93) 35831 34603 00014 H-1 997888rarr L (93)2 31218 39715 00000 H 997888rarr L (99) 31369 39524 00000 H 997888rarr L (99)3 254 27592 44934 00043 H-4 997888rarr L (24) 27477 45123 00041 H-4 997888rarr L (28)4 27266 45473 00006 H-4 997888rarr L (50) 27227 45538 00004 H-4 997888rarr L (44)5 26956 45994 00001 H-4 997888rarr L (19) 26847 46182 00001 H-4 997888rarr L (20)6 26121 47465 00000 H 997888rarr L+1 (100) 26316 47113 00000 H 997888rarr L+1 (100)
200 250 300 350 400 450 5000
50
100
150
200
250
300
350
wavelength (nm)
Epsi
lon
B3LYP
200 250 300 350 400 450 5000
50100150200250300350400
Wavelength (nm)
Epsi
lon
B3PW91
UV vis spectrumOscillator strength
UV vis spectrumOscillator strength
Figure 5 Theoretical absorption spectra of Rubescin E at the B3PW91 and B3LYP levels in gas with the 6-311++G(dp) basis set
the theoretical and experimental results range from - 473 nmto 2192 nm at the B3PW91 and from - 669 nm to 2077 nm atthe B3LYP levelThese errors are due to the fact that only onemolecule was considered for simulationThe theoretical UV-vis absorption spectra of Rubescin E in gas phase are shownin Figure 5
345 Dipole Moment (120583119863119872) Average Polarizability (120572) FirstStatic Hyperpolarizability (120573) and Anisotropy of PolarizationIn this work the dipole moment 120583119863119872 average polarizability120572 first static hyperpolarizability 120573 and anisotropy of polar-izability Δ120572 of Rubescin E were evaluated in both gas phaseand chloroform solution in order to define the nonlinearityof Rubescin E The finite-field approach was used for thispurpose Equations (2) (3) (4) and (5) were used to calculatethe polarizability dipole moment anisotropy of polarizabil-ity and first static hyperpolarizability respectively using thex 119910 119911 components obtained from Gaussian 09 W outputThe calculated parameters were presented in Table 5 at thethree levels with the 6-311++G(dp) basis set
The calculated values of polarizability and first static hyper-polarizability obtained from Gaussian output are in atomicunit These values were then converted into electrostatic unit(esu) for comparison purpose (for 120572 1 au = 01482 x 10minus24esu for 120573 1 au = 86393 x 10minus33 esu) [19ndash22] From a givingmolecule when these values (120583119863119872 and 120573) are greater thanthose of urea the molecule is said to have good active NLOproperties We observed from our results that the values of120572 120573 and 120583119863119872 are higher in solvent than their correspondingvalue in gas phase 120573 and 120583119863119872 of Rubescin E calculated at the6-311++G(dp) basis set using different methods were greaterthan those of urea These values calculated using the HF6-311D(dp)method (120583119863119872 = 52175Dand120573 = 17603169x10minus33esu) were also higher than those of urea (120583119863119872 = 38851D and120573 = 372811990910minus33esu) obtained using the same method and
12 Advances in Condensed Matter Physics
Table 5 Electric dipole moment polarizability anisotropy of polarization first-order hyperpolarizability and molar refractivity of RubescinE at the RHF B3LYP and B3PW91 levels with the 6-311G (d p) and 6-311++G (d p) basis sets
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
Table 6 Calculated values of polarization density (P) average electric field (E) electric susceptibility (120594) refractive index (120578) dielectricconstant (E) magnitude of the displacement (D) and molar refractivity (MR) of Rubescin E molecule obtained at the RHF B3LYP andB3PW91 levels with the 6-311++G(dp) basis set
Parameters RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
basis set [21] Hence Rubescin E can be considered to havegood active NLO properties and this is due to the delocalize electron on the furan ring
346 Optoelectronic Properties In order to recognize theoptoelectronic nature of Rubescin E for different devicesapplications some parameters such as electric field (E) elec-tric polarization (P) electric susceptibility (120594) permittivity(E) refractive index (120578) and electric displacement (D) werecalculated using equations given in the literature [23ndash25]We observed from Table 6 that the results of the calculatedparameters are slightly different when we move from onelevel to another and also when the medium changes Thevalue of electric field is greater in a solution of chloroformthan its corresponding value in gas phase This is because the
polarizability increases in presence of a solvent The valuesof electric susceptibility dielectric constant and refractiveindex are greater at B3LYP level compared to their corre-sponding value at the RHF All the calculated parametersof optoelectronic properties obtained at the B3LYP level aresimilar to those obtained at the B3PW91 level None of theseparameters have been determined before either theoreticallyor experimentally
One of the central goals of this study is to understandthe underlying structurendashproperty relationships whichmightform the basis for a ldquomolecular engineeringrdquo approachto electronics optoelectronics and photonics The molarrefractivity of our molecule known to be an importantparameter in quantitative structurendashproperty relationshipanalysis was calculated for this purpose The value of the
Advances in Condensed Matter Physics 13
Table 7 Experimental and calculated 1HNMR chemical shifts 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
molar refractivity was calculated at the three levels in bothgas and chloroform using the 6-311++G(dp) basis set TheLorenz-Lorentz equation was used for this calculation [2627] and its results are listed in Table 6
The high values of molar refractivity polarizabilityanisotropy of polarizability and first static hyperpolarizabil-ity of Rubescin E molecule show that the molecule has goodquantitative structurendashproperty relationship analysis andmight therefore form the basis for a ldquomolecular engineeringrdquoapproach to electronics optoelectronics and photonics
35 NMR Study of Rubescin E After the optimization ofthe Rubescin E molecule the 1H and 13C chemical shiftswere calculated at the RHF B3LYP and B3PW91 levels of thetheory using the 6-311++G(dp) basis set In order to comparethe calculated values of 1H and 13C chemical shifts withexperimental results we also need to calculate the absoluteshielding value of 1Hand 13C for the tetramethylsilane (TMS)using the same methods above The GIAO (Gauge InvariantAtomic Orbitals) approach known to provide satisfactorychemical shifts for different nuclei with larger molecules [28]was used for this purpose and the following equation
120575119894 (119901119901119898) = 119894119904119900119905119903119900119901119894119888 (119879119872119878119894) minus 119894119904119900119905119903119900119901119894119888 (119894) (6)
where 119894 is the atom type and was used to convert the chemicalshielding to chemical shifts
The experimental and calculated chemical shifts of 1Halong with their corresponding error are listed in Table 7From our results we observed that all the methods provideresults which are very close to experiment since the errorsbetween the experimental and calculated results are smaller
In order to compare experimental and theoretical resultsa linear correlation of 1H-NMR chemical shifts was estab-lished as shown in Figure 6 The regression line was plottedusing the following equations 120575119888119886119897 = 098880120575119890119909119901 minus 017198120575119888119886119897 = 097379120575119890119909119901 + 018796 and 120575119888119886119897 = 097069120575119890119909119901 +019387 respectively at the RHF B3PW91 and B3LYP levelsof the theory The theoretical results obtained from usingthe 6-311++G(dp) basis set show good correlation withexperiment since and the calculated R-square values arefound to be close to 1 at each level as shown by Figure 6
The calculated and experimental 13C chemical shifts ofour molecule are given in Table 8 and their comparison canbe found in Figure 7 The linear regression line plotted inFigure 7 shows that theoretical results are in good agreementwith experiment This is confirmed by the linear correlationcoefficient calculated here as R-square at the RHF B3PW91and B3LYP levels using the 6-311++G(dp) basis set
The following regression line plotted for each level usingthe general equation 120575119888119886119897 = 119886120575119890119909119901 + 119887 where a and b are givenin Figure 7 shows that the calculated 13C chemical shiftscorrelate very well with experiment The linear correlationcoefficient calculated as R-square found in Figure 7 alsoconfirms this
36 Vibrational Frequencies Analysis The vibrational fre-quencies of our molecule were computed by using B3LYP6-311G(dp) method in both gas phase and chloroform Theexperimental IR vibrational frequencies obtained for the twocarbonyl moiety present in our structure along with thecalculated scaled and unscaled vibrational frequencies IRand Raman frequencies with their approximate descriptions
14 Advances in Condensed Matter Physics
Table 8 Experimental and calculated 13C NMR chemical shift 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
y = +100x -0254 max dev150 r=0960 y = +0987x +0127 max dev104 r=0979
y = +0980x +0141 max dev103 r=0981
y = +100x -0254 max dev150 y = +0987x +0127 max dev104
y = +0980x +0141 max dev103
Figure 6 Comparison of experimental and theoretical 1H chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set in chloroform
Advances in Condensed Matter Physics 15
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3LYP6-311++G(dp)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3PW916-311++G(dp)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
minus250
255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
RHF6-311++G(dp)
y = +107x -517 max dev836 r=0994 y = +105x +238 max dev648 r=0998
y = +105x +354 max dev541 r=0998
y = +107x -517 max dev836 y = +105x +238 max dev648
y = +105x +354 max dev541
Figure 7 Comparison of experimental and theoretical 13C chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set
are given in Table 9 The rest of the vibrational parameterof Rubescin E molecule which is not described in Table 9can be obtained from Supplementary Material S2 The scalefactor was determined as the mean value of the scale factorthat matches correctly for the C=O stretching and the givenexperimental valueThe obtained scale factor was 09706 Noimaginary frequencies were found showing that structure ofthe molecule Rubescin E is stable in both gas and solventFigure 8 gives the representation of the scaled IR intensity andRaman scattering activity
The C=O double bond gives rise to a very intenseabsorption band in IR spectrum The position and intensityof this band range from 1870 cmminus1 to 1540 cmminus1 dependingon the physical state electronic andmass effects of neighbor-ing substituents intra- and intermolecular interactions andconjugations [29] The C=O double bond absorption spectra
were observed experimentally at 1720 cmminus1 and 1664 cmminus1[1] In this study the vibrational mode of C=O was found at172620 cmminus1 and 169057 cmminus1 gas phase and at 170101 cmminus1and 166759 cmminus1 in chloroform There is good agreementbetween the vibrational modes with experimental values
4 Conclusion
In this study the geometry optimization of Rubescin E hasbeen carried out using ab initio HF and density functionaltheoryDFT (B3LYP and B3PW91)methods in both gas phaseand chloroform solution with the 6-311++G(dp) basis setThe optimized parameters were compared to those of someexisting groups of compound present in our molecule sincenone of this have been done before for the title molecule andgood agreement was found In order to confirm the geometry
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
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Advances in Condensed Matter Physics 3
Table 1 Optimized geometric parameters in gas phase and in chloroform solution of Rubescin E at the RHF B3LYP and B3PW91 level withthe 6-311++G (dp) basis sets
Levels RHF B3LYP B3PW91Theory a[11] b[12] c[13]Basis set Gaz CDCl3 Gaz CDCl3 Gaz CDCl3
B3LYP and B3PW91 level of the theory In CDCl3 the C-C-C bond angles are similar to those obtained at the gasphase The smallest value of C-C-C bond angle was C20-C8-C29 bond angle and the largest C51-C14-C57 bond angle Forthe C-C-O angle the smallest value was 1044386∘ obtainedat the RHF and the largest value was 123472∘ obtained at theB3LYP level both in the gas phaseTheC-O-C bond angle wasfound between 1071084∘ and 1234264∘ obtained at the RHFlevel These bonds angles compared to some known valuesfound in literature [12 14] for specific compound present inour structure show good similaritiesThe little differences arefound between 00268∘ and 15507∘ for C-C-C bond between00595∘ and 30614∘ for C-C-O bond and between 00202∘and 0781∘ for C-O-C bond These observed differences aredue to the fact that these groups of compounds were notisolated
33 Calculated 3119869119867-119867 Coupling Constant The chemical 3JH-Hproton-proton coupling constant was calculated using theoriginal Karplus [10] equation in gas and solvent and itsresults compared to experimental values [1] obtained byextracting Rubescin E in a solution of chloroform From ourresults we found that the calculated parameters both in gasand in chloroform are all similar at all the levels used Theseobtained results are also very close to experiment As pre-dicted in literature [10] we observed from Table 2 that whenthe angles between the two C-H vectors are close enough to00 or 1800 the value of 3JH-H coupling constant is greater (with31198691800 gt 311986900) and is very small when the angle is close to 900
34 Electronic Properties341 Mulliken ESP and Natural Charge Distribution TheMulliken atomic charges of our molecule calculated at all
6 Advances in Condensed Matter Physics
Figure 1 Ground state geometry of Rubescin E at B3LYP6-311++G(dp) in chloroform solution
the levels in gas phase and chloroform show positive chargefor all the hydrogen atoms The net charge on all theatoms varies from -1109653e to 1980512e from -1164916eto 1904034e and from -0891775e to 1524787e respectivelyin gas phase at the RHF B3PW91 and B3LYP levels In asolution of chloroform the charges varied from -1064962e to1826589e from -1206706e to 1904292e and from -0945041eto 1550492e with some oxygen atoms charges being positiveand can be explained by the fact that the oxygen is related toextremely negative carbon atoms The most positive chargeatoms are C63 C5 C8 and the most negative charge atoms areC71 C62 C67
The electrostatic charges were evaluated in this workusing the CHelpG scheme of Breneman model We foundfrom our results that the most positive charges atom is C4followed by C62 and C2 and the most negative charge atom isC12 followed by C5 and C7 The observation made at all levelsand basis set in gas phase and in a solution of chloroform isthat the most positive charge atoms are directly related to themost negative charge atoms
The natural atomic charges obtained using the naturalbonding orbitalmethodwere also used to evaluate the atomiccharge of Rubescin E Positive and negative charges werefound for all hydrogen and oxygen atoms respectively Inthis case all carbon atoms directly linked to hydrogen atomswere found to have negative charges except for those linked tooxygen atomsThemost negative charge atom was calculatedusing HF method and was observed for O65 (-069456e) andO60 (-068330e) respectively in chloroform and gas phaseThemost positive charge atomwas found to beC62 in both gas(097067e 080601e and 081407e respectively at the RHF
B3PW91 and B3LYP levels) and solvent (098887e 081804eand 082650e respectively at the RHF B3PW91 and B3LYPlevels) this is due to the fact that C62 is related to negativecharge atoms (O65 O60 and C63) Mulliken electrostatic andnatural atomic charge distributions are graphically shown inFigure 2 From Figure 2 one can observe that for almost allthe methods used for charge description the most positiveand negative charge atoms were calculated at the RHF levelin both gas and chloroform and this is due to the fact thatthe effect of electron correlation is not well described in HFmethod
342 Global Reactivity Descriptors In order to understandthe relationships between structure stability and reactivity ofRubescin Emolecule the global reactivity descriptors param-eters such as chemical hardness (H) chemical potential (120583119888119901)chemical softness (s) electronegativity (119883) and electrophilic-ity index (120596) were calculated The finite difference equationgiven by (1) was used to calculate the ionization potentialand electron affinity which are generally used to calculate theabove cited parameters
119868119875 = 119864119902=119873+1 minus 119864119902=119873119864119860 = 119864119902=119873 minus 119864119902=119873minus1
(1)
The IP and EA calculated from (1) were then used to calculate119867 120583119888119901 s119883 and120596 using equations found in the literature [15ndash17] All these parameters calculated using the twomethods ingas phase are presented in Table 3 A high value of 120583119888119901 and 120596characterizes a good electrophile while a small value standsfor good nucleophile
Advances in Condensed Matter Physics 7
Table2Ex
perim
entaland
calculated3J H
-Hproton
-protoncoup
lingconstant
ofRu
bescin
Ein
gasp
hase
andin
chloroform
solutio
n
PARA
MET
ERS
RHF
B3LY
PB3
PW91
EXP[1]
Gaz
CDCl3
Gaz
CDCl3
Gaz
CDCl3
Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)H10-C9-C12-H13
455506
620
438143
649
4813
93579
459537
614
4832
85576
4616
62610
40
H10-C9-C20-H21
1695
395
1265
1698
194
1267
168824
1261
168658
1259
1685
1258
1682201
1256
120
H27-C26-C40-H41
-110
718
1065
-120311
1059
-101794
1070
-1089
1066
-104324
1069
-112
981064
65
H28-C26-C40-H41
1053029
296
103995
283
1063433
307
1053319
296
1061668
305
10496
4292
13H33-C32-C34-H35
-02873
11-012
311
-05893
11-0366
11-0566
11-033
3111
100
H47-C46-C48-H49
-613
614
382
-611286
385
-619
356
374
-618
438
375
-615
482
379
-614
875
380
42
H47-C46-C48-H50
5874
37417
587503
417
580428
427
578579
430
5853
4420
58304
4424
42
H49-C48-C51-H52
-425704
669
-421786
675
-439616
646
-433642
656
-445718
636
-439227
647
42
H50-C48-C51-H52
-164
093
1221
-163817
1218
-16522
1232
-164
673
1227
-165874
1237
-165259
1232
11H54-C53-C55-H56
-03838
11-02856
11-032
7511
-02429
11-039
2111
-03074
11H66-C64-C67-H68
-177906
1299
-177979
1299
17846
741299
1787874
131784147
1299
178548
1299
H66-C64-C67-H69
-569125
443
-569428
443
-603746
395
-599
903
4-6040
07395
-601923
397
70H66-C64-C67-H70
606324
391
604696
394
566811
447
56944
9442
566504
447
567234
446
70
8 Advances in Condensed Matter Physics
05
minus15
minus10
minus05
0
05
10
15
20
25
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Gas
minus15
minus10
minus05
0
05
10
15
20
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Mul
liken
char
ges
Mul
liken
char
ges
Chloroform
minus10
minus05
0
05
10
15
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
ESP
char
ges
ESP
char
ges
Chloroform
minus10
minus05
0
05
10
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Chloroform
minus10
minus05
0
10
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Nat
ural
atom
ic ch
arge
s
Nat
ural
atom
ic ch
arge
s
Gas
minus10
minus05
0
05
10
15
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Gas
Figure 2 Charge distribution on Rubescin E calculated at the RHF B3PW91 and B3LYP levels in both gas phase and chloroform solutionand with the 6-311++G(dp) basis set
Advances in Condensed Matter Physics 9
Table 3 Global reactivity descriptors of Rubescin E at the RHF B3LYP and B3PW91 levels in gas phase and in chloroform solution using the6-311++G(dp) basis set
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
Figure 3 Molecular orbital and the HOMO and LUMO energy of Rubescin E in gas phase
The calculated vertical IP values in gas phase are biggerthan their corresponding values in solvent From Table 3we also found that putting the molecule in solvent increasesits electron affinity From the calculated IP and EA valuesone can conclude that solvent effect increases the capacityof molecule of gaining an electron compared to donating itIt also reduces the harness of our molecule and increasesthe softness Hence the presence of solvent increases thereactivity of the molecule Rubescin
343 Frontier Molecular Orbitals The frontier molecularorbitals of Rubescin E were evaluated using the ab initio andDFT methods The 6-311G(dp) and 6-311++G(dp) basis setswere used for this purpose in gas phase and in chloroformsolutionThe results show that the energy gap of ourmoleculedecreases when diffuse functions are added onto all theatoms We also found that whenever the basis set andmethods used the energy gap is greater than 4 showing thatour molecule is hard and can be used as insulator in manyelectronic devices In Figure 3 the 3Dplots of theHOMOandLUMO orbitals computed at the RHF B3PW91 and B3LYPlevels with the 6-311G(dp) basis set are illustrated in gasphase We observed that the HOMO of Rubescin E is locatedover the furan ring at the three levels and also at the C-Cof cyclohexane ring and C-O of oxiran ring By contrast the
LUMO orbital is located over the cyclohex-2-enone ring C-C and C-O bond of tetrahydrofuran ring We can thereforeconclude that electron can easily be transferred from furanring to tetrahydrofuran ring
The total density of states (DOS) spectrum of RubescinE at the gas phase and in chloroform is given in Figure 4for each level at the 6-311++G(dp) basis set These DOSsspectra presented in Figure 4 were obtained from Gauss-Sum 30 program [18] which was used in order to show thecontributions of different group tomolecular orbital (HOMOand LUMO) From Figure 4 we observe that the HOMO-LUMO energy gap is smaller when we move from RHF toB3PW91 and from B3PW91 to B3LYP level respectively forboth gas and chloroform phases with larger values obtainedin chloroform
344 UV-Vis SpectraAnalysis Timedependent density func-tional theory (TD-DFT) was used in gas phase at the twolevels B3PW91 and B3LYP with the 6-311++G(dp) basis setin order to determine the first six excited states to investigatethe UV-vis absorption spectra of themoleculeThe excitationenergy (E) wavelength (120582) and oscillator strength (f) alongwith their major contributions are given in Table 4 and theirresults are compared to experiment
10 Advances in Condensed Matter Physics
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3LYP Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
Energy (eV)
B3LYP Gas
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Gas
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Chloroform
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Gas
4293 eV
9797 eV9516 eV
4315 eV 4333 eV
4314 eV
Figure 4 Total density of state (DOS) spectrum of Rubescin E at the RHF B3PW91 and B3LYP levels in both gas and chloroform phase andwith the 6-311++G(dp) basis set
Two intense electronic transitions were predicted at44934 eV (27592 nm) and 34415 eV (36027 nm) withoscillator strengths of 00043 and 00014 respectively at theB3PW91 level and 45123 eV (27477 nm) and 34603 eV(35831 nm) with oscillator strengths of 00041 and 00014respectively at the B3LYP levelWe observed from the spectra
that the maximum absorption wavelength corresponds tothe electronic transition from HOMO to LUMO+1 with100 contribution followed by the electronic transition fromHOMO to LUMO with 99 contribution at the two levelsThe experimental absorption spectra of the title moleculepredict two bands at 254 nm and 365 nm The error between
Advances in Condensed Matter Physics 11
Table 4Theoretical absorption wavelength (120582) excitation energy (E) and oscillator strengths of Rubescin E at the B3PW91 and B3LYP levelsin gas with the 6-311++G(dp) basis set
Excited states Exp [1] B3PW91 B3LYP120582 (nm) 120582 (nm) E (eV) f Major contributions 120582 (nm) E (eV) f Major contributions
1 365 36027 34415 00014 H-1 997888rarr L (93) 35831 34603 00014 H-1 997888rarr L (93)2 31218 39715 00000 H 997888rarr L (99) 31369 39524 00000 H 997888rarr L (99)3 254 27592 44934 00043 H-4 997888rarr L (24) 27477 45123 00041 H-4 997888rarr L (28)4 27266 45473 00006 H-4 997888rarr L (50) 27227 45538 00004 H-4 997888rarr L (44)5 26956 45994 00001 H-4 997888rarr L (19) 26847 46182 00001 H-4 997888rarr L (20)6 26121 47465 00000 H 997888rarr L+1 (100) 26316 47113 00000 H 997888rarr L+1 (100)
200 250 300 350 400 450 5000
50
100
150
200
250
300
350
wavelength (nm)
Epsi
lon
B3LYP
200 250 300 350 400 450 5000
50100150200250300350400
Wavelength (nm)
Epsi
lon
B3PW91
UV vis spectrumOscillator strength
UV vis spectrumOscillator strength
Figure 5 Theoretical absorption spectra of Rubescin E at the B3PW91 and B3LYP levels in gas with the 6-311++G(dp) basis set
the theoretical and experimental results range from - 473 nmto 2192 nm at the B3PW91 and from - 669 nm to 2077 nm atthe B3LYP levelThese errors are due to the fact that only onemolecule was considered for simulationThe theoretical UV-vis absorption spectra of Rubescin E in gas phase are shownin Figure 5
345 Dipole Moment (120583119863119872) Average Polarizability (120572) FirstStatic Hyperpolarizability (120573) and Anisotropy of PolarizationIn this work the dipole moment 120583119863119872 average polarizability120572 first static hyperpolarizability 120573 and anisotropy of polar-izability Δ120572 of Rubescin E were evaluated in both gas phaseand chloroform solution in order to define the nonlinearityof Rubescin E The finite-field approach was used for thispurpose Equations (2) (3) (4) and (5) were used to calculatethe polarizability dipole moment anisotropy of polarizabil-ity and first static hyperpolarizability respectively using thex 119910 119911 components obtained from Gaussian 09 W outputThe calculated parameters were presented in Table 5 at thethree levels with the 6-311++G(dp) basis set
The calculated values of polarizability and first static hyper-polarizability obtained from Gaussian output are in atomicunit These values were then converted into electrostatic unit(esu) for comparison purpose (for 120572 1 au = 01482 x 10minus24esu for 120573 1 au = 86393 x 10minus33 esu) [19ndash22] From a givingmolecule when these values (120583119863119872 and 120573) are greater thanthose of urea the molecule is said to have good active NLOproperties We observed from our results that the values of120572 120573 and 120583119863119872 are higher in solvent than their correspondingvalue in gas phase 120573 and 120583119863119872 of Rubescin E calculated at the6-311++G(dp) basis set using different methods were greaterthan those of urea These values calculated using the HF6-311D(dp)method (120583119863119872 = 52175Dand120573 = 17603169x10minus33esu) were also higher than those of urea (120583119863119872 = 38851D and120573 = 372811990910minus33esu) obtained using the same method and
12 Advances in Condensed Matter Physics
Table 5 Electric dipole moment polarizability anisotropy of polarization first-order hyperpolarizability and molar refractivity of RubescinE at the RHF B3LYP and B3PW91 levels with the 6-311G (d p) and 6-311++G (d p) basis sets
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
Table 6 Calculated values of polarization density (P) average electric field (E) electric susceptibility (120594) refractive index (120578) dielectricconstant (E) magnitude of the displacement (D) and molar refractivity (MR) of Rubescin E molecule obtained at the RHF B3LYP andB3PW91 levels with the 6-311++G(dp) basis set
Parameters RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
basis set [21] Hence Rubescin E can be considered to havegood active NLO properties and this is due to the delocalize electron on the furan ring
346 Optoelectronic Properties In order to recognize theoptoelectronic nature of Rubescin E for different devicesapplications some parameters such as electric field (E) elec-tric polarization (P) electric susceptibility (120594) permittivity(E) refractive index (120578) and electric displacement (D) werecalculated using equations given in the literature [23ndash25]We observed from Table 6 that the results of the calculatedparameters are slightly different when we move from onelevel to another and also when the medium changes Thevalue of electric field is greater in a solution of chloroformthan its corresponding value in gas phase This is because the
polarizability increases in presence of a solvent The valuesof electric susceptibility dielectric constant and refractiveindex are greater at B3LYP level compared to their corre-sponding value at the RHF All the calculated parametersof optoelectronic properties obtained at the B3LYP level aresimilar to those obtained at the B3PW91 level None of theseparameters have been determined before either theoreticallyor experimentally
One of the central goals of this study is to understandthe underlying structurendashproperty relationships whichmightform the basis for a ldquomolecular engineeringrdquo approachto electronics optoelectronics and photonics The molarrefractivity of our molecule known to be an importantparameter in quantitative structurendashproperty relationshipanalysis was calculated for this purpose The value of the
Advances in Condensed Matter Physics 13
Table 7 Experimental and calculated 1HNMR chemical shifts 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
molar refractivity was calculated at the three levels in bothgas and chloroform using the 6-311++G(dp) basis set TheLorenz-Lorentz equation was used for this calculation [2627] and its results are listed in Table 6
The high values of molar refractivity polarizabilityanisotropy of polarizability and first static hyperpolarizabil-ity of Rubescin E molecule show that the molecule has goodquantitative structurendashproperty relationship analysis andmight therefore form the basis for a ldquomolecular engineeringrdquoapproach to electronics optoelectronics and photonics
35 NMR Study of Rubescin E After the optimization ofthe Rubescin E molecule the 1H and 13C chemical shiftswere calculated at the RHF B3LYP and B3PW91 levels of thetheory using the 6-311++G(dp) basis set In order to comparethe calculated values of 1H and 13C chemical shifts withexperimental results we also need to calculate the absoluteshielding value of 1Hand 13C for the tetramethylsilane (TMS)using the same methods above The GIAO (Gauge InvariantAtomic Orbitals) approach known to provide satisfactorychemical shifts for different nuclei with larger molecules [28]was used for this purpose and the following equation
120575119894 (119901119901119898) = 119894119904119900119905119903119900119901119894119888 (119879119872119878119894) minus 119894119904119900119905119903119900119901119894119888 (119894) (6)
where 119894 is the atom type and was used to convert the chemicalshielding to chemical shifts
The experimental and calculated chemical shifts of 1Halong with their corresponding error are listed in Table 7From our results we observed that all the methods provideresults which are very close to experiment since the errorsbetween the experimental and calculated results are smaller
In order to compare experimental and theoretical resultsa linear correlation of 1H-NMR chemical shifts was estab-lished as shown in Figure 6 The regression line was plottedusing the following equations 120575119888119886119897 = 098880120575119890119909119901 minus 017198120575119888119886119897 = 097379120575119890119909119901 + 018796 and 120575119888119886119897 = 097069120575119890119909119901 +019387 respectively at the RHF B3PW91 and B3LYP levelsof the theory The theoretical results obtained from usingthe 6-311++G(dp) basis set show good correlation withexperiment since and the calculated R-square values arefound to be close to 1 at each level as shown by Figure 6
The calculated and experimental 13C chemical shifts ofour molecule are given in Table 8 and their comparison canbe found in Figure 7 The linear regression line plotted inFigure 7 shows that theoretical results are in good agreementwith experiment This is confirmed by the linear correlationcoefficient calculated here as R-square at the RHF B3PW91and B3LYP levels using the 6-311++G(dp) basis set
The following regression line plotted for each level usingthe general equation 120575119888119886119897 = 119886120575119890119909119901 + 119887 where a and b are givenin Figure 7 shows that the calculated 13C chemical shiftscorrelate very well with experiment The linear correlationcoefficient calculated as R-square found in Figure 7 alsoconfirms this
36 Vibrational Frequencies Analysis The vibrational fre-quencies of our molecule were computed by using B3LYP6-311G(dp) method in both gas phase and chloroform Theexperimental IR vibrational frequencies obtained for the twocarbonyl moiety present in our structure along with thecalculated scaled and unscaled vibrational frequencies IRand Raman frequencies with their approximate descriptions
14 Advances in Condensed Matter Physics
Table 8 Experimental and calculated 13C NMR chemical shift 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
y = +100x -0254 max dev150 r=0960 y = +0987x +0127 max dev104 r=0979
y = +0980x +0141 max dev103 r=0981
y = +100x -0254 max dev150 y = +0987x +0127 max dev104
y = +0980x +0141 max dev103
Figure 6 Comparison of experimental and theoretical 1H chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set in chloroform
Advances in Condensed Matter Physics 15
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3LYP6-311++G(dp)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3PW916-311++G(dp)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
minus250
255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
RHF6-311++G(dp)
y = +107x -517 max dev836 r=0994 y = +105x +238 max dev648 r=0998
y = +105x +354 max dev541 r=0998
y = +107x -517 max dev836 y = +105x +238 max dev648
y = +105x +354 max dev541
Figure 7 Comparison of experimental and theoretical 13C chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set
are given in Table 9 The rest of the vibrational parameterof Rubescin E molecule which is not described in Table 9can be obtained from Supplementary Material S2 The scalefactor was determined as the mean value of the scale factorthat matches correctly for the C=O stretching and the givenexperimental valueThe obtained scale factor was 09706 Noimaginary frequencies were found showing that structure ofthe molecule Rubescin E is stable in both gas and solventFigure 8 gives the representation of the scaled IR intensity andRaman scattering activity
The C=O double bond gives rise to a very intenseabsorption band in IR spectrum The position and intensityof this band range from 1870 cmminus1 to 1540 cmminus1 dependingon the physical state electronic andmass effects of neighbor-ing substituents intra- and intermolecular interactions andconjugations [29] The C=O double bond absorption spectra
were observed experimentally at 1720 cmminus1 and 1664 cmminus1[1] In this study the vibrational mode of C=O was found at172620 cmminus1 and 169057 cmminus1 gas phase and at 170101 cmminus1and 166759 cmminus1 in chloroform There is good agreementbetween the vibrational modes with experimental values
4 Conclusion
In this study the geometry optimization of Rubescin E hasbeen carried out using ab initio HF and density functionaltheoryDFT (B3LYP and B3PW91)methods in both gas phaseand chloroform solution with the 6-311++G(dp) basis setThe optimized parameters were compared to those of someexisting groups of compound present in our molecule sincenone of this have been done before for the title molecule andgood agreement was found In order to confirm the geometry
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
B3LYP and B3PW91 level of the theory In CDCl3 the C-C-C bond angles are similar to those obtained at the gasphase The smallest value of C-C-C bond angle was C20-C8-C29 bond angle and the largest C51-C14-C57 bond angle Forthe C-C-O angle the smallest value was 1044386∘ obtainedat the RHF and the largest value was 123472∘ obtained at theB3LYP level both in the gas phaseTheC-O-C bond angle wasfound between 1071084∘ and 1234264∘ obtained at the RHFlevel These bonds angles compared to some known valuesfound in literature [12 14] for specific compound present inour structure show good similaritiesThe little differences arefound between 00268∘ and 15507∘ for C-C-C bond between00595∘ and 30614∘ for C-C-O bond and between 00202∘and 0781∘ for C-O-C bond These observed differences aredue to the fact that these groups of compounds were notisolated
33 Calculated 3119869119867-119867 Coupling Constant The chemical 3JH-Hproton-proton coupling constant was calculated using theoriginal Karplus [10] equation in gas and solvent and itsresults compared to experimental values [1] obtained byextracting Rubescin E in a solution of chloroform From ourresults we found that the calculated parameters both in gasand in chloroform are all similar at all the levels used Theseobtained results are also very close to experiment As pre-dicted in literature [10] we observed from Table 2 that whenthe angles between the two C-H vectors are close enough to00 or 1800 the value of 3JH-H coupling constant is greater (with31198691800 gt 311986900) and is very small when the angle is close to 900
34 Electronic Properties341 Mulliken ESP and Natural Charge Distribution TheMulliken atomic charges of our molecule calculated at all
6 Advances in Condensed Matter Physics
Figure 1 Ground state geometry of Rubescin E at B3LYP6-311++G(dp) in chloroform solution
the levels in gas phase and chloroform show positive chargefor all the hydrogen atoms The net charge on all theatoms varies from -1109653e to 1980512e from -1164916eto 1904034e and from -0891775e to 1524787e respectivelyin gas phase at the RHF B3PW91 and B3LYP levels In asolution of chloroform the charges varied from -1064962e to1826589e from -1206706e to 1904292e and from -0945041eto 1550492e with some oxygen atoms charges being positiveand can be explained by the fact that the oxygen is related toextremely negative carbon atoms The most positive chargeatoms are C63 C5 C8 and the most negative charge atoms areC71 C62 C67
The electrostatic charges were evaluated in this workusing the CHelpG scheme of Breneman model We foundfrom our results that the most positive charges atom is C4followed by C62 and C2 and the most negative charge atom isC12 followed by C5 and C7 The observation made at all levelsand basis set in gas phase and in a solution of chloroform isthat the most positive charge atoms are directly related to themost negative charge atoms
The natural atomic charges obtained using the naturalbonding orbitalmethodwere also used to evaluate the atomiccharge of Rubescin E Positive and negative charges werefound for all hydrogen and oxygen atoms respectively Inthis case all carbon atoms directly linked to hydrogen atomswere found to have negative charges except for those linked tooxygen atomsThemost negative charge atom was calculatedusing HF method and was observed for O65 (-069456e) andO60 (-068330e) respectively in chloroform and gas phaseThemost positive charge atomwas found to beC62 in both gas(097067e 080601e and 081407e respectively at the RHF
B3PW91 and B3LYP levels) and solvent (098887e 081804eand 082650e respectively at the RHF B3PW91 and B3LYPlevels) this is due to the fact that C62 is related to negativecharge atoms (O65 O60 and C63) Mulliken electrostatic andnatural atomic charge distributions are graphically shown inFigure 2 From Figure 2 one can observe that for almost allthe methods used for charge description the most positiveand negative charge atoms were calculated at the RHF levelin both gas and chloroform and this is due to the fact thatthe effect of electron correlation is not well described in HFmethod
342 Global Reactivity Descriptors In order to understandthe relationships between structure stability and reactivity ofRubescin Emolecule the global reactivity descriptors param-eters such as chemical hardness (H) chemical potential (120583119888119901)chemical softness (s) electronegativity (119883) and electrophilic-ity index (120596) were calculated The finite difference equationgiven by (1) was used to calculate the ionization potentialand electron affinity which are generally used to calculate theabove cited parameters
119868119875 = 119864119902=119873+1 minus 119864119902=119873119864119860 = 119864119902=119873 minus 119864119902=119873minus1
(1)
The IP and EA calculated from (1) were then used to calculate119867 120583119888119901 s119883 and120596 using equations found in the literature [15ndash17] All these parameters calculated using the twomethods ingas phase are presented in Table 3 A high value of 120583119888119901 and 120596characterizes a good electrophile while a small value standsfor good nucleophile
Advances in Condensed Matter Physics 7
Table2Ex
perim
entaland
calculated3J H
-Hproton
-protoncoup
lingconstant
ofRu
bescin
Ein
gasp
hase
andin
chloroform
solutio
n
PARA
MET
ERS
RHF
B3LY
PB3
PW91
EXP[1]
Gaz
CDCl3
Gaz
CDCl3
Gaz
CDCl3
Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)H10-C9-C12-H13
455506
620
438143
649
4813
93579
459537
614
4832
85576
4616
62610
40
H10-C9-C20-H21
1695
395
1265
1698
194
1267
168824
1261
168658
1259
1685
1258
1682201
1256
120
H27-C26-C40-H41
-110
718
1065
-120311
1059
-101794
1070
-1089
1066
-104324
1069
-112
981064
65
H28-C26-C40-H41
1053029
296
103995
283
1063433
307
1053319
296
1061668
305
10496
4292
13H33-C32-C34-H35
-02873
11-012
311
-05893
11-0366
11-0566
11-033
3111
100
H47-C46-C48-H49
-613
614
382
-611286
385
-619
356
374
-618
438
375
-615
482
379
-614
875
380
42
H47-C46-C48-H50
5874
37417
587503
417
580428
427
578579
430
5853
4420
58304
4424
42
H49-C48-C51-H52
-425704
669
-421786
675
-439616
646
-433642
656
-445718
636
-439227
647
42
H50-C48-C51-H52
-164
093
1221
-163817
1218
-16522
1232
-164
673
1227
-165874
1237
-165259
1232
11H54-C53-C55-H56
-03838
11-02856
11-032
7511
-02429
11-039
2111
-03074
11H66-C64-C67-H68
-177906
1299
-177979
1299
17846
741299
1787874
131784147
1299
178548
1299
H66-C64-C67-H69
-569125
443
-569428
443
-603746
395
-599
903
4-6040
07395
-601923
397
70H66-C64-C67-H70
606324
391
604696
394
566811
447
56944
9442
566504
447
567234
446
70
8 Advances in Condensed Matter Physics
05
minus15
minus10
minus05
0
05
10
15
20
25
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Gas
minus15
minus10
minus05
0
05
10
15
20
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Mul
liken
char
ges
Mul
liken
char
ges
Chloroform
minus10
minus05
0
05
10
15
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
ESP
char
ges
ESP
char
ges
Chloroform
minus10
minus05
0
05
10
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Chloroform
minus10
minus05
0
10
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Nat
ural
atom
ic ch
arge
s
Nat
ural
atom
ic ch
arge
s
Gas
minus10
minus05
0
05
10
15
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Gas
Figure 2 Charge distribution on Rubescin E calculated at the RHF B3PW91 and B3LYP levels in both gas phase and chloroform solutionand with the 6-311++G(dp) basis set
Advances in Condensed Matter Physics 9
Table 3 Global reactivity descriptors of Rubescin E at the RHF B3LYP and B3PW91 levels in gas phase and in chloroform solution using the6-311++G(dp) basis set
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
Figure 3 Molecular orbital and the HOMO and LUMO energy of Rubescin E in gas phase
The calculated vertical IP values in gas phase are biggerthan their corresponding values in solvent From Table 3we also found that putting the molecule in solvent increasesits electron affinity From the calculated IP and EA valuesone can conclude that solvent effect increases the capacityof molecule of gaining an electron compared to donating itIt also reduces the harness of our molecule and increasesthe softness Hence the presence of solvent increases thereactivity of the molecule Rubescin
343 Frontier Molecular Orbitals The frontier molecularorbitals of Rubescin E were evaluated using the ab initio andDFT methods The 6-311G(dp) and 6-311++G(dp) basis setswere used for this purpose in gas phase and in chloroformsolutionThe results show that the energy gap of ourmoleculedecreases when diffuse functions are added onto all theatoms We also found that whenever the basis set andmethods used the energy gap is greater than 4 showing thatour molecule is hard and can be used as insulator in manyelectronic devices In Figure 3 the 3Dplots of theHOMOandLUMO orbitals computed at the RHF B3PW91 and B3LYPlevels with the 6-311G(dp) basis set are illustrated in gasphase We observed that the HOMO of Rubescin E is locatedover the furan ring at the three levels and also at the C-Cof cyclohexane ring and C-O of oxiran ring By contrast the
LUMO orbital is located over the cyclohex-2-enone ring C-C and C-O bond of tetrahydrofuran ring We can thereforeconclude that electron can easily be transferred from furanring to tetrahydrofuran ring
The total density of states (DOS) spectrum of RubescinE at the gas phase and in chloroform is given in Figure 4for each level at the 6-311++G(dp) basis set These DOSsspectra presented in Figure 4 were obtained from Gauss-Sum 30 program [18] which was used in order to show thecontributions of different group tomolecular orbital (HOMOand LUMO) From Figure 4 we observe that the HOMO-LUMO energy gap is smaller when we move from RHF toB3PW91 and from B3PW91 to B3LYP level respectively forboth gas and chloroform phases with larger values obtainedin chloroform
344 UV-Vis SpectraAnalysis Timedependent density func-tional theory (TD-DFT) was used in gas phase at the twolevels B3PW91 and B3LYP with the 6-311++G(dp) basis setin order to determine the first six excited states to investigatethe UV-vis absorption spectra of themoleculeThe excitationenergy (E) wavelength (120582) and oscillator strength (f) alongwith their major contributions are given in Table 4 and theirresults are compared to experiment
10 Advances in Condensed Matter Physics
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3LYP Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
Energy (eV)
B3LYP Gas
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Gas
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Chloroform
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Gas
4293 eV
9797 eV9516 eV
4315 eV 4333 eV
4314 eV
Figure 4 Total density of state (DOS) spectrum of Rubescin E at the RHF B3PW91 and B3LYP levels in both gas and chloroform phase andwith the 6-311++G(dp) basis set
Two intense electronic transitions were predicted at44934 eV (27592 nm) and 34415 eV (36027 nm) withoscillator strengths of 00043 and 00014 respectively at theB3PW91 level and 45123 eV (27477 nm) and 34603 eV(35831 nm) with oscillator strengths of 00041 and 00014respectively at the B3LYP levelWe observed from the spectra
that the maximum absorption wavelength corresponds tothe electronic transition from HOMO to LUMO+1 with100 contribution followed by the electronic transition fromHOMO to LUMO with 99 contribution at the two levelsThe experimental absorption spectra of the title moleculepredict two bands at 254 nm and 365 nm The error between
Advances in Condensed Matter Physics 11
Table 4Theoretical absorption wavelength (120582) excitation energy (E) and oscillator strengths of Rubescin E at the B3PW91 and B3LYP levelsin gas with the 6-311++G(dp) basis set
Excited states Exp [1] B3PW91 B3LYP120582 (nm) 120582 (nm) E (eV) f Major contributions 120582 (nm) E (eV) f Major contributions
1 365 36027 34415 00014 H-1 997888rarr L (93) 35831 34603 00014 H-1 997888rarr L (93)2 31218 39715 00000 H 997888rarr L (99) 31369 39524 00000 H 997888rarr L (99)3 254 27592 44934 00043 H-4 997888rarr L (24) 27477 45123 00041 H-4 997888rarr L (28)4 27266 45473 00006 H-4 997888rarr L (50) 27227 45538 00004 H-4 997888rarr L (44)5 26956 45994 00001 H-4 997888rarr L (19) 26847 46182 00001 H-4 997888rarr L (20)6 26121 47465 00000 H 997888rarr L+1 (100) 26316 47113 00000 H 997888rarr L+1 (100)
200 250 300 350 400 450 5000
50
100
150
200
250
300
350
wavelength (nm)
Epsi
lon
B3LYP
200 250 300 350 400 450 5000
50100150200250300350400
Wavelength (nm)
Epsi
lon
B3PW91
UV vis spectrumOscillator strength
UV vis spectrumOscillator strength
Figure 5 Theoretical absorption spectra of Rubescin E at the B3PW91 and B3LYP levels in gas with the 6-311++G(dp) basis set
the theoretical and experimental results range from - 473 nmto 2192 nm at the B3PW91 and from - 669 nm to 2077 nm atthe B3LYP levelThese errors are due to the fact that only onemolecule was considered for simulationThe theoretical UV-vis absorption spectra of Rubescin E in gas phase are shownin Figure 5
345 Dipole Moment (120583119863119872) Average Polarizability (120572) FirstStatic Hyperpolarizability (120573) and Anisotropy of PolarizationIn this work the dipole moment 120583119863119872 average polarizability120572 first static hyperpolarizability 120573 and anisotropy of polar-izability Δ120572 of Rubescin E were evaluated in both gas phaseand chloroform solution in order to define the nonlinearityof Rubescin E The finite-field approach was used for thispurpose Equations (2) (3) (4) and (5) were used to calculatethe polarizability dipole moment anisotropy of polarizabil-ity and first static hyperpolarizability respectively using thex 119910 119911 components obtained from Gaussian 09 W outputThe calculated parameters were presented in Table 5 at thethree levels with the 6-311++G(dp) basis set
The calculated values of polarizability and first static hyper-polarizability obtained from Gaussian output are in atomicunit These values were then converted into electrostatic unit(esu) for comparison purpose (for 120572 1 au = 01482 x 10minus24esu for 120573 1 au = 86393 x 10minus33 esu) [19ndash22] From a givingmolecule when these values (120583119863119872 and 120573) are greater thanthose of urea the molecule is said to have good active NLOproperties We observed from our results that the values of120572 120573 and 120583119863119872 are higher in solvent than their correspondingvalue in gas phase 120573 and 120583119863119872 of Rubescin E calculated at the6-311++G(dp) basis set using different methods were greaterthan those of urea These values calculated using the HF6-311D(dp)method (120583119863119872 = 52175Dand120573 = 17603169x10minus33esu) were also higher than those of urea (120583119863119872 = 38851D and120573 = 372811990910minus33esu) obtained using the same method and
12 Advances in Condensed Matter Physics
Table 5 Electric dipole moment polarizability anisotropy of polarization first-order hyperpolarizability and molar refractivity of RubescinE at the RHF B3LYP and B3PW91 levels with the 6-311G (d p) and 6-311++G (d p) basis sets
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
Table 6 Calculated values of polarization density (P) average electric field (E) electric susceptibility (120594) refractive index (120578) dielectricconstant (E) magnitude of the displacement (D) and molar refractivity (MR) of Rubescin E molecule obtained at the RHF B3LYP andB3PW91 levels with the 6-311++G(dp) basis set
Parameters RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
basis set [21] Hence Rubescin E can be considered to havegood active NLO properties and this is due to the delocalize electron on the furan ring
346 Optoelectronic Properties In order to recognize theoptoelectronic nature of Rubescin E for different devicesapplications some parameters such as electric field (E) elec-tric polarization (P) electric susceptibility (120594) permittivity(E) refractive index (120578) and electric displacement (D) werecalculated using equations given in the literature [23ndash25]We observed from Table 6 that the results of the calculatedparameters are slightly different when we move from onelevel to another and also when the medium changes Thevalue of electric field is greater in a solution of chloroformthan its corresponding value in gas phase This is because the
polarizability increases in presence of a solvent The valuesof electric susceptibility dielectric constant and refractiveindex are greater at B3LYP level compared to their corre-sponding value at the RHF All the calculated parametersof optoelectronic properties obtained at the B3LYP level aresimilar to those obtained at the B3PW91 level None of theseparameters have been determined before either theoreticallyor experimentally
One of the central goals of this study is to understandthe underlying structurendashproperty relationships whichmightform the basis for a ldquomolecular engineeringrdquo approachto electronics optoelectronics and photonics The molarrefractivity of our molecule known to be an importantparameter in quantitative structurendashproperty relationshipanalysis was calculated for this purpose The value of the
Advances in Condensed Matter Physics 13
Table 7 Experimental and calculated 1HNMR chemical shifts 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
molar refractivity was calculated at the three levels in bothgas and chloroform using the 6-311++G(dp) basis set TheLorenz-Lorentz equation was used for this calculation [2627] and its results are listed in Table 6
The high values of molar refractivity polarizabilityanisotropy of polarizability and first static hyperpolarizabil-ity of Rubescin E molecule show that the molecule has goodquantitative structurendashproperty relationship analysis andmight therefore form the basis for a ldquomolecular engineeringrdquoapproach to electronics optoelectronics and photonics
35 NMR Study of Rubescin E After the optimization ofthe Rubescin E molecule the 1H and 13C chemical shiftswere calculated at the RHF B3LYP and B3PW91 levels of thetheory using the 6-311++G(dp) basis set In order to comparethe calculated values of 1H and 13C chemical shifts withexperimental results we also need to calculate the absoluteshielding value of 1Hand 13C for the tetramethylsilane (TMS)using the same methods above The GIAO (Gauge InvariantAtomic Orbitals) approach known to provide satisfactorychemical shifts for different nuclei with larger molecules [28]was used for this purpose and the following equation
120575119894 (119901119901119898) = 119894119904119900119905119903119900119901119894119888 (119879119872119878119894) minus 119894119904119900119905119903119900119901119894119888 (119894) (6)
where 119894 is the atom type and was used to convert the chemicalshielding to chemical shifts
The experimental and calculated chemical shifts of 1Halong with their corresponding error are listed in Table 7From our results we observed that all the methods provideresults which are very close to experiment since the errorsbetween the experimental and calculated results are smaller
In order to compare experimental and theoretical resultsa linear correlation of 1H-NMR chemical shifts was estab-lished as shown in Figure 6 The regression line was plottedusing the following equations 120575119888119886119897 = 098880120575119890119909119901 minus 017198120575119888119886119897 = 097379120575119890119909119901 + 018796 and 120575119888119886119897 = 097069120575119890119909119901 +019387 respectively at the RHF B3PW91 and B3LYP levelsof the theory The theoretical results obtained from usingthe 6-311++G(dp) basis set show good correlation withexperiment since and the calculated R-square values arefound to be close to 1 at each level as shown by Figure 6
The calculated and experimental 13C chemical shifts ofour molecule are given in Table 8 and their comparison canbe found in Figure 7 The linear regression line plotted inFigure 7 shows that theoretical results are in good agreementwith experiment This is confirmed by the linear correlationcoefficient calculated here as R-square at the RHF B3PW91and B3LYP levels using the 6-311++G(dp) basis set
The following regression line plotted for each level usingthe general equation 120575119888119886119897 = 119886120575119890119909119901 + 119887 where a and b are givenin Figure 7 shows that the calculated 13C chemical shiftscorrelate very well with experiment The linear correlationcoefficient calculated as R-square found in Figure 7 alsoconfirms this
36 Vibrational Frequencies Analysis The vibrational fre-quencies of our molecule were computed by using B3LYP6-311G(dp) method in both gas phase and chloroform Theexperimental IR vibrational frequencies obtained for the twocarbonyl moiety present in our structure along with thecalculated scaled and unscaled vibrational frequencies IRand Raman frequencies with their approximate descriptions
14 Advances in Condensed Matter Physics
Table 8 Experimental and calculated 13C NMR chemical shift 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
y = +100x -0254 max dev150 r=0960 y = +0987x +0127 max dev104 r=0979
y = +0980x +0141 max dev103 r=0981
y = +100x -0254 max dev150 y = +0987x +0127 max dev104
y = +0980x +0141 max dev103
Figure 6 Comparison of experimental and theoretical 1H chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set in chloroform
Advances in Condensed Matter Physics 15
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3LYP6-311++G(dp)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3PW916-311++G(dp)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
minus250
255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
RHF6-311++G(dp)
y = +107x -517 max dev836 r=0994 y = +105x +238 max dev648 r=0998
y = +105x +354 max dev541 r=0998
y = +107x -517 max dev836 y = +105x +238 max dev648
y = +105x +354 max dev541
Figure 7 Comparison of experimental and theoretical 13C chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set
are given in Table 9 The rest of the vibrational parameterof Rubescin E molecule which is not described in Table 9can be obtained from Supplementary Material S2 The scalefactor was determined as the mean value of the scale factorthat matches correctly for the C=O stretching and the givenexperimental valueThe obtained scale factor was 09706 Noimaginary frequencies were found showing that structure ofthe molecule Rubescin E is stable in both gas and solventFigure 8 gives the representation of the scaled IR intensity andRaman scattering activity
The C=O double bond gives rise to a very intenseabsorption band in IR spectrum The position and intensityof this band range from 1870 cmminus1 to 1540 cmminus1 dependingon the physical state electronic andmass effects of neighbor-ing substituents intra- and intermolecular interactions andconjugations [29] The C=O double bond absorption spectra
were observed experimentally at 1720 cmminus1 and 1664 cmminus1[1] In this study the vibrational mode of C=O was found at172620 cmminus1 and 169057 cmminus1 gas phase and at 170101 cmminus1and 166759 cmminus1 in chloroform There is good agreementbetween the vibrational modes with experimental values
4 Conclusion
In this study the geometry optimization of Rubescin E hasbeen carried out using ab initio HF and density functionaltheoryDFT (B3LYP and B3PW91)methods in both gas phaseand chloroform solution with the 6-311++G(dp) basis setThe optimized parameters were compared to those of someexisting groups of compound present in our molecule sincenone of this have been done before for the title molecule andgood agreement was found In order to confirm the geometry
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
B3LYP and B3PW91 level of the theory In CDCl3 the C-C-C bond angles are similar to those obtained at the gasphase The smallest value of C-C-C bond angle was C20-C8-C29 bond angle and the largest C51-C14-C57 bond angle Forthe C-C-O angle the smallest value was 1044386∘ obtainedat the RHF and the largest value was 123472∘ obtained at theB3LYP level both in the gas phaseTheC-O-C bond angle wasfound between 1071084∘ and 1234264∘ obtained at the RHFlevel These bonds angles compared to some known valuesfound in literature [12 14] for specific compound present inour structure show good similaritiesThe little differences arefound between 00268∘ and 15507∘ for C-C-C bond between00595∘ and 30614∘ for C-C-O bond and between 00202∘and 0781∘ for C-O-C bond These observed differences aredue to the fact that these groups of compounds were notisolated
33 Calculated 3119869119867-119867 Coupling Constant The chemical 3JH-Hproton-proton coupling constant was calculated using theoriginal Karplus [10] equation in gas and solvent and itsresults compared to experimental values [1] obtained byextracting Rubescin E in a solution of chloroform From ourresults we found that the calculated parameters both in gasand in chloroform are all similar at all the levels used Theseobtained results are also very close to experiment As pre-dicted in literature [10] we observed from Table 2 that whenthe angles between the two C-H vectors are close enough to00 or 1800 the value of 3JH-H coupling constant is greater (with31198691800 gt 311986900) and is very small when the angle is close to 900
34 Electronic Properties341 Mulliken ESP and Natural Charge Distribution TheMulliken atomic charges of our molecule calculated at all
6 Advances in Condensed Matter Physics
Figure 1 Ground state geometry of Rubescin E at B3LYP6-311++G(dp) in chloroform solution
the levels in gas phase and chloroform show positive chargefor all the hydrogen atoms The net charge on all theatoms varies from -1109653e to 1980512e from -1164916eto 1904034e and from -0891775e to 1524787e respectivelyin gas phase at the RHF B3PW91 and B3LYP levels In asolution of chloroform the charges varied from -1064962e to1826589e from -1206706e to 1904292e and from -0945041eto 1550492e with some oxygen atoms charges being positiveand can be explained by the fact that the oxygen is related toextremely negative carbon atoms The most positive chargeatoms are C63 C5 C8 and the most negative charge atoms areC71 C62 C67
The electrostatic charges were evaluated in this workusing the CHelpG scheme of Breneman model We foundfrom our results that the most positive charges atom is C4followed by C62 and C2 and the most negative charge atom isC12 followed by C5 and C7 The observation made at all levelsand basis set in gas phase and in a solution of chloroform isthat the most positive charge atoms are directly related to themost negative charge atoms
The natural atomic charges obtained using the naturalbonding orbitalmethodwere also used to evaluate the atomiccharge of Rubescin E Positive and negative charges werefound for all hydrogen and oxygen atoms respectively Inthis case all carbon atoms directly linked to hydrogen atomswere found to have negative charges except for those linked tooxygen atomsThemost negative charge atom was calculatedusing HF method and was observed for O65 (-069456e) andO60 (-068330e) respectively in chloroform and gas phaseThemost positive charge atomwas found to beC62 in both gas(097067e 080601e and 081407e respectively at the RHF
B3PW91 and B3LYP levels) and solvent (098887e 081804eand 082650e respectively at the RHF B3PW91 and B3LYPlevels) this is due to the fact that C62 is related to negativecharge atoms (O65 O60 and C63) Mulliken electrostatic andnatural atomic charge distributions are graphically shown inFigure 2 From Figure 2 one can observe that for almost allthe methods used for charge description the most positiveand negative charge atoms were calculated at the RHF levelin both gas and chloroform and this is due to the fact thatthe effect of electron correlation is not well described in HFmethod
342 Global Reactivity Descriptors In order to understandthe relationships between structure stability and reactivity ofRubescin Emolecule the global reactivity descriptors param-eters such as chemical hardness (H) chemical potential (120583119888119901)chemical softness (s) electronegativity (119883) and electrophilic-ity index (120596) were calculated The finite difference equationgiven by (1) was used to calculate the ionization potentialand electron affinity which are generally used to calculate theabove cited parameters
119868119875 = 119864119902=119873+1 minus 119864119902=119873119864119860 = 119864119902=119873 minus 119864119902=119873minus1
(1)
The IP and EA calculated from (1) were then used to calculate119867 120583119888119901 s119883 and120596 using equations found in the literature [15ndash17] All these parameters calculated using the twomethods ingas phase are presented in Table 3 A high value of 120583119888119901 and 120596characterizes a good electrophile while a small value standsfor good nucleophile
Advances in Condensed Matter Physics 7
Table2Ex
perim
entaland
calculated3J H
-Hproton
-protoncoup
lingconstant
ofRu
bescin
Ein
gasp
hase
andin
chloroform
solutio
n
PARA
MET
ERS
RHF
B3LY
PB3
PW91
EXP[1]
Gaz
CDCl3
Gaz
CDCl3
Gaz
CDCl3
Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)H10-C9-C12-H13
455506
620
438143
649
4813
93579
459537
614
4832
85576
4616
62610
40
H10-C9-C20-H21
1695
395
1265
1698
194
1267
168824
1261
168658
1259
1685
1258
1682201
1256
120
H27-C26-C40-H41
-110
718
1065
-120311
1059
-101794
1070
-1089
1066
-104324
1069
-112
981064
65
H28-C26-C40-H41
1053029
296
103995
283
1063433
307
1053319
296
1061668
305
10496
4292
13H33-C32-C34-H35
-02873
11-012
311
-05893
11-0366
11-0566
11-033
3111
100
H47-C46-C48-H49
-613
614
382
-611286
385
-619
356
374
-618
438
375
-615
482
379
-614
875
380
42
H47-C46-C48-H50
5874
37417
587503
417
580428
427
578579
430
5853
4420
58304
4424
42
H49-C48-C51-H52
-425704
669
-421786
675
-439616
646
-433642
656
-445718
636
-439227
647
42
H50-C48-C51-H52
-164
093
1221
-163817
1218
-16522
1232
-164
673
1227
-165874
1237
-165259
1232
11H54-C53-C55-H56
-03838
11-02856
11-032
7511
-02429
11-039
2111
-03074
11H66-C64-C67-H68
-177906
1299
-177979
1299
17846
741299
1787874
131784147
1299
178548
1299
H66-C64-C67-H69
-569125
443
-569428
443
-603746
395
-599
903
4-6040
07395
-601923
397
70H66-C64-C67-H70
606324
391
604696
394
566811
447
56944
9442
566504
447
567234
446
70
8 Advances in Condensed Matter Physics
05
minus15
minus10
minus05
0
05
10
15
20
25
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Gas
minus15
minus10
minus05
0
05
10
15
20
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Mul
liken
char
ges
Mul
liken
char
ges
Chloroform
minus10
minus05
0
05
10
15
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
ESP
char
ges
ESP
char
ges
Chloroform
minus10
minus05
0
05
10
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Chloroform
minus10
minus05
0
10
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Nat
ural
atom
ic ch
arge
s
Nat
ural
atom
ic ch
arge
s
Gas
minus10
minus05
0
05
10
15
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Gas
Figure 2 Charge distribution on Rubescin E calculated at the RHF B3PW91 and B3LYP levels in both gas phase and chloroform solutionand with the 6-311++G(dp) basis set
Advances in Condensed Matter Physics 9
Table 3 Global reactivity descriptors of Rubescin E at the RHF B3LYP and B3PW91 levels in gas phase and in chloroform solution using the6-311++G(dp) basis set
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
Figure 3 Molecular orbital and the HOMO and LUMO energy of Rubescin E in gas phase
The calculated vertical IP values in gas phase are biggerthan their corresponding values in solvent From Table 3we also found that putting the molecule in solvent increasesits electron affinity From the calculated IP and EA valuesone can conclude that solvent effect increases the capacityof molecule of gaining an electron compared to donating itIt also reduces the harness of our molecule and increasesthe softness Hence the presence of solvent increases thereactivity of the molecule Rubescin
343 Frontier Molecular Orbitals The frontier molecularorbitals of Rubescin E were evaluated using the ab initio andDFT methods The 6-311G(dp) and 6-311++G(dp) basis setswere used for this purpose in gas phase and in chloroformsolutionThe results show that the energy gap of ourmoleculedecreases when diffuse functions are added onto all theatoms We also found that whenever the basis set andmethods used the energy gap is greater than 4 showing thatour molecule is hard and can be used as insulator in manyelectronic devices In Figure 3 the 3Dplots of theHOMOandLUMO orbitals computed at the RHF B3PW91 and B3LYPlevels with the 6-311G(dp) basis set are illustrated in gasphase We observed that the HOMO of Rubescin E is locatedover the furan ring at the three levels and also at the C-Cof cyclohexane ring and C-O of oxiran ring By contrast the
LUMO orbital is located over the cyclohex-2-enone ring C-C and C-O bond of tetrahydrofuran ring We can thereforeconclude that electron can easily be transferred from furanring to tetrahydrofuran ring
The total density of states (DOS) spectrum of RubescinE at the gas phase and in chloroform is given in Figure 4for each level at the 6-311++G(dp) basis set These DOSsspectra presented in Figure 4 were obtained from Gauss-Sum 30 program [18] which was used in order to show thecontributions of different group tomolecular orbital (HOMOand LUMO) From Figure 4 we observe that the HOMO-LUMO energy gap is smaller when we move from RHF toB3PW91 and from B3PW91 to B3LYP level respectively forboth gas and chloroform phases with larger values obtainedin chloroform
344 UV-Vis SpectraAnalysis Timedependent density func-tional theory (TD-DFT) was used in gas phase at the twolevels B3PW91 and B3LYP with the 6-311++G(dp) basis setin order to determine the first six excited states to investigatethe UV-vis absorption spectra of themoleculeThe excitationenergy (E) wavelength (120582) and oscillator strength (f) alongwith their major contributions are given in Table 4 and theirresults are compared to experiment
10 Advances in Condensed Matter Physics
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3LYP Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
Energy (eV)
B3LYP Gas
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Gas
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Chloroform
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Gas
4293 eV
9797 eV9516 eV
4315 eV 4333 eV
4314 eV
Figure 4 Total density of state (DOS) spectrum of Rubescin E at the RHF B3PW91 and B3LYP levels in both gas and chloroform phase andwith the 6-311++G(dp) basis set
Two intense electronic transitions were predicted at44934 eV (27592 nm) and 34415 eV (36027 nm) withoscillator strengths of 00043 and 00014 respectively at theB3PW91 level and 45123 eV (27477 nm) and 34603 eV(35831 nm) with oscillator strengths of 00041 and 00014respectively at the B3LYP levelWe observed from the spectra
that the maximum absorption wavelength corresponds tothe electronic transition from HOMO to LUMO+1 with100 contribution followed by the electronic transition fromHOMO to LUMO with 99 contribution at the two levelsThe experimental absorption spectra of the title moleculepredict two bands at 254 nm and 365 nm The error between
Advances in Condensed Matter Physics 11
Table 4Theoretical absorption wavelength (120582) excitation energy (E) and oscillator strengths of Rubescin E at the B3PW91 and B3LYP levelsin gas with the 6-311++G(dp) basis set
Excited states Exp [1] B3PW91 B3LYP120582 (nm) 120582 (nm) E (eV) f Major contributions 120582 (nm) E (eV) f Major contributions
1 365 36027 34415 00014 H-1 997888rarr L (93) 35831 34603 00014 H-1 997888rarr L (93)2 31218 39715 00000 H 997888rarr L (99) 31369 39524 00000 H 997888rarr L (99)3 254 27592 44934 00043 H-4 997888rarr L (24) 27477 45123 00041 H-4 997888rarr L (28)4 27266 45473 00006 H-4 997888rarr L (50) 27227 45538 00004 H-4 997888rarr L (44)5 26956 45994 00001 H-4 997888rarr L (19) 26847 46182 00001 H-4 997888rarr L (20)6 26121 47465 00000 H 997888rarr L+1 (100) 26316 47113 00000 H 997888rarr L+1 (100)
200 250 300 350 400 450 5000
50
100
150
200
250
300
350
wavelength (nm)
Epsi
lon
B3LYP
200 250 300 350 400 450 5000
50100150200250300350400
Wavelength (nm)
Epsi
lon
B3PW91
UV vis spectrumOscillator strength
UV vis spectrumOscillator strength
Figure 5 Theoretical absorption spectra of Rubescin E at the B3PW91 and B3LYP levels in gas with the 6-311++G(dp) basis set
the theoretical and experimental results range from - 473 nmto 2192 nm at the B3PW91 and from - 669 nm to 2077 nm atthe B3LYP levelThese errors are due to the fact that only onemolecule was considered for simulationThe theoretical UV-vis absorption spectra of Rubescin E in gas phase are shownin Figure 5
345 Dipole Moment (120583119863119872) Average Polarizability (120572) FirstStatic Hyperpolarizability (120573) and Anisotropy of PolarizationIn this work the dipole moment 120583119863119872 average polarizability120572 first static hyperpolarizability 120573 and anisotropy of polar-izability Δ120572 of Rubescin E were evaluated in both gas phaseand chloroform solution in order to define the nonlinearityof Rubescin E The finite-field approach was used for thispurpose Equations (2) (3) (4) and (5) were used to calculatethe polarizability dipole moment anisotropy of polarizabil-ity and first static hyperpolarizability respectively using thex 119910 119911 components obtained from Gaussian 09 W outputThe calculated parameters were presented in Table 5 at thethree levels with the 6-311++G(dp) basis set
The calculated values of polarizability and first static hyper-polarizability obtained from Gaussian output are in atomicunit These values were then converted into electrostatic unit(esu) for comparison purpose (for 120572 1 au = 01482 x 10minus24esu for 120573 1 au = 86393 x 10minus33 esu) [19ndash22] From a givingmolecule when these values (120583119863119872 and 120573) are greater thanthose of urea the molecule is said to have good active NLOproperties We observed from our results that the values of120572 120573 and 120583119863119872 are higher in solvent than their correspondingvalue in gas phase 120573 and 120583119863119872 of Rubescin E calculated at the6-311++G(dp) basis set using different methods were greaterthan those of urea These values calculated using the HF6-311D(dp)method (120583119863119872 = 52175Dand120573 = 17603169x10minus33esu) were also higher than those of urea (120583119863119872 = 38851D and120573 = 372811990910minus33esu) obtained using the same method and
12 Advances in Condensed Matter Physics
Table 5 Electric dipole moment polarizability anisotropy of polarization first-order hyperpolarizability and molar refractivity of RubescinE at the RHF B3LYP and B3PW91 levels with the 6-311G (d p) and 6-311++G (d p) basis sets
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
Table 6 Calculated values of polarization density (P) average electric field (E) electric susceptibility (120594) refractive index (120578) dielectricconstant (E) magnitude of the displacement (D) and molar refractivity (MR) of Rubescin E molecule obtained at the RHF B3LYP andB3PW91 levels with the 6-311++G(dp) basis set
Parameters RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
basis set [21] Hence Rubescin E can be considered to havegood active NLO properties and this is due to the delocalize electron on the furan ring
346 Optoelectronic Properties In order to recognize theoptoelectronic nature of Rubescin E for different devicesapplications some parameters such as electric field (E) elec-tric polarization (P) electric susceptibility (120594) permittivity(E) refractive index (120578) and electric displacement (D) werecalculated using equations given in the literature [23ndash25]We observed from Table 6 that the results of the calculatedparameters are slightly different when we move from onelevel to another and also when the medium changes Thevalue of electric field is greater in a solution of chloroformthan its corresponding value in gas phase This is because the
polarizability increases in presence of a solvent The valuesof electric susceptibility dielectric constant and refractiveindex are greater at B3LYP level compared to their corre-sponding value at the RHF All the calculated parametersof optoelectronic properties obtained at the B3LYP level aresimilar to those obtained at the B3PW91 level None of theseparameters have been determined before either theoreticallyor experimentally
One of the central goals of this study is to understandthe underlying structurendashproperty relationships whichmightform the basis for a ldquomolecular engineeringrdquo approachto electronics optoelectronics and photonics The molarrefractivity of our molecule known to be an importantparameter in quantitative structurendashproperty relationshipanalysis was calculated for this purpose The value of the
Advances in Condensed Matter Physics 13
Table 7 Experimental and calculated 1HNMR chemical shifts 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
molar refractivity was calculated at the three levels in bothgas and chloroform using the 6-311++G(dp) basis set TheLorenz-Lorentz equation was used for this calculation [2627] and its results are listed in Table 6
The high values of molar refractivity polarizabilityanisotropy of polarizability and first static hyperpolarizabil-ity of Rubescin E molecule show that the molecule has goodquantitative structurendashproperty relationship analysis andmight therefore form the basis for a ldquomolecular engineeringrdquoapproach to electronics optoelectronics and photonics
35 NMR Study of Rubescin E After the optimization ofthe Rubescin E molecule the 1H and 13C chemical shiftswere calculated at the RHF B3LYP and B3PW91 levels of thetheory using the 6-311++G(dp) basis set In order to comparethe calculated values of 1H and 13C chemical shifts withexperimental results we also need to calculate the absoluteshielding value of 1Hand 13C for the tetramethylsilane (TMS)using the same methods above The GIAO (Gauge InvariantAtomic Orbitals) approach known to provide satisfactorychemical shifts for different nuclei with larger molecules [28]was used for this purpose and the following equation
120575119894 (119901119901119898) = 119894119904119900119905119903119900119901119894119888 (119879119872119878119894) minus 119894119904119900119905119903119900119901119894119888 (119894) (6)
where 119894 is the atom type and was used to convert the chemicalshielding to chemical shifts
The experimental and calculated chemical shifts of 1Halong with their corresponding error are listed in Table 7From our results we observed that all the methods provideresults which are very close to experiment since the errorsbetween the experimental and calculated results are smaller
In order to compare experimental and theoretical resultsa linear correlation of 1H-NMR chemical shifts was estab-lished as shown in Figure 6 The regression line was plottedusing the following equations 120575119888119886119897 = 098880120575119890119909119901 minus 017198120575119888119886119897 = 097379120575119890119909119901 + 018796 and 120575119888119886119897 = 097069120575119890119909119901 +019387 respectively at the RHF B3PW91 and B3LYP levelsof the theory The theoretical results obtained from usingthe 6-311++G(dp) basis set show good correlation withexperiment since and the calculated R-square values arefound to be close to 1 at each level as shown by Figure 6
The calculated and experimental 13C chemical shifts ofour molecule are given in Table 8 and their comparison canbe found in Figure 7 The linear regression line plotted inFigure 7 shows that theoretical results are in good agreementwith experiment This is confirmed by the linear correlationcoefficient calculated here as R-square at the RHF B3PW91and B3LYP levels using the 6-311++G(dp) basis set
The following regression line plotted for each level usingthe general equation 120575119888119886119897 = 119886120575119890119909119901 + 119887 where a and b are givenin Figure 7 shows that the calculated 13C chemical shiftscorrelate very well with experiment The linear correlationcoefficient calculated as R-square found in Figure 7 alsoconfirms this
36 Vibrational Frequencies Analysis The vibrational fre-quencies of our molecule were computed by using B3LYP6-311G(dp) method in both gas phase and chloroform Theexperimental IR vibrational frequencies obtained for the twocarbonyl moiety present in our structure along with thecalculated scaled and unscaled vibrational frequencies IRand Raman frequencies with their approximate descriptions
14 Advances in Condensed Matter Physics
Table 8 Experimental and calculated 13C NMR chemical shift 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
y = +100x -0254 max dev150 r=0960 y = +0987x +0127 max dev104 r=0979
y = +0980x +0141 max dev103 r=0981
y = +100x -0254 max dev150 y = +0987x +0127 max dev104
y = +0980x +0141 max dev103
Figure 6 Comparison of experimental and theoretical 1H chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set in chloroform
Advances in Condensed Matter Physics 15
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3LYP6-311++G(dp)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3PW916-311++G(dp)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
minus250
255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
RHF6-311++G(dp)
y = +107x -517 max dev836 r=0994 y = +105x +238 max dev648 r=0998
y = +105x +354 max dev541 r=0998
y = +107x -517 max dev836 y = +105x +238 max dev648
y = +105x +354 max dev541
Figure 7 Comparison of experimental and theoretical 13C chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set
are given in Table 9 The rest of the vibrational parameterof Rubescin E molecule which is not described in Table 9can be obtained from Supplementary Material S2 The scalefactor was determined as the mean value of the scale factorthat matches correctly for the C=O stretching and the givenexperimental valueThe obtained scale factor was 09706 Noimaginary frequencies were found showing that structure ofthe molecule Rubescin E is stable in both gas and solventFigure 8 gives the representation of the scaled IR intensity andRaman scattering activity
The C=O double bond gives rise to a very intenseabsorption band in IR spectrum The position and intensityof this band range from 1870 cmminus1 to 1540 cmminus1 dependingon the physical state electronic andmass effects of neighbor-ing substituents intra- and intermolecular interactions andconjugations [29] The C=O double bond absorption spectra
were observed experimentally at 1720 cmminus1 and 1664 cmminus1[1] In this study the vibrational mode of C=O was found at172620 cmminus1 and 169057 cmminus1 gas phase and at 170101 cmminus1and 166759 cmminus1 in chloroform There is good agreementbetween the vibrational modes with experimental values
4 Conclusion
In this study the geometry optimization of Rubescin E hasbeen carried out using ab initio HF and density functionaltheoryDFT (B3LYP and B3PW91)methods in both gas phaseand chloroform solution with the 6-311++G(dp) basis setThe optimized parameters were compared to those of someexisting groups of compound present in our molecule sincenone of this have been done before for the title molecule andgood agreement was found In order to confirm the geometry
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
Applied Bionics and BiomechanicsHindawiwwwhindawicom Volume 2018
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Hindawiwwwhindawicom
Volume 2018
Hindawiwwwhindawicom Volume 2018
Mathematical PhysicsAdvances in
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Hindawiwwwhindawicom Volume 2018
Journal of
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Hindawiwwwhindawicom Volume 2018
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International Journal of
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Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom
Journal ofEngineeringVolume 2018
Submit your manuscripts atwwwhindawicom
6 Advances in Condensed Matter Physics
Figure 1 Ground state geometry of Rubescin E at B3LYP6-311++G(dp) in chloroform solution
the levels in gas phase and chloroform show positive chargefor all the hydrogen atoms The net charge on all theatoms varies from -1109653e to 1980512e from -1164916eto 1904034e and from -0891775e to 1524787e respectivelyin gas phase at the RHF B3PW91 and B3LYP levels In asolution of chloroform the charges varied from -1064962e to1826589e from -1206706e to 1904292e and from -0945041eto 1550492e with some oxygen atoms charges being positiveand can be explained by the fact that the oxygen is related toextremely negative carbon atoms The most positive chargeatoms are C63 C5 C8 and the most negative charge atoms areC71 C62 C67
The electrostatic charges were evaluated in this workusing the CHelpG scheme of Breneman model We foundfrom our results that the most positive charges atom is C4followed by C62 and C2 and the most negative charge atom isC12 followed by C5 and C7 The observation made at all levelsand basis set in gas phase and in a solution of chloroform isthat the most positive charge atoms are directly related to themost negative charge atoms
The natural atomic charges obtained using the naturalbonding orbitalmethodwere also used to evaluate the atomiccharge of Rubescin E Positive and negative charges werefound for all hydrogen and oxygen atoms respectively Inthis case all carbon atoms directly linked to hydrogen atomswere found to have negative charges except for those linked tooxygen atomsThemost negative charge atom was calculatedusing HF method and was observed for O65 (-069456e) andO60 (-068330e) respectively in chloroform and gas phaseThemost positive charge atomwas found to beC62 in both gas(097067e 080601e and 081407e respectively at the RHF
B3PW91 and B3LYP levels) and solvent (098887e 081804eand 082650e respectively at the RHF B3PW91 and B3LYPlevels) this is due to the fact that C62 is related to negativecharge atoms (O65 O60 and C63) Mulliken electrostatic andnatural atomic charge distributions are graphically shown inFigure 2 From Figure 2 one can observe that for almost allthe methods used for charge description the most positiveand negative charge atoms were calculated at the RHF levelin both gas and chloroform and this is due to the fact thatthe effect of electron correlation is not well described in HFmethod
342 Global Reactivity Descriptors In order to understandthe relationships between structure stability and reactivity ofRubescin Emolecule the global reactivity descriptors param-eters such as chemical hardness (H) chemical potential (120583119888119901)chemical softness (s) electronegativity (119883) and electrophilic-ity index (120596) were calculated The finite difference equationgiven by (1) was used to calculate the ionization potentialand electron affinity which are generally used to calculate theabove cited parameters
119868119875 = 119864119902=119873+1 minus 119864119902=119873119864119860 = 119864119902=119873 minus 119864119902=119873minus1
(1)
The IP and EA calculated from (1) were then used to calculate119867 120583119888119901 s119883 and120596 using equations found in the literature [15ndash17] All these parameters calculated using the twomethods ingas phase are presented in Table 3 A high value of 120583119888119901 and 120596characterizes a good electrophile while a small value standsfor good nucleophile
Advances in Condensed Matter Physics 7
Table2Ex
perim
entaland
calculated3J H
-Hproton
-protoncoup
lingconstant
ofRu
bescin
Ein
gasp
hase
andin
chloroform
solutio
n
PARA
MET
ERS
RHF
B3LY
PB3
PW91
EXP[1]
Gaz
CDCl3
Gaz
CDCl3
Gaz
CDCl3
Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)H10-C9-C12-H13
455506
620
438143
649
4813
93579
459537
614
4832
85576
4616
62610
40
H10-C9-C20-H21
1695
395
1265
1698
194
1267
168824
1261
168658
1259
1685
1258
1682201
1256
120
H27-C26-C40-H41
-110
718
1065
-120311
1059
-101794
1070
-1089
1066
-104324
1069
-112
981064
65
H28-C26-C40-H41
1053029
296
103995
283
1063433
307
1053319
296
1061668
305
10496
4292
13H33-C32-C34-H35
-02873
11-012
311
-05893
11-0366
11-0566
11-033
3111
100
H47-C46-C48-H49
-613
614
382
-611286
385
-619
356
374
-618
438
375
-615
482
379
-614
875
380
42
H47-C46-C48-H50
5874
37417
587503
417
580428
427
578579
430
5853
4420
58304
4424
42
H49-C48-C51-H52
-425704
669
-421786
675
-439616
646
-433642
656
-445718
636
-439227
647
42
H50-C48-C51-H52
-164
093
1221
-163817
1218
-16522
1232
-164
673
1227
-165874
1237
-165259
1232
11H54-C53-C55-H56
-03838
11-02856
11-032
7511
-02429
11-039
2111
-03074
11H66-C64-C67-H68
-177906
1299
-177979
1299
17846
741299
1787874
131784147
1299
178548
1299
H66-C64-C67-H69
-569125
443
-569428
443
-603746
395
-599
903
4-6040
07395
-601923
397
70H66-C64-C67-H70
606324
391
604696
394
566811
447
56944
9442
566504
447
567234
446
70
8 Advances in Condensed Matter Physics
05
minus15
minus10
minus05
0
05
10
15
20
25
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Gas
minus15
minus10
minus05
0
05
10
15
20
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Mul
liken
char
ges
Mul
liken
char
ges
Chloroform
minus10
minus05
0
05
10
15
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
ESP
char
ges
ESP
char
ges
Chloroform
minus10
minus05
0
05
10
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Chloroform
minus10
minus05
0
10
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Nat
ural
atom
ic ch
arge
s
Nat
ural
atom
ic ch
arge
s
Gas
minus10
minus05
0
05
10
15
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Gas
Figure 2 Charge distribution on Rubescin E calculated at the RHF B3PW91 and B3LYP levels in both gas phase and chloroform solutionand with the 6-311++G(dp) basis set
Advances in Condensed Matter Physics 9
Table 3 Global reactivity descriptors of Rubescin E at the RHF B3LYP and B3PW91 levels in gas phase and in chloroform solution using the6-311++G(dp) basis set
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
Figure 3 Molecular orbital and the HOMO and LUMO energy of Rubescin E in gas phase
The calculated vertical IP values in gas phase are biggerthan their corresponding values in solvent From Table 3we also found that putting the molecule in solvent increasesits electron affinity From the calculated IP and EA valuesone can conclude that solvent effect increases the capacityof molecule of gaining an electron compared to donating itIt also reduces the harness of our molecule and increasesthe softness Hence the presence of solvent increases thereactivity of the molecule Rubescin
343 Frontier Molecular Orbitals The frontier molecularorbitals of Rubescin E were evaluated using the ab initio andDFT methods The 6-311G(dp) and 6-311++G(dp) basis setswere used for this purpose in gas phase and in chloroformsolutionThe results show that the energy gap of ourmoleculedecreases when diffuse functions are added onto all theatoms We also found that whenever the basis set andmethods used the energy gap is greater than 4 showing thatour molecule is hard and can be used as insulator in manyelectronic devices In Figure 3 the 3Dplots of theHOMOandLUMO orbitals computed at the RHF B3PW91 and B3LYPlevels with the 6-311G(dp) basis set are illustrated in gasphase We observed that the HOMO of Rubescin E is locatedover the furan ring at the three levels and also at the C-Cof cyclohexane ring and C-O of oxiran ring By contrast the
LUMO orbital is located over the cyclohex-2-enone ring C-C and C-O bond of tetrahydrofuran ring We can thereforeconclude that electron can easily be transferred from furanring to tetrahydrofuran ring
The total density of states (DOS) spectrum of RubescinE at the gas phase and in chloroform is given in Figure 4for each level at the 6-311++G(dp) basis set These DOSsspectra presented in Figure 4 were obtained from Gauss-Sum 30 program [18] which was used in order to show thecontributions of different group tomolecular orbital (HOMOand LUMO) From Figure 4 we observe that the HOMO-LUMO energy gap is smaller when we move from RHF toB3PW91 and from B3PW91 to B3LYP level respectively forboth gas and chloroform phases with larger values obtainedin chloroform
344 UV-Vis SpectraAnalysis Timedependent density func-tional theory (TD-DFT) was used in gas phase at the twolevels B3PW91 and B3LYP with the 6-311++G(dp) basis setin order to determine the first six excited states to investigatethe UV-vis absorption spectra of themoleculeThe excitationenergy (E) wavelength (120582) and oscillator strength (f) alongwith their major contributions are given in Table 4 and theirresults are compared to experiment
10 Advances in Condensed Matter Physics
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3LYP Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
Energy (eV)
B3LYP Gas
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Gas
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Chloroform
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Gas
4293 eV
9797 eV9516 eV
4315 eV 4333 eV
4314 eV
Figure 4 Total density of state (DOS) spectrum of Rubescin E at the RHF B3PW91 and B3LYP levels in both gas and chloroform phase andwith the 6-311++G(dp) basis set
Two intense electronic transitions were predicted at44934 eV (27592 nm) and 34415 eV (36027 nm) withoscillator strengths of 00043 and 00014 respectively at theB3PW91 level and 45123 eV (27477 nm) and 34603 eV(35831 nm) with oscillator strengths of 00041 and 00014respectively at the B3LYP levelWe observed from the spectra
that the maximum absorption wavelength corresponds tothe electronic transition from HOMO to LUMO+1 with100 contribution followed by the electronic transition fromHOMO to LUMO with 99 contribution at the two levelsThe experimental absorption spectra of the title moleculepredict two bands at 254 nm and 365 nm The error between
Advances in Condensed Matter Physics 11
Table 4Theoretical absorption wavelength (120582) excitation energy (E) and oscillator strengths of Rubescin E at the B3PW91 and B3LYP levelsin gas with the 6-311++G(dp) basis set
Excited states Exp [1] B3PW91 B3LYP120582 (nm) 120582 (nm) E (eV) f Major contributions 120582 (nm) E (eV) f Major contributions
1 365 36027 34415 00014 H-1 997888rarr L (93) 35831 34603 00014 H-1 997888rarr L (93)2 31218 39715 00000 H 997888rarr L (99) 31369 39524 00000 H 997888rarr L (99)3 254 27592 44934 00043 H-4 997888rarr L (24) 27477 45123 00041 H-4 997888rarr L (28)4 27266 45473 00006 H-4 997888rarr L (50) 27227 45538 00004 H-4 997888rarr L (44)5 26956 45994 00001 H-4 997888rarr L (19) 26847 46182 00001 H-4 997888rarr L (20)6 26121 47465 00000 H 997888rarr L+1 (100) 26316 47113 00000 H 997888rarr L+1 (100)
200 250 300 350 400 450 5000
50
100
150
200
250
300
350
wavelength (nm)
Epsi
lon
B3LYP
200 250 300 350 400 450 5000
50100150200250300350400
Wavelength (nm)
Epsi
lon
B3PW91
UV vis spectrumOscillator strength
UV vis spectrumOscillator strength
Figure 5 Theoretical absorption spectra of Rubescin E at the B3PW91 and B3LYP levels in gas with the 6-311++G(dp) basis set
the theoretical and experimental results range from - 473 nmto 2192 nm at the B3PW91 and from - 669 nm to 2077 nm atthe B3LYP levelThese errors are due to the fact that only onemolecule was considered for simulationThe theoretical UV-vis absorption spectra of Rubescin E in gas phase are shownin Figure 5
345 Dipole Moment (120583119863119872) Average Polarizability (120572) FirstStatic Hyperpolarizability (120573) and Anisotropy of PolarizationIn this work the dipole moment 120583119863119872 average polarizability120572 first static hyperpolarizability 120573 and anisotropy of polar-izability Δ120572 of Rubescin E were evaluated in both gas phaseand chloroform solution in order to define the nonlinearityof Rubescin E The finite-field approach was used for thispurpose Equations (2) (3) (4) and (5) were used to calculatethe polarizability dipole moment anisotropy of polarizabil-ity and first static hyperpolarizability respectively using thex 119910 119911 components obtained from Gaussian 09 W outputThe calculated parameters were presented in Table 5 at thethree levels with the 6-311++G(dp) basis set
The calculated values of polarizability and first static hyper-polarizability obtained from Gaussian output are in atomicunit These values were then converted into electrostatic unit(esu) for comparison purpose (for 120572 1 au = 01482 x 10minus24esu for 120573 1 au = 86393 x 10minus33 esu) [19ndash22] From a givingmolecule when these values (120583119863119872 and 120573) are greater thanthose of urea the molecule is said to have good active NLOproperties We observed from our results that the values of120572 120573 and 120583119863119872 are higher in solvent than their correspondingvalue in gas phase 120573 and 120583119863119872 of Rubescin E calculated at the6-311++G(dp) basis set using different methods were greaterthan those of urea These values calculated using the HF6-311D(dp)method (120583119863119872 = 52175Dand120573 = 17603169x10minus33esu) were also higher than those of urea (120583119863119872 = 38851D and120573 = 372811990910minus33esu) obtained using the same method and
12 Advances in Condensed Matter Physics
Table 5 Electric dipole moment polarizability anisotropy of polarization first-order hyperpolarizability and molar refractivity of RubescinE at the RHF B3LYP and B3PW91 levels with the 6-311G (d p) and 6-311++G (d p) basis sets
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
Table 6 Calculated values of polarization density (P) average electric field (E) electric susceptibility (120594) refractive index (120578) dielectricconstant (E) magnitude of the displacement (D) and molar refractivity (MR) of Rubescin E molecule obtained at the RHF B3LYP andB3PW91 levels with the 6-311++G(dp) basis set
Parameters RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
basis set [21] Hence Rubescin E can be considered to havegood active NLO properties and this is due to the delocalize electron on the furan ring
346 Optoelectronic Properties In order to recognize theoptoelectronic nature of Rubescin E for different devicesapplications some parameters such as electric field (E) elec-tric polarization (P) electric susceptibility (120594) permittivity(E) refractive index (120578) and electric displacement (D) werecalculated using equations given in the literature [23ndash25]We observed from Table 6 that the results of the calculatedparameters are slightly different when we move from onelevel to another and also when the medium changes Thevalue of electric field is greater in a solution of chloroformthan its corresponding value in gas phase This is because the
polarizability increases in presence of a solvent The valuesof electric susceptibility dielectric constant and refractiveindex are greater at B3LYP level compared to their corre-sponding value at the RHF All the calculated parametersof optoelectronic properties obtained at the B3LYP level aresimilar to those obtained at the B3PW91 level None of theseparameters have been determined before either theoreticallyor experimentally
One of the central goals of this study is to understandthe underlying structurendashproperty relationships whichmightform the basis for a ldquomolecular engineeringrdquo approachto electronics optoelectronics and photonics The molarrefractivity of our molecule known to be an importantparameter in quantitative structurendashproperty relationshipanalysis was calculated for this purpose The value of the
Advances in Condensed Matter Physics 13
Table 7 Experimental and calculated 1HNMR chemical shifts 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
molar refractivity was calculated at the three levels in bothgas and chloroform using the 6-311++G(dp) basis set TheLorenz-Lorentz equation was used for this calculation [2627] and its results are listed in Table 6
The high values of molar refractivity polarizabilityanisotropy of polarizability and first static hyperpolarizabil-ity of Rubescin E molecule show that the molecule has goodquantitative structurendashproperty relationship analysis andmight therefore form the basis for a ldquomolecular engineeringrdquoapproach to electronics optoelectronics and photonics
35 NMR Study of Rubescin E After the optimization ofthe Rubescin E molecule the 1H and 13C chemical shiftswere calculated at the RHF B3LYP and B3PW91 levels of thetheory using the 6-311++G(dp) basis set In order to comparethe calculated values of 1H and 13C chemical shifts withexperimental results we also need to calculate the absoluteshielding value of 1Hand 13C for the tetramethylsilane (TMS)using the same methods above The GIAO (Gauge InvariantAtomic Orbitals) approach known to provide satisfactorychemical shifts for different nuclei with larger molecules [28]was used for this purpose and the following equation
120575119894 (119901119901119898) = 119894119904119900119905119903119900119901119894119888 (119879119872119878119894) minus 119894119904119900119905119903119900119901119894119888 (119894) (6)
where 119894 is the atom type and was used to convert the chemicalshielding to chemical shifts
The experimental and calculated chemical shifts of 1Halong with their corresponding error are listed in Table 7From our results we observed that all the methods provideresults which are very close to experiment since the errorsbetween the experimental and calculated results are smaller
In order to compare experimental and theoretical resultsa linear correlation of 1H-NMR chemical shifts was estab-lished as shown in Figure 6 The regression line was plottedusing the following equations 120575119888119886119897 = 098880120575119890119909119901 minus 017198120575119888119886119897 = 097379120575119890119909119901 + 018796 and 120575119888119886119897 = 097069120575119890119909119901 +019387 respectively at the RHF B3PW91 and B3LYP levelsof the theory The theoretical results obtained from usingthe 6-311++G(dp) basis set show good correlation withexperiment since and the calculated R-square values arefound to be close to 1 at each level as shown by Figure 6
The calculated and experimental 13C chemical shifts ofour molecule are given in Table 8 and their comparison canbe found in Figure 7 The linear regression line plotted inFigure 7 shows that theoretical results are in good agreementwith experiment This is confirmed by the linear correlationcoefficient calculated here as R-square at the RHF B3PW91and B3LYP levels using the 6-311++G(dp) basis set
The following regression line plotted for each level usingthe general equation 120575119888119886119897 = 119886120575119890119909119901 + 119887 where a and b are givenin Figure 7 shows that the calculated 13C chemical shiftscorrelate very well with experiment The linear correlationcoefficient calculated as R-square found in Figure 7 alsoconfirms this
36 Vibrational Frequencies Analysis The vibrational fre-quencies of our molecule were computed by using B3LYP6-311G(dp) method in both gas phase and chloroform Theexperimental IR vibrational frequencies obtained for the twocarbonyl moiety present in our structure along with thecalculated scaled and unscaled vibrational frequencies IRand Raman frequencies with their approximate descriptions
14 Advances in Condensed Matter Physics
Table 8 Experimental and calculated 13C NMR chemical shift 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
y = +100x -0254 max dev150 r=0960 y = +0987x +0127 max dev104 r=0979
y = +0980x +0141 max dev103 r=0981
y = +100x -0254 max dev150 y = +0987x +0127 max dev104
y = +0980x +0141 max dev103
Figure 6 Comparison of experimental and theoretical 1H chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set in chloroform
Advances in Condensed Matter Physics 15
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3LYP6-311++G(dp)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3PW916-311++G(dp)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
minus250
255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
RHF6-311++G(dp)
y = +107x -517 max dev836 r=0994 y = +105x +238 max dev648 r=0998
y = +105x +354 max dev541 r=0998
y = +107x -517 max dev836 y = +105x +238 max dev648
y = +105x +354 max dev541
Figure 7 Comparison of experimental and theoretical 13C chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set
are given in Table 9 The rest of the vibrational parameterof Rubescin E molecule which is not described in Table 9can be obtained from Supplementary Material S2 The scalefactor was determined as the mean value of the scale factorthat matches correctly for the C=O stretching and the givenexperimental valueThe obtained scale factor was 09706 Noimaginary frequencies were found showing that structure ofthe molecule Rubescin E is stable in both gas and solventFigure 8 gives the representation of the scaled IR intensity andRaman scattering activity
The C=O double bond gives rise to a very intenseabsorption band in IR spectrum The position and intensityof this band range from 1870 cmminus1 to 1540 cmminus1 dependingon the physical state electronic andmass effects of neighbor-ing substituents intra- and intermolecular interactions andconjugations [29] The C=O double bond absorption spectra
were observed experimentally at 1720 cmminus1 and 1664 cmminus1[1] In this study the vibrational mode of C=O was found at172620 cmminus1 and 169057 cmminus1 gas phase and at 170101 cmminus1and 166759 cmminus1 in chloroform There is good agreementbetween the vibrational modes with experimental values
4 Conclusion
In this study the geometry optimization of Rubescin E hasbeen carried out using ab initio HF and density functionaltheoryDFT (B3LYP and B3PW91)methods in both gas phaseand chloroform solution with the 6-311++G(dp) basis setThe optimized parameters were compared to those of someexisting groups of compound present in our molecule sincenone of this have been done before for the title molecule andgood agreement was found In order to confirm the geometry
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
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Journal ofEngineeringVolume 2018
Submit your manuscripts atwwwhindawicom
Advances in Condensed Matter Physics 7
Table2Ex
perim
entaland
calculated3J H
-Hproton
-protoncoup
lingconstant
ofRu
bescin
Ein
gasp
hase
andin
chloroform
solutio
n
PARA
MET
ERS
RHF
B3LY
PB3
PW91
EXP[1]
Gaz
CDCl3
Gaz
CDCl3
Gaz
CDCl3
Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)Ang
les(∘ )3J H
-H(H
z)H10-C9-C12-H13
455506
620
438143
649
4813
93579
459537
614
4832
85576
4616
62610
40
H10-C9-C20-H21
1695
395
1265
1698
194
1267
168824
1261
168658
1259
1685
1258
1682201
1256
120
H27-C26-C40-H41
-110
718
1065
-120311
1059
-101794
1070
-1089
1066
-104324
1069
-112
981064
65
H28-C26-C40-H41
1053029
296
103995
283
1063433
307
1053319
296
1061668
305
10496
4292
13H33-C32-C34-H35
-02873
11-012
311
-05893
11-0366
11-0566
11-033
3111
100
H47-C46-C48-H49
-613
614
382
-611286
385
-619
356
374
-618
438
375
-615
482
379
-614
875
380
42
H47-C46-C48-H50
5874
37417
587503
417
580428
427
578579
430
5853
4420
58304
4424
42
H49-C48-C51-H52
-425704
669
-421786
675
-439616
646
-433642
656
-445718
636
-439227
647
42
H50-C48-C51-H52
-164
093
1221
-163817
1218
-16522
1232
-164
673
1227
-165874
1237
-165259
1232
11H54-C53-C55-H56
-03838
11-02856
11-032
7511
-02429
11-039
2111
-03074
11H66-C64-C67-H68
-177906
1299
-177979
1299
17846
741299
1787874
131784147
1299
178548
1299
H66-C64-C67-H69
-569125
443
-569428
443
-603746
395
-599
903
4-6040
07395
-601923
397
70H66-C64-C67-H70
606324
391
604696
394
566811
447
56944
9442
566504
447
567234
446
70
8 Advances in Condensed Matter Physics
05
minus15
minus10
minus05
0
05
10
15
20
25
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Gas
minus15
minus10
minus05
0
05
10
15
20
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Mul
liken
char
ges
Mul
liken
char
ges
Chloroform
minus10
minus05
0
05
10
15
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
ESP
char
ges
ESP
char
ges
Chloroform
minus10
minus05
0
05
10
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Chloroform
minus10
minus05
0
10
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Nat
ural
atom
ic ch
arge
s
Nat
ural
atom
ic ch
arge
s
Gas
minus10
minus05
0
05
10
15
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Gas
Figure 2 Charge distribution on Rubescin E calculated at the RHF B3PW91 and B3LYP levels in both gas phase and chloroform solutionand with the 6-311++G(dp) basis set
Advances in Condensed Matter Physics 9
Table 3 Global reactivity descriptors of Rubescin E at the RHF B3LYP and B3PW91 levels in gas phase and in chloroform solution using the6-311++G(dp) basis set
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
Figure 3 Molecular orbital and the HOMO and LUMO energy of Rubescin E in gas phase
The calculated vertical IP values in gas phase are biggerthan their corresponding values in solvent From Table 3we also found that putting the molecule in solvent increasesits electron affinity From the calculated IP and EA valuesone can conclude that solvent effect increases the capacityof molecule of gaining an electron compared to donating itIt also reduces the harness of our molecule and increasesthe softness Hence the presence of solvent increases thereactivity of the molecule Rubescin
343 Frontier Molecular Orbitals The frontier molecularorbitals of Rubescin E were evaluated using the ab initio andDFT methods The 6-311G(dp) and 6-311++G(dp) basis setswere used for this purpose in gas phase and in chloroformsolutionThe results show that the energy gap of ourmoleculedecreases when diffuse functions are added onto all theatoms We also found that whenever the basis set andmethods used the energy gap is greater than 4 showing thatour molecule is hard and can be used as insulator in manyelectronic devices In Figure 3 the 3Dplots of theHOMOandLUMO orbitals computed at the RHF B3PW91 and B3LYPlevels with the 6-311G(dp) basis set are illustrated in gasphase We observed that the HOMO of Rubescin E is locatedover the furan ring at the three levels and also at the C-Cof cyclohexane ring and C-O of oxiran ring By contrast the
LUMO orbital is located over the cyclohex-2-enone ring C-C and C-O bond of tetrahydrofuran ring We can thereforeconclude that electron can easily be transferred from furanring to tetrahydrofuran ring
The total density of states (DOS) spectrum of RubescinE at the gas phase and in chloroform is given in Figure 4for each level at the 6-311++G(dp) basis set These DOSsspectra presented in Figure 4 were obtained from Gauss-Sum 30 program [18] which was used in order to show thecontributions of different group tomolecular orbital (HOMOand LUMO) From Figure 4 we observe that the HOMO-LUMO energy gap is smaller when we move from RHF toB3PW91 and from B3PW91 to B3LYP level respectively forboth gas and chloroform phases with larger values obtainedin chloroform
344 UV-Vis SpectraAnalysis Timedependent density func-tional theory (TD-DFT) was used in gas phase at the twolevels B3PW91 and B3LYP with the 6-311++G(dp) basis setin order to determine the first six excited states to investigatethe UV-vis absorption spectra of themoleculeThe excitationenergy (E) wavelength (120582) and oscillator strength (f) alongwith their major contributions are given in Table 4 and theirresults are compared to experiment
10 Advances in Condensed Matter Physics
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3LYP Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
Energy (eV)
B3LYP Gas
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Gas
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Chloroform
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Gas
4293 eV
9797 eV9516 eV
4315 eV 4333 eV
4314 eV
Figure 4 Total density of state (DOS) spectrum of Rubescin E at the RHF B3PW91 and B3LYP levels in both gas and chloroform phase andwith the 6-311++G(dp) basis set
Two intense electronic transitions were predicted at44934 eV (27592 nm) and 34415 eV (36027 nm) withoscillator strengths of 00043 and 00014 respectively at theB3PW91 level and 45123 eV (27477 nm) and 34603 eV(35831 nm) with oscillator strengths of 00041 and 00014respectively at the B3LYP levelWe observed from the spectra
that the maximum absorption wavelength corresponds tothe electronic transition from HOMO to LUMO+1 with100 contribution followed by the electronic transition fromHOMO to LUMO with 99 contribution at the two levelsThe experimental absorption spectra of the title moleculepredict two bands at 254 nm and 365 nm The error between
Advances in Condensed Matter Physics 11
Table 4Theoretical absorption wavelength (120582) excitation energy (E) and oscillator strengths of Rubescin E at the B3PW91 and B3LYP levelsin gas with the 6-311++G(dp) basis set
Excited states Exp [1] B3PW91 B3LYP120582 (nm) 120582 (nm) E (eV) f Major contributions 120582 (nm) E (eV) f Major contributions
1 365 36027 34415 00014 H-1 997888rarr L (93) 35831 34603 00014 H-1 997888rarr L (93)2 31218 39715 00000 H 997888rarr L (99) 31369 39524 00000 H 997888rarr L (99)3 254 27592 44934 00043 H-4 997888rarr L (24) 27477 45123 00041 H-4 997888rarr L (28)4 27266 45473 00006 H-4 997888rarr L (50) 27227 45538 00004 H-4 997888rarr L (44)5 26956 45994 00001 H-4 997888rarr L (19) 26847 46182 00001 H-4 997888rarr L (20)6 26121 47465 00000 H 997888rarr L+1 (100) 26316 47113 00000 H 997888rarr L+1 (100)
200 250 300 350 400 450 5000
50
100
150
200
250
300
350
wavelength (nm)
Epsi
lon
B3LYP
200 250 300 350 400 450 5000
50100150200250300350400
Wavelength (nm)
Epsi
lon
B3PW91
UV vis spectrumOscillator strength
UV vis spectrumOscillator strength
Figure 5 Theoretical absorption spectra of Rubescin E at the B3PW91 and B3LYP levels in gas with the 6-311++G(dp) basis set
the theoretical and experimental results range from - 473 nmto 2192 nm at the B3PW91 and from - 669 nm to 2077 nm atthe B3LYP levelThese errors are due to the fact that only onemolecule was considered for simulationThe theoretical UV-vis absorption spectra of Rubescin E in gas phase are shownin Figure 5
345 Dipole Moment (120583119863119872) Average Polarizability (120572) FirstStatic Hyperpolarizability (120573) and Anisotropy of PolarizationIn this work the dipole moment 120583119863119872 average polarizability120572 first static hyperpolarizability 120573 and anisotropy of polar-izability Δ120572 of Rubescin E were evaluated in both gas phaseand chloroform solution in order to define the nonlinearityof Rubescin E The finite-field approach was used for thispurpose Equations (2) (3) (4) and (5) were used to calculatethe polarizability dipole moment anisotropy of polarizabil-ity and first static hyperpolarizability respectively using thex 119910 119911 components obtained from Gaussian 09 W outputThe calculated parameters were presented in Table 5 at thethree levels with the 6-311++G(dp) basis set
The calculated values of polarizability and first static hyper-polarizability obtained from Gaussian output are in atomicunit These values were then converted into electrostatic unit(esu) for comparison purpose (for 120572 1 au = 01482 x 10minus24esu for 120573 1 au = 86393 x 10minus33 esu) [19ndash22] From a givingmolecule when these values (120583119863119872 and 120573) are greater thanthose of urea the molecule is said to have good active NLOproperties We observed from our results that the values of120572 120573 and 120583119863119872 are higher in solvent than their correspondingvalue in gas phase 120573 and 120583119863119872 of Rubescin E calculated at the6-311++G(dp) basis set using different methods were greaterthan those of urea These values calculated using the HF6-311D(dp)method (120583119863119872 = 52175Dand120573 = 17603169x10minus33esu) were also higher than those of urea (120583119863119872 = 38851D and120573 = 372811990910minus33esu) obtained using the same method and
12 Advances in Condensed Matter Physics
Table 5 Electric dipole moment polarizability anisotropy of polarization first-order hyperpolarizability and molar refractivity of RubescinE at the RHF B3LYP and B3PW91 levels with the 6-311G (d p) and 6-311++G (d p) basis sets
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
Table 6 Calculated values of polarization density (P) average electric field (E) electric susceptibility (120594) refractive index (120578) dielectricconstant (E) magnitude of the displacement (D) and molar refractivity (MR) of Rubescin E molecule obtained at the RHF B3LYP andB3PW91 levels with the 6-311++G(dp) basis set
Parameters RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
basis set [21] Hence Rubescin E can be considered to havegood active NLO properties and this is due to the delocalize electron on the furan ring
346 Optoelectronic Properties In order to recognize theoptoelectronic nature of Rubescin E for different devicesapplications some parameters such as electric field (E) elec-tric polarization (P) electric susceptibility (120594) permittivity(E) refractive index (120578) and electric displacement (D) werecalculated using equations given in the literature [23ndash25]We observed from Table 6 that the results of the calculatedparameters are slightly different when we move from onelevel to another and also when the medium changes Thevalue of electric field is greater in a solution of chloroformthan its corresponding value in gas phase This is because the
polarizability increases in presence of a solvent The valuesof electric susceptibility dielectric constant and refractiveindex are greater at B3LYP level compared to their corre-sponding value at the RHF All the calculated parametersof optoelectronic properties obtained at the B3LYP level aresimilar to those obtained at the B3PW91 level None of theseparameters have been determined before either theoreticallyor experimentally
One of the central goals of this study is to understandthe underlying structurendashproperty relationships whichmightform the basis for a ldquomolecular engineeringrdquo approachto electronics optoelectronics and photonics The molarrefractivity of our molecule known to be an importantparameter in quantitative structurendashproperty relationshipanalysis was calculated for this purpose The value of the
Advances in Condensed Matter Physics 13
Table 7 Experimental and calculated 1HNMR chemical shifts 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
molar refractivity was calculated at the three levels in bothgas and chloroform using the 6-311++G(dp) basis set TheLorenz-Lorentz equation was used for this calculation [2627] and its results are listed in Table 6
The high values of molar refractivity polarizabilityanisotropy of polarizability and first static hyperpolarizabil-ity of Rubescin E molecule show that the molecule has goodquantitative structurendashproperty relationship analysis andmight therefore form the basis for a ldquomolecular engineeringrdquoapproach to electronics optoelectronics and photonics
35 NMR Study of Rubescin E After the optimization ofthe Rubescin E molecule the 1H and 13C chemical shiftswere calculated at the RHF B3LYP and B3PW91 levels of thetheory using the 6-311++G(dp) basis set In order to comparethe calculated values of 1H and 13C chemical shifts withexperimental results we also need to calculate the absoluteshielding value of 1Hand 13C for the tetramethylsilane (TMS)using the same methods above The GIAO (Gauge InvariantAtomic Orbitals) approach known to provide satisfactorychemical shifts for different nuclei with larger molecules [28]was used for this purpose and the following equation
120575119894 (119901119901119898) = 119894119904119900119905119903119900119901119894119888 (119879119872119878119894) minus 119894119904119900119905119903119900119901119894119888 (119894) (6)
where 119894 is the atom type and was used to convert the chemicalshielding to chemical shifts
The experimental and calculated chemical shifts of 1Halong with their corresponding error are listed in Table 7From our results we observed that all the methods provideresults which are very close to experiment since the errorsbetween the experimental and calculated results are smaller
In order to compare experimental and theoretical resultsa linear correlation of 1H-NMR chemical shifts was estab-lished as shown in Figure 6 The regression line was plottedusing the following equations 120575119888119886119897 = 098880120575119890119909119901 minus 017198120575119888119886119897 = 097379120575119890119909119901 + 018796 and 120575119888119886119897 = 097069120575119890119909119901 +019387 respectively at the RHF B3PW91 and B3LYP levelsof the theory The theoretical results obtained from usingthe 6-311++G(dp) basis set show good correlation withexperiment since and the calculated R-square values arefound to be close to 1 at each level as shown by Figure 6
The calculated and experimental 13C chemical shifts ofour molecule are given in Table 8 and their comparison canbe found in Figure 7 The linear regression line plotted inFigure 7 shows that theoretical results are in good agreementwith experiment This is confirmed by the linear correlationcoefficient calculated here as R-square at the RHF B3PW91and B3LYP levels using the 6-311++G(dp) basis set
The following regression line plotted for each level usingthe general equation 120575119888119886119897 = 119886120575119890119909119901 + 119887 where a and b are givenin Figure 7 shows that the calculated 13C chemical shiftscorrelate very well with experiment The linear correlationcoefficient calculated as R-square found in Figure 7 alsoconfirms this
36 Vibrational Frequencies Analysis The vibrational fre-quencies of our molecule were computed by using B3LYP6-311G(dp) method in both gas phase and chloroform Theexperimental IR vibrational frequencies obtained for the twocarbonyl moiety present in our structure along with thecalculated scaled and unscaled vibrational frequencies IRand Raman frequencies with their approximate descriptions
14 Advances in Condensed Matter Physics
Table 8 Experimental and calculated 13C NMR chemical shift 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
y = +100x -0254 max dev150 r=0960 y = +0987x +0127 max dev104 r=0979
y = +0980x +0141 max dev103 r=0981
y = +100x -0254 max dev150 y = +0987x +0127 max dev104
y = +0980x +0141 max dev103
Figure 6 Comparison of experimental and theoretical 1H chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set in chloroform
Advances in Condensed Matter Physics 15
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3LYP6-311++G(dp)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3PW916-311++G(dp)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
minus250
255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
RHF6-311++G(dp)
y = +107x -517 max dev836 r=0994 y = +105x +238 max dev648 r=0998
y = +105x +354 max dev541 r=0998
y = +107x -517 max dev836 y = +105x +238 max dev648
y = +105x +354 max dev541
Figure 7 Comparison of experimental and theoretical 13C chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set
are given in Table 9 The rest of the vibrational parameterof Rubescin E molecule which is not described in Table 9can be obtained from Supplementary Material S2 The scalefactor was determined as the mean value of the scale factorthat matches correctly for the C=O stretching and the givenexperimental valueThe obtained scale factor was 09706 Noimaginary frequencies were found showing that structure ofthe molecule Rubescin E is stable in both gas and solventFigure 8 gives the representation of the scaled IR intensity andRaman scattering activity
The C=O double bond gives rise to a very intenseabsorption band in IR spectrum The position and intensityof this band range from 1870 cmminus1 to 1540 cmminus1 dependingon the physical state electronic andmass effects of neighbor-ing substituents intra- and intermolecular interactions andconjugations [29] The C=O double bond absorption spectra
were observed experimentally at 1720 cmminus1 and 1664 cmminus1[1] In this study the vibrational mode of C=O was found at172620 cmminus1 and 169057 cmminus1 gas phase and at 170101 cmminus1and 166759 cmminus1 in chloroform There is good agreementbetween the vibrational modes with experimental values
4 Conclusion
In this study the geometry optimization of Rubescin E hasbeen carried out using ab initio HF and density functionaltheoryDFT (B3LYP and B3PW91)methods in both gas phaseand chloroform solution with the 6-311++G(dp) basis setThe optimized parameters were compared to those of someexisting groups of compound present in our molecule sincenone of this have been done before for the title molecule andgood agreement was found In order to confirm the geometry
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
Applied Bionics and BiomechanicsHindawiwwwhindawicom Volume 2018
Advances inOptoElectronics
Hindawiwwwhindawicom
Volume 2018
Hindawiwwwhindawicom Volume 2018
Mathematical PhysicsAdvances in
Hindawiwwwhindawicom Volume 2018
ChemistryAdvances in
Hindawiwwwhindawicom Volume 2018
Journal of
Chemistry
Hindawiwwwhindawicom Volume 2018
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International Journal of
RotatingMachinery
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom
Journal ofEngineeringVolume 2018
Submit your manuscripts atwwwhindawicom
8 Advances in Condensed Matter Physics
05
minus15
minus10
minus05
0
05
10
15
20
25
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Gas
minus15
minus10
minus05
0
05
10
15
20
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Mul
liken
char
ges
Mul
liken
char
ges
Chloroform
minus10
minus05
0
05
10
15
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
ESP
char
ges
ESP
char
ges
Chloroform
minus10
minus05
0
05
10
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Chloroform
minus10
minus05
0
10
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Nat
ural
atom
ic ch
arge
s
Nat
ural
atom
ic ch
arge
s
Gas
minus10
minus05
0
05
10
15
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
B3LYPB3PW91RHF
Atoms number
Gas
Figure 2 Charge distribution on Rubescin E calculated at the RHF B3PW91 and B3LYP levels in both gas phase and chloroform solutionand with the 6-311++G(dp) basis set
Advances in Condensed Matter Physics 9
Table 3 Global reactivity descriptors of Rubescin E at the RHF B3LYP and B3PW91 levels in gas phase and in chloroform solution using the6-311++G(dp) basis set
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
Figure 3 Molecular orbital and the HOMO and LUMO energy of Rubescin E in gas phase
The calculated vertical IP values in gas phase are biggerthan their corresponding values in solvent From Table 3we also found that putting the molecule in solvent increasesits electron affinity From the calculated IP and EA valuesone can conclude that solvent effect increases the capacityof molecule of gaining an electron compared to donating itIt also reduces the harness of our molecule and increasesthe softness Hence the presence of solvent increases thereactivity of the molecule Rubescin
343 Frontier Molecular Orbitals The frontier molecularorbitals of Rubescin E were evaluated using the ab initio andDFT methods The 6-311G(dp) and 6-311++G(dp) basis setswere used for this purpose in gas phase and in chloroformsolutionThe results show that the energy gap of ourmoleculedecreases when diffuse functions are added onto all theatoms We also found that whenever the basis set andmethods used the energy gap is greater than 4 showing thatour molecule is hard and can be used as insulator in manyelectronic devices In Figure 3 the 3Dplots of theHOMOandLUMO orbitals computed at the RHF B3PW91 and B3LYPlevels with the 6-311G(dp) basis set are illustrated in gasphase We observed that the HOMO of Rubescin E is locatedover the furan ring at the three levels and also at the C-Cof cyclohexane ring and C-O of oxiran ring By contrast the
LUMO orbital is located over the cyclohex-2-enone ring C-C and C-O bond of tetrahydrofuran ring We can thereforeconclude that electron can easily be transferred from furanring to tetrahydrofuran ring
The total density of states (DOS) spectrum of RubescinE at the gas phase and in chloroform is given in Figure 4for each level at the 6-311++G(dp) basis set These DOSsspectra presented in Figure 4 were obtained from Gauss-Sum 30 program [18] which was used in order to show thecontributions of different group tomolecular orbital (HOMOand LUMO) From Figure 4 we observe that the HOMO-LUMO energy gap is smaller when we move from RHF toB3PW91 and from B3PW91 to B3LYP level respectively forboth gas and chloroform phases with larger values obtainedin chloroform
344 UV-Vis SpectraAnalysis Timedependent density func-tional theory (TD-DFT) was used in gas phase at the twolevels B3PW91 and B3LYP with the 6-311++G(dp) basis setin order to determine the first six excited states to investigatethe UV-vis absorption spectra of themoleculeThe excitationenergy (E) wavelength (120582) and oscillator strength (f) alongwith their major contributions are given in Table 4 and theirresults are compared to experiment
10 Advances in Condensed Matter Physics
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3LYP Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
Energy (eV)
B3LYP Gas
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Gas
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Chloroform
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Gas
4293 eV
9797 eV9516 eV
4315 eV 4333 eV
4314 eV
Figure 4 Total density of state (DOS) spectrum of Rubescin E at the RHF B3PW91 and B3LYP levels in both gas and chloroform phase andwith the 6-311++G(dp) basis set
Two intense electronic transitions were predicted at44934 eV (27592 nm) and 34415 eV (36027 nm) withoscillator strengths of 00043 and 00014 respectively at theB3PW91 level and 45123 eV (27477 nm) and 34603 eV(35831 nm) with oscillator strengths of 00041 and 00014respectively at the B3LYP levelWe observed from the spectra
that the maximum absorption wavelength corresponds tothe electronic transition from HOMO to LUMO+1 with100 contribution followed by the electronic transition fromHOMO to LUMO with 99 contribution at the two levelsThe experimental absorption spectra of the title moleculepredict two bands at 254 nm and 365 nm The error between
Advances in Condensed Matter Physics 11
Table 4Theoretical absorption wavelength (120582) excitation energy (E) and oscillator strengths of Rubescin E at the B3PW91 and B3LYP levelsin gas with the 6-311++G(dp) basis set
Excited states Exp [1] B3PW91 B3LYP120582 (nm) 120582 (nm) E (eV) f Major contributions 120582 (nm) E (eV) f Major contributions
1 365 36027 34415 00014 H-1 997888rarr L (93) 35831 34603 00014 H-1 997888rarr L (93)2 31218 39715 00000 H 997888rarr L (99) 31369 39524 00000 H 997888rarr L (99)3 254 27592 44934 00043 H-4 997888rarr L (24) 27477 45123 00041 H-4 997888rarr L (28)4 27266 45473 00006 H-4 997888rarr L (50) 27227 45538 00004 H-4 997888rarr L (44)5 26956 45994 00001 H-4 997888rarr L (19) 26847 46182 00001 H-4 997888rarr L (20)6 26121 47465 00000 H 997888rarr L+1 (100) 26316 47113 00000 H 997888rarr L+1 (100)
200 250 300 350 400 450 5000
50
100
150
200
250
300
350
wavelength (nm)
Epsi
lon
B3LYP
200 250 300 350 400 450 5000
50100150200250300350400
Wavelength (nm)
Epsi
lon
B3PW91
UV vis spectrumOscillator strength
UV vis spectrumOscillator strength
Figure 5 Theoretical absorption spectra of Rubescin E at the B3PW91 and B3LYP levels in gas with the 6-311++G(dp) basis set
the theoretical and experimental results range from - 473 nmto 2192 nm at the B3PW91 and from - 669 nm to 2077 nm atthe B3LYP levelThese errors are due to the fact that only onemolecule was considered for simulationThe theoretical UV-vis absorption spectra of Rubescin E in gas phase are shownin Figure 5
345 Dipole Moment (120583119863119872) Average Polarizability (120572) FirstStatic Hyperpolarizability (120573) and Anisotropy of PolarizationIn this work the dipole moment 120583119863119872 average polarizability120572 first static hyperpolarizability 120573 and anisotropy of polar-izability Δ120572 of Rubescin E were evaluated in both gas phaseand chloroform solution in order to define the nonlinearityof Rubescin E The finite-field approach was used for thispurpose Equations (2) (3) (4) and (5) were used to calculatethe polarizability dipole moment anisotropy of polarizabil-ity and first static hyperpolarizability respectively using thex 119910 119911 components obtained from Gaussian 09 W outputThe calculated parameters were presented in Table 5 at thethree levels with the 6-311++G(dp) basis set
The calculated values of polarizability and first static hyper-polarizability obtained from Gaussian output are in atomicunit These values were then converted into electrostatic unit(esu) for comparison purpose (for 120572 1 au = 01482 x 10minus24esu for 120573 1 au = 86393 x 10minus33 esu) [19ndash22] From a givingmolecule when these values (120583119863119872 and 120573) are greater thanthose of urea the molecule is said to have good active NLOproperties We observed from our results that the values of120572 120573 and 120583119863119872 are higher in solvent than their correspondingvalue in gas phase 120573 and 120583119863119872 of Rubescin E calculated at the6-311++G(dp) basis set using different methods were greaterthan those of urea These values calculated using the HF6-311D(dp)method (120583119863119872 = 52175Dand120573 = 17603169x10minus33esu) were also higher than those of urea (120583119863119872 = 38851D and120573 = 372811990910minus33esu) obtained using the same method and
12 Advances in Condensed Matter Physics
Table 5 Electric dipole moment polarizability anisotropy of polarization first-order hyperpolarizability and molar refractivity of RubescinE at the RHF B3LYP and B3PW91 levels with the 6-311G (d p) and 6-311++G (d p) basis sets
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
Table 6 Calculated values of polarization density (P) average electric field (E) electric susceptibility (120594) refractive index (120578) dielectricconstant (E) magnitude of the displacement (D) and molar refractivity (MR) of Rubescin E molecule obtained at the RHF B3LYP andB3PW91 levels with the 6-311++G(dp) basis set
Parameters RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
basis set [21] Hence Rubescin E can be considered to havegood active NLO properties and this is due to the delocalize electron on the furan ring
346 Optoelectronic Properties In order to recognize theoptoelectronic nature of Rubescin E for different devicesapplications some parameters such as electric field (E) elec-tric polarization (P) electric susceptibility (120594) permittivity(E) refractive index (120578) and electric displacement (D) werecalculated using equations given in the literature [23ndash25]We observed from Table 6 that the results of the calculatedparameters are slightly different when we move from onelevel to another and also when the medium changes Thevalue of electric field is greater in a solution of chloroformthan its corresponding value in gas phase This is because the
polarizability increases in presence of a solvent The valuesof electric susceptibility dielectric constant and refractiveindex are greater at B3LYP level compared to their corre-sponding value at the RHF All the calculated parametersof optoelectronic properties obtained at the B3LYP level aresimilar to those obtained at the B3PW91 level None of theseparameters have been determined before either theoreticallyor experimentally
One of the central goals of this study is to understandthe underlying structurendashproperty relationships whichmightform the basis for a ldquomolecular engineeringrdquo approachto electronics optoelectronics and photonics The molarrefractivity of our molecule known to be an importantparameter in quantitative structurendashproperty relationshipanalysis was calculated for this purpose The value of the
Advances in Condensed Matter Physics 13
Table 7 Experimental and calculated 1HNMR chemical shifts 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
molar refractivity was calculated at the three levels in bothgas and chloroform using the 6-311++G(dp) basis set TheLorenz-Lorentz equation was used for this calculation [2627] and its results are listed in Table 6
The high values of molar refractivity polarizabilityanisotropy of polarizability and first static hyperpolarizabil-ity of Rubescin E molecule show that the molecule has goodquantitative structurendashproperty relationship analysis andmight therefore form the basis for a ldquomolecular engineeringrdquoapproach to electronics optoelectronics and photonics
35 NMR Study of Rubescin E After the optimization ofthe Rubescin E molecule the 1H and 13C chemical shiftswere calculated at the RHF B3LYP and B3PW91 levels of thetheory using the 6-311++G(dp) basis set In order to comparethe calculated values of 1H and 13C chemical shifts withexperimental results we also need to calculate the absoluteshielding value of 1Hand 13C for the tetramethylsilane (TMS)using the same methods above The GIAO (Gauge InvariantAtomic Orbitals) approach known to provide satisfactorychemical shifts for different nuclei with larger molecules [28]was used for this purpose and the following equation
120575119894 (119901119901119898) = 119894119904119900119905119903119900119901119894119888 (119879119872119878119894) minus 119894119904119900119905119903119900119901119894119888 (119894) (6)
where 119894 is the atom type and was used to convert the chemicalshielding to chemical shifts
The experimental and calculated chemical shifts of 1Halong with their corresponding error are listed in Table 7From our results we observed that all the methods provideresults which are very close to experiment since the errorsbetween the experimental and calculated results are smaller
In order to compare experimental and theoretical resultsa linear correlation of 1H-NMR chemical shifts was estab-lished as shown in Figure 6 The regression line was plottedusing the following equations 120575119888119886119897 = 098880120575119890119909119901 minus 017198120575119888119886119897 = 097379120575119890119909119901 + 018796 and 120575119888119886119897 = 097069120575119890119909119901 +019387 respectively at the RHF B3PW91 and B3LYP levelsof the theory The theoretical results obtained from usingthe 6-311++G(dp) basis set show good correlation withexperiment since and the calculated R-square values arefound to be close to 1 at each level as shown by Figure 6
The calculated and experimental 13C chemical shifts ofour molecule are given in Table 8 and their comparison canbe found in Figure 7 The linear regression line plotted inFigure 7 shows that theoretical results are in good agreementwith experiment This is confirmed by the linear correlationcoefficient calculated here as R-square at the RHF B3PW91and B3LYP levels using the 6-311++G(dp) basis set
The following regression line plotted for each level usingthe general equation 120575119888119886119897 = 119886120575119890119909119901 + 119887 where a and b are givenin Figure 7 shows that the calculated 13C chemical shiftscorrelate very well with experiment The linear correlationcoefficient calculated as R-square found in Figure 7 alsoconfirms this
36 Vibrational Frequencies Analysis The vibrational fre-quencies of our molecule were computed by using B3LYP6-311G(dp) method in both gas phase and chloroform Theexperimental IR vibrational frequencies obtained for the twocarbonyl moiety present in our structure along with thecalculated scaled and unscaled vibrational frequencies IRand Raman frequencies with their approximate descriptions
14 Advances in Condensed Matter Physics
Table 8 Experimental and calculated 13C NMR chemical shift 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
y = +100x -0254 max dev150 r=0960 y = +0987x +0127 max dev104 r=0979
y = +0980x +0141 max dev103 r=0981
y = +100x -0254 max dev150 y = +0987x +0127 max dev104
y = +0980x +0141 max dev103
Figure 6 Comparison of experimental and theoretical 1H chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set in chloroform
Advances in Condensed Matter Physics 15
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3LYP6-311++G(dp)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3PW916-311++G(dp)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
minus250
255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
RHF6-311++G(dp)
y = +107x -517 max dev836 r=0994 y = +105x +238 max dev648 r=0998
y = +105x +354 max dev541 r=0998
y = +107x -517 max dev836 y = +105x +238 max dev648
y = +105x +354 max dev541
Figure 7 Comparison of experimental and theoretical 13C chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set
are given in Table 9 The rest of the vibrational parameterof Rubescin E molecule which is not described in Table 9can be obtained from Supplementary Material S2 The scalefactor was determined as the mean value of the scale factorthat matches correctly for the C=O stretching and the givenexperimental valueThe obtained scale factor was 09706 Noimaginary frequencies were found showing that structure ofthe molecule Rubescin E is stable in both gas and solventFigure 8 gives the representation of the scaled IR intensity andRaman scattering activity
The C=O double bond gives rise to a very intenseabsorption band in IR spectrum The position and intensityof this band range from 1870 cmminus1 to 1540 cmminus1 dependingon the physical state electronic andmass effects of neighbor-ing substituents intra- and intermolecular interactions andconjugations [29] The C=O double bond absorption spectra
were observed experimentally at 1720 cmminus1 and 1664 cmminus1[1] In this study the vibrational mode of C=O was found at172620 cmminus1 and 169057 cmminus1 gas phase and at 170101 cmminus1and 166759 cmminus1 in chloroform There is good agreementbetween the vibrational modes with experimental values
4 Conclusion
In this study the geometry optimization of Rubescin E hasbeen carried out using ab initio HF and density functionaltheoryDFT (B3LYP and B3PW91)methods in both gas phaseand chloroform solution with the 6-311++G(dp) basis setThe optimized parameters were compared to those of someexisting groups of compound present in our molecule sincenone of this have been done before for the title molecule andgood agreement was found In order to confirm the geometry
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
Applied Bionics and BiomechanicsHindawiwwwhindawicom Volume 2018
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Volume 2018
Hindawiwwwhindawicom Volume 2018
Mathematical PhysicsAdvances in
Hindawiwwwhindawicom Volume 2018
ChemistryAdvances in
Hindawiwwwhindawicom Volume 2018
Journal of
Chemistry
Hindawiwwwhindawicom Volume 2018
Advances inPhysical Chemistry
International Journal of
RotatingMachinery
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom
Journal ofEngineeringVolume 2018
Submit your manuscripts atwwwhindawicom
Advances in Condensed Matter Physics 9
Table 3 Global reactivity descriptors of Rubescin E at the RHF B3LYP and B3PW91 levels in gas phase and in chloroform solution using the6-311++G(dp) basis set
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
Figure 3 Molecular orbital and the HOMO and LUMO energy of Rubescin E in gas phase
The calculated vertical IP values in gas phase are biggerthan their corresponding values in solvent From Table 3we also found that putting the molecule in solvent increasesits electron affinity From the calculated IP and EA valuesone can conclude that solvent effect increases the capacityof molecule of gaining an electron compared to donating itIt also reduces the harness of our molecule and increasesthe softness Hence the presence of solvent increases thereactivity of the molecule Rubescin
343 Frontier Molecular Orbitals The frontier molecularorbitals of Rubescin E were evaluated using the ab initio andDFT methods The 6-311G(dp) and 6-311++G(dp) basis setswere used for this purpose in gas phase and in chloroformsolutionThe results show that the energy gap of ourmoleculedecreases when diffuse functions are added onto all theatoms We also found that whenever the basis set andmethods used the energy gap is greater than 4 showing thatour molecule is hard and can be used as insulator in manyelectronic devices In Figure 3 the 3Dplots of theHOMOandLUMO orbitals computed at the RHF B3PW91 and B3LYPlevels with the 6-311G(dp) basis set are illustrated in gasphase We observed that the HOMO of Rubescin E is locatedover the furan ring at the three levels and also at the C-Cof cyclohexane ring and C-O of oxiran ring By contrast the
LUMO orbital is located over the cyclohex-2-enone ring C-C and C-O bond of tetrahydrofuran ring We can thereforeconclude that electron can easily be transferred from furanring to tetrahydrofuran ring
The total density of states (DOS) spectrum of RubescinE at the gas phase and in chloroform is given in Figure 4for each level at the 6-311++G(dp) basis set These DOSsspectra presented in Figure 4 were obtained from Gauss-Sum 30 program [18] which was used in order to show thecontributions of different group tomolecular orbital (HOMOand LUMO) From Figure 4 we observe that the HOMO-LUMO energy gap is smaller when we move from RHF toB3PW91 and from B3PW91 to B3LYP level respectively forboth gas and chloroform phases with larger values obtainedin chloroform
344 UV-Vis SpectraAnalysis Timedependent density func-tional theory (TD-DFT) was used in gas phase at the twolevels B3PW91 and B3LYP with the 6-311++G(dp) basis setin order to determine the first six excited states to investigatethe UV-vis absorption spectra of themoleculeThe excitationenergy (E) wavelength (120582) and oscillator strength (f) alongwith their major contributions are given in Table 4 and theirresults are compared to experiment
10 Advances in Condensed Matter Physics
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3LYP Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
Energy (eV)
B3LYP Gas
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Gas
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Chloroform
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Gas
4293 eV
9797 eV9516 eV
4315 eV 4333 eV
4314 eV
Figure 4 Total density of state (DOS) spectrum of Rubescin E at the RHF B3PW91 and B3LYP levels in both gas and chloroform phase andwith the 6-311++G(dp) basis set
Two intense electronic transitions were predicted at44934 eV (27592 nm) and 34415 eV (36027 nm) withoscillator strengths of 00043 and 00014 respectively at theB3PW91 level and 45123 eV (27477 nm) and 34603 eV(35831 nm) with oscillator strengths of 00041 and 00014respectively at the B3LYP levelWe observed from the spectra
that the maximum absorption wavelength corresponds tothe electronic transition from HOMO to LUMO+1 with100 contribution followed by the electronic transition fromHOMO to LUMO with 99 contribution at the two levelsThe experimental absorption spectra of the title moleculepredict two bands at 254 nm and 365 nm The error between
Advances in Condensed Matter Physics 11
Table 4Theoretical absorption wavelength (120582) excitation energy (E) and oscillator strengths of Rubescin E at the B3PW91 and B3LYP levelsin gas with the 6-311++G(dp) basis set
Excited states Exp [1] B3PW91 B3LYP120582 (nm) 120582 (nm) E (eV) f Major contributions 120582 (nm) E (eV) f Major contributions
1 365 36027 34415 00014 H-1 997888rarr L (93) 35831 34603 00014 H-1 997888rarr L (93)2 31218 39715 00000 H 997888rarr L (99) 31369 39524 00000 H 997888rarr L (99)3 254 27592 44934 00043 H-4 997888rarr L (24) 27477 45123 00041 H-4 997888rarr L (28)4 27266 45473 00006 H-4 997888rarr L (50) 27227 45538 00004 H-4 997888rarr L (44)5 26956 45994 00001 H-4 997888rarr L (19) 26847 46182 00001 H-4 997888rarr L (20)6 26121 47465 00000 H 997888rarr L+1 (100) 26316 47113 00000 H 997888rarr L+1 (100)
200 250 300 350 400 450 5000
50
100
150
200
250
300
350
wavelength (nm)
Epsi
lon
B3LYP
200 250 300 350 400 450 5000
50100150200250300350400
Wavelength (nm)
Epsi
lon
B3PW91
UV vis spectrumOscillator strength
UV vis spectrumOscillator strength
Figure 5 Theoretical absorption spectra of Rubescin E at the B3PW91 and B3LYP levels in gas with the 6-311++G(dp) basis set
the theoretical and experimental results range from - 473 nmto 2192 nm at the B3PW91 and from - 669 nm to 2077 nm atthe B3LYP levelThese errors are due to the fact that only onemolecule was considered for simulationThe theoretical UV-vis absorption spectra of Rubescin E in gas phase are shownin Figure 5
345 Dipole Moment (120583119863119872) Average Polarizability (120572) FirstStatic Hyperpolarizability (120573) and Anisotropy of PolarizationIn this work the dipole moment 120583119863119872 average polarizability120572 first static hyperpolarizability 120573 and anisotropy of polar-izability Δ120572 of Rubescin E were evaluated in both gas phaseand chloroform solution in order to define the nonlinearityof Rubescin E The finite-field approach was used for thispurpose Equations (2) (3) (4) and (5) were used to calculatethe polarizability dipole moment anisotropy of polarizabil-ity and first static hyperpolarizability respectively using thex 119910 119911 components obtained from Gaussian 09 W outputThe calculated parameters were presented in Table 5 at thethree levels with the 6-311++G(dp) basis set
The calculated values of polarizability and first static hyper-polarizability obtained from Gaussian output are in atomicunit These values were then converted into electrostatic unit(esu) for comparison purpose (for 120572 1 au = 01482 x 10minus24esu for 120573 1 au = 86393 x 10minus33 esu) [19ndash22] From a givingmolecule when these values (120583119863119872 and 120573) are greater thanthose of urea the molecule is said to have good active NLOproperties We observed from our results that the values of120572 120573 and 120583119863119872 are higher in solvent than their correspondingvalue in gas phase 120573 and 120583119863119872 of Rubescin E calculated at the6-311++G(dp) basis set using different methods were greaterthan those of urea These values calculated using the HF6-311D(dp)method (120583119863119872 = 52175Dand120573 = 17603169x10minus33esu) were also higher than those of urea (120583119863119872 = 38851D and120573 = 372811990910minus33esu) obtained using the same method and
12 Advances in Condensed Matter Physics
Table 5 Electric dipole moment polarizability anisotropy of polarization first-order hyperpolarizability and molar refractivity of RubescinE at the RHF B3LYP and B3PW91 levels with the 6-311G (d p) and 6-311++G (d p) basis sets
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
Table 6 Calculated values of polarization density (P) average electric field (E) electric susceptibility (120594) refractive index (120578) dielectricconstant (E) magnitude of the displacement (D) and molar refractivity (MR) of Rubescin E molecule obtained at the RHF B3LYP andB3PW91 levels with the 6-311++G(dp) basis set
Parameters RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
basis set [21] Hence Rubescin E can be considered to havegood active NLO properties and this is due to the delocalize electron on the furan ring
346 Optoelectronic Properties In order to recognize theoptoelectronic nature of Rubescin E for different devicesapplications some parameters such as electric field (E) elec-tric polarization (P) electric susceptibility (120594) permittivity(E) refractive index (120578) and electric displacement (D) werecalculated using equations given in the literature [23ndash25]We observed from Table 6 that the results of the calculatedparameters are slightly different when we move from onelevel to another and also when the medium changes Thevalue of electric field is greater in a solution of chloroformthan its corresponding value in gas phase This is because the
polarizability increases in presence of a solvent The valuesof electric susceptibility dielectric constant and refractiveindex are greater at B3LYP level compared to their corre-sponding value at the RHF All the calculated parametersof optoelectronic properties obtained at the B3LYP level aresimilar to those obtained at the B3PW91 level None of theseparameters have been determined before either theoreticallyor experimentally
One of the central goals of this study is to understandthe underlying structurendashproperty relationships whichmightform the basis for a ldquomolecular engineeringrdquo approachto electronics optoelectronics and photonics The molarrefractivity of our molecule known to be an importantparameter in quantitative structurendashproperty relationshipanalysis was calculated for this purpose The value of the
Advances in Condensed Matter Physics 13
Table 7 Experimental and calculated 1HNMR chemical shifts 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
molar refractivity was calculated at the three levels in bothgas and chloroform using the 6-311++G(dp) basis set TheLorenz-Lorentz equation was used for this calculation [2627] and its results are listed in Table 6
The high values of molar refractivity polarizabilityanisotropy of polarizability and first static hyperpolarizabil-ity of Rubescin E molecule show that the molecule has goodquantitative structurendashproperty relationship analysis andmight therefore form the basis for a ldquomolecular engineeringrdquoapproach to electronics optoelectronics and photonics
35 NMR Study of Rubescin E After the optimization ofthe Rubescin E molecule the 1H and 13C chemical shiftswere calculated at the RHF B3LYP and B3PW91 levels of thetheory using the 6-311++G(dp) basis set In order to comparethe calculated values of 1H and 13C chemical shifts withexperimental results we also need to calculate the absoluteshielding value of 1Hand 13C for the tetramethylsilane (TMS)using the same methods above The GIAO (Gauge InvariantAtomic Orbitals) approach known to provide satisfactorychemical shifts for different nuclei with larger molecules [28]was used for this purpose and the following equation
120575119894 (119901119901119898) = 119894119904119900119905119903119900119901119894119888 (119879119872119878119894) minus 119894119904119900119905119903119900119901119894119888 (119894) (6)
where 119894 is the atom type and was used to convert the chemicalshielding to chemical shifts
The experimental and calculated chemical shifts of 1Halong with their corresponding error are listed in Table 7From our results we observed that all the methods provideresults which are very close to experiment since the errorsbetween the experimental and calculated results are smaller
In order to compare experimental and theoretical resultsa linear correlation of 1H-NMR chemical shifts was estab-lished as shown in Figure 6 The regression line was plottedusing the following equations 120575119888119886119897 = 098880120575119890119909119901 minus 017198120575119888119886119897 = 097379120575119890119909119901 + 018796 and 120575119888119886119897 = 097069120575119890119909119901 +019387 respectively at the RHF B3PW91 and B3LYP levelsof the theory The theoretical results obtained from usingthe 6-311++G(dp) basis set show good correlation withexperiment since and the calculated R-square values arefound to be close to 1 at each level as shown by Figure 6
The calculated and experimental 13C chemical shifts ofour molecule are given in Table 8 and their comparison canbe found in Figure 7 The linear regression line plotted inFigure 7 shows that theoretical results are in good agreementwith experiment This is confirmed by the linear correlationcoefficient calculated here as R-square at the RHF B3PW91and B3LYP levels using the 6-311++G(dp) basis set
The following regression line plotted for each level usingthe general equation 120575119888119886119897 = 119886120575119890119909119901 + 119887 where a and b are givenin Figure 7 shows that the calculated 13C chemical shiftscorrelate very well with experiment The linear correlationcoefficient calculated as R-square found in Figure 7 alsoconfirms this
36 Vibrational Frequencies Analysis The vibrational fre-quencies of our molecule were computed by using B3LYP6-311G(dp) method in both gas phase and chloroform Theexperimental IR vibrational frequencies obtained for the twocarbonyl moiety present in our structure along with thecalculated scaled and unscaled vibrational frequencies IRand Raman frequencies with their approximate descriptions
14 Advances in Condensed Matter Physics
Table 8 Experimental and calculated 13C NMR chemical shift 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
y = +100x -0254 max dev150 r=0960 y = +0987x +0127 max dev104 r=0979
y = +0980x +0141 max dev103 r=0981
y = +100x -0254 max dev150 y = +0987x +0127 max dev104
y = +0980x +0141 max dev103
Figure 6 Comparison of experimental and theoretical 1H chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set in chloroform
Advances in Condensed Matter Physics 15
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3LYP6-311++G(dp)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3PW916-311++G(dp)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
minus250
255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
RHF6-311++G(dp)
y = +107x -517 max dev836 r=0994 y = +105x +238 max dev648 r=0998
y = +105x +354 max dev541 r=0998
y = +107x -517 max dev836 y = +105x +238 max dev648
y = +105x +354 max dev541
Figure 7 Comparison of experimental and theoretical 13C chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set
are given in Table 9 The rest of the vibrational parameterof Rubescin E molecule which is not described in Table 9can be obtained from Supplementary Material S2 The scalefactor was determined as the mean value of the scale factorthat matches correctly for the C=O stretching and the givenexperimental valueThe obtained scale factor was 09706 Noimaginary frequencies were found showing that structure ofthe molecule Rubescin E is stable in both gas and solventFigure 8 gives the representation of the scaled IR intensity andRaman scattering activity
The C=O double bond gives rise to a very intenseabsorption band in IR spectrum The position and intensityof this band range from 1870 cmminus1 to 1540 cmminus1 dependingon the physical state electronic andmass effects of neighbor-ing substituents intra- and intermolecular interactions andconjugations [29] The C=O double bond absorption spectra
were observed experimentally at 1720 cmminus1 and 1664 cmminus1[1] In this study the vibrational mode of C=O was found at172620 cmminus1 and 169057 cmminus1 gas phase and at 170101 cmminus1and 166759 cmminus1 in chloroform There is good agreementbetween the vibrational modes with experimental values
4 Conclusion
In this study the geometry optimization of Rubescin E hasbeen carried out using ab initio HF and density functionaltheoryDFT (B3LYP and B3PW91)methods in both gas phaseand chloroform solution with the 6-311++G(dp) basis setThe optimized parameters were compared to those of someexisting groups of compound present in our molecule sincenone of this have been done before for the title molecule andgood agreement was found In order to confirm the geometry
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
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10 Advances in Condensed Matter Physics
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3LYP Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
Energy (eV)
B3LYP Gas
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
DOS spectrumOccupied orbitalsVirtual orbitals
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Chloroform
minus20 minus15 minus10 minus5 0 5
0123456789
10
Energy (eV)
B3PW91 Gas
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Chloroform
minus20 minus15 minus10 minus5 0 5
0
1
2
3
4
5
6
7
Energy (eV)
RHF Gas
4293 eV
9797 eV9516 eV
4315 eV 4333 eV
4314 eV
Figure 4 Total density of state (DOS) spectrum of Rubescin E at the RHF B3PW91 and B3LYP levels in both gas and chloroform phase andwith the 6-311++G(dp) basis set
Two intense electronic transitions were predicted at44934 eV (27592 nm) and 34415 eV (36027 nm) withoscillator strengths of 00043 and 00014 respectively at theB3PW91 level and 45123 eV (27477 nm) and 34603 eV(35831 nm) with oscillator strengths of 00041 and 00014respectively at the B3LYP levelWe observed from the spectra
that the maximum absorption wavelength corresponds tothe electronic transition from HOMO to LUMO+1 with100 contribution followed by the electronic transition fromHOMO to LUMO with 99 contribution at the two levelsThe experimental absorption spectra of the title moleculepredict two bands at 254 nm and 365 nm The error between
Advances in Condensed Matter Physics 11
Table 4Theoretical absorption wavelength (120582) excitation energy (E) and oscillator strengths of Rubescin E at the B3PW91 and B3LYP levelsin gas with the 6-311++G(dp) basis set
Excited states Exp [1] B3PW91 B3LYP120582 (nm) 120582 (nm) E (eV) f Major contributions 120582 (nm) E (eV) f Major contributions
1 365 36027 34415 00014 H-1 997888rarr L (93) 35831 34603 00014 H-1 997888rarr L (93)2 31218 39715 00000 H 997888rarr L (99) 31369 39524 00000 H 997888rarr L (99)3 254 27592 44934 00043 H-4 997888rarr L (24) 27477 45123 00041 H-4 997888rarr L (28)4 27266 45473 00006 H-4 997888rarr L (50) 27227 45538 00004 H-4 997888rarr L (44)5 26956 45994 00001 H-4 997888rarr L (19) 26847 46182 00001 H-4 997888rarr L (20)6 26121 47465 00000 H 997888rarr L+1 (100) 26316 47113 00000 H 997888rarr L+1 (100)
200 250 300 350 400 450 5000
50
100
150
200
250
300
350
wavelength (nm)
Epsi
lon
B3LYP
200 250 300 350 400 450 5000
50100150200250300350400
Wavelength (nm)
Epsi
lon
B3PW91
UV vis spectrumOscillator strength
UV vis spectrumOscillator strength
Figure 5 Theoretical absorption spectra of Rubescin E at the B3PW91 and B3LYP levels in gas with the 6-311++G(dp) basis set
the theoretical and experimental results range from - 473 nmto 2192 nm at the B3PW91 and from - 669 nm to 2077 nm atthe B3LYP levelThese errors are due to the fact that only onemolecule was considered for simulationThe theoretical UV-vis absorption spectra of Rubescin E in gas phase are shownin Figure 5
345 Dipole Moment (120583119863119872) Average Polarizability (120572) FirstStatic Hyperpolarizability (120573) and Anisotropy of PolarizationIn this work the dipole moment 120583119863119872 average polarizability120572 first static hyperpolarizability 120573 and anisotropy of polar-izability Δ120572 of Rubescin E were evaluated in both gas phaseand chloroform solution in order to define the nonlinearityof Rubescin E The finite-field approach was used for thispurpose Equations (2) (3) (4) and (5) were used to calculatethe polarizability dipole moment anisotropy of polarizabil-ity and first static hyperpolarizability respectively using thex 119910 119911 components obtained from Gaussian 09 W outputThe calculated parameters were presented in Table 5 at thethree levels with the 6-311++G(dp) basis set
The calculated values of polarizability and first static hyper-polarizability obtained from Gaussian output are in atomicunit These values were then converted into electrostatic unit(esu) for comparison purpose (for 120572 1 au = 01482 x 10minus24esu for 120573 1 au = 86393 x 10minus33 esu) [19ndash22] From a givingmolecule when these values (120583119863119872 and 120573) are greater thanthose of urea the molecule is said to have good active NLOproperties We observed from our results that the values of120572 120573 and 120583119863119872 are higher in solvent than their correspondingvalue in gas phase 120573 and 120583119863119872 of Rubescin E calculated at the6-311++G(dp) basis set using different methods were greaterthan those of urea These values calculated using the HF6-311D(dp)method (120583119863119872 = 52175Dand120573 = 17603169x10minus33esu) were also higher than those of urea (120583119863119872 = 38851D and120573 = 372811990910minus33esu) obtained using the same method and
12 Advances in Condensed Matter Physics
Table 5 Electric dipole moment polarizability anisotropy of polarization first-order hyperpolarizability and molar refractivity of RubescinE at the RHF B3LYP and B3PW91 levels with the 6-311G (d p) and 6-311++G (d p) basis sets
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
Table 6 Calculated values of polarization density (P) average electric field (E) electric susceptibility (120594) refractive index (120578) dielectricconstant (E) magnitude of the displacement (D) and molar refractivity (MR) of Rubescin E molecule obtained at the RHF B3LYP andB3PW91 levels with the 6-311++G(dp) basis set
Parameters RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
basis set [21] Hence Rubescin E can be considered to havegood active NLO properties and this is due to the delocalize electron on the furan ring
346 Optoelectronic Properties In order to recognize theoptoelectronic nature of Rubescin E for different devicesapplications some parameters such as electric field (E) elec-tric polarization (P) electric susceptibility (120594) permittivity(E) refractive index (120578) and electric displacement (D) werecalculated using equations given in the literature [23ndash25]We observed from Table 6 that the results of the calculatedparameters are slightly different when we move from onelevel to another and also when the medium changes Thevalue of electric field is greater in a solution of chloroformthan its corresponding value in gas phase This is because the
polarizability increases in presence of a solvent The valuesof electric susceptibility dielectric constant and refractiveindex are greater at B3LYP level compared to their corre-sponding value at the RHF All the calculated parametersof optoelectronic properties obtained at the B3LYP level aresimilar to those obtained at the B3PW91 level None of theseparameters have been determined before either theoreticallyor experimentally
One of the central goals of this study is to understandthe underlying structurendashproperty relationships whichmightform the basis for a ldquomolecular engineeringrdquo approachto electronics optoelectronics and photonics The molarrefractivity of our molecule known to be an importantparameter in quantitative structurendashproperty relationshipanalysis was calculated for this purpose The value of the
Advances in Condensed Matter Physics 13
Table 7 Experimental and calculated 1HNMR chemical shifts 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
molar refractivity was calculated at the three levels in bothgas and chloroform using the 6-311++G(dp) basis set TheLorenz-Lorentz equation was used for this calculation [2627] and its results are listed in Table 6
The high values of molar refractivity polarizabilityanisotropy of polarizability and first static hyperpolarizabil-ity of Rubescin E molecule show that the molecule has goodquantitative structurendashproperty relationship analysis andmight therefore form the basis for a ldquomolecular engineeringrdquoapproach to electronics optoelectronics and photonics
35 NMR Study of Rubescin E After the optimization ofthe Rubescin E molecule the 1H and 13C chemical shiftswere calculated at the RHF B3LYP and B3PW91 levels of thetheory using the 6-311++G(dp) basis set In order to comparethe calculated values of 1H and 13C chemical shifts withexperimental results we also need to calculate the absoluteshielding value of 1Hand 13C for the tetramethylsilane (TMS)using the same methods above The GIAO (Gauge InvariantAtomic Orbitals) approach known to provide satisfactorychemical shifts for different nuclei with larger molecules [28]was used for this purpose and the following equation
120575119894 (119901119901119898) = 119894119904119900119905119903119900119901119894119888 (119879119872119878119894) minus 119894119904119900119905119903119900119901119894119888 (119894) (6)
where 119894 is the atom type and was used to convert the chemicalshielding to chemical shifts
The experimental and calculated chemical shifts of 1Halong with their corresponding error are listed in Table 7From our results we observed that all the methods provideresults which are very close to experiment since the errorsbetween the experimental and calculated results are smaller
In order to compare experimental and theoretical resultsa linear correlation of 1H-NMR chemical shifts was estab-lished as shown in Figure 6 The regression line was plottedusing the following equations 120575119888119886119897 = 098880120575119890119909119901 minus 017198120575119888119886119897 = 097379120575119890119909119901 + 018796 and 120575119888119886119897 = 097069120575119890119909119901 +019387 respectively at the RHF B3PW91 and B3LYP levelsof the theory The theoretical results obtained from usingthe 6-311++G(dp) basis set show good correlation withexperiment since and the calculated R-square values arefound to be close to 1 at each level as shown by Figure 6
The calculated and experimental 13C chemical shifts ofour molecule are given in Table 8 and their comparison canbe found in Figure 7 The linear regression line plotted inFigure 7 shows that theoretical results are in good agreementwith experiment This is confirmed by the linear correlationcoefficient calculated here as R-square at the RHF B3PW91and B3LYP levels using the 6-311++G(dp) basis set
The following regression line plotted for each level usingthe general equation 120575119888119886119897 = 119886120575119890119909119901 + 119887 where a and b are givenin Figure 7 shows that the calculated 13C chemical shiftscorrelate very well with experiment The linear correlationcoefficient calculated as R-square found in Figure 7 alsoconfirms this
36 Vibrational Frequencies Analysis The vibrational fre-quencies of our molecule were computed by using B3LYP6-311G(dp) method in both gas phase and chloroform Theexperimental IR vibrational frequencies obtained for the twocarbonyl moiety present in our structure along with thecalculated scaled and unscaled vibrational frequencies IRand Raman frequencies with their approximate descriptions
14 Advances in Condensed Matter Physics
Table 8 Experimental and calculated 13C NMR chemical shift 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
y = +100x -0254 max dev150 r=0960 y = +0987x +0127 max dev104 r=0979
y = +0980x +0141 max dev103 r=0981
y = +100x -0254 max dev150 y = +0987x +0127 max dev104
y = +0980x +0141 max dev103
Figure 6 Comparison of experimental and theoretical 1H chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set in chloroform
Advances in Condensed Matter Physics 15
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3LYP6-311++G(dp)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3PW916-311++G(dp)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
minus250
255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
RHF6-311++G(dp)
y = +107x -517 max dev836 r=0994 y = +105x +238 max dev648 r=0998
y = +105x +354 max dev541 r=0998
y = +107x -517 max dev836 y = +105x +238 max dev648
y = +105x +354 max dev541
Figure 7 Comparison of experimental and theoretical 13C chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set
are given in Table 9 The rest of the vibrational parameterof Rubescin E molecule which is not described in Table 9can be obtained from Supplementary Material S2 The scalefactor was determined as the mean value of the scale factorthat matches correctly for the C=O stretching and the givenexperimental valueThe obtained scale factor was 09706 Noimaginary frequencies were found showing that structure ofthe molecule Rubescin E is stable in both gas and solventFigure 8 gives the representation of the scaled IR intensity andRaman scattering activity
The C=O double bond gives rise to a very intenseabsorption band in IR spectrum The position and intensityof this band range from 1870 cmminus1 to 1540 cmminus1 dependingon the physical state electronic andmass effects of neighbor-ing substituents intra- and intermolecular interactions andconjugations [29] The C=O double bond absorption spectra
were observed experimentally at 1720 cmminus1 and 1664 cmminus1[1] In this study the vibrational mode of C=O was found at172620 cmminus1 and 169057 cmminus1 gas phase and at 170101 cmminus1and 166759 cmminus1 in chloroform There is good agreementbetween the vibrational modes with experimental values
4 Conclusion
In this study the geometry optimization of Rubescin E hasbeen carried out using ab initio HF and density functionaltheoryDFT (B3LYP and B3PW91)methods in both gas phaseand chloroform solution with the 6-311++G(dp) basis setThe optimized parameters were compared to those of someexisting groups of compound present in our molecule sincenone of this have been done before for the title molecule andgood agreement was found In order to confirm the geometry
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
Applied Bionics and BiomechanicsHindawiwwwhindawicom Volume 2018
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Volume 2018
Hindawiwwwhindawicom Volume 2018
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Hindawiwwwhindawicom Volume 2018
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Journal ofEngineeringVolume 2018
Submit your manuscripts atwwwhindawicom
Advances in Condensed Matter Physics 11
Table 4Theoretical absorption wavelength (120582) excitation energy (E) and oscillator strengths of Rubescin E at the B3PW91 and B3LYP levelsin gas with the 6-311++G(dp) basis set
Excited states Exp [1] B3PW91 B3LYP120582 (nm) 120582 (nm) E (eV) f Major contributions 120582 (nm) E (eV) f Major contributions
1 365 36027 34415 00014 H-1 997888rarr L (93) 35831 34603 00014 H-1 997888rarr L (93)2 31218 39715 00000 H 997888rarr L (99) 31369 39524 00000 H 997888rarr L (99)3 254 27592 44934 00043 H-4 997888rarr L (24) 27477 45123 00041 H-4 997888rarr L (28)4 27266 45473 00006 H-4 997888rarr L (50) 27227 45538 00004 H-4 997888rarr L (44)5 26956 45994 00001 H-4 997888rarr L (19) 26847 46182 00001 H-4 997888rarr L (20)6 26121 47465 00000 H 997888rarr L+1 (100) 26316 47113 00000 H 997888rarr L+1 (100)
200 250 300 350 400 450 5000
50
100
150
200
250
300
350
wavelength (nm)
Epsi
lon
B3LYP
200 250 300 350 400 450 5000
50100150200250300350400
Wavelength (nm)
Epsi
lon
B3PW91
UV vis spectrumOscillator strength
UV vis spectrumOscillator strength
Figure 5 Theoretical absorption spectra of Rubescin E at the B3PW91 and B3LYP levels in gas with the 6-311++G(dp) basis set
the theoretical and experimental results range from - 473 nmto 2192 nm at the B3PW91 and from - 669 nm to 2077 nm atthe B3LYP levelThese errors are due to the fact that only onemolecule was considered for simulationThe theoretical UV-vis absorption spectra of Rubescin E in gas phase are shownin Figure 5
345 Dipole Moment (120583119863119872) Average Polarizability (120572) FirstStatic Hyperpolarizability (120573) and Anisotropy of PolarizationIn this work the dipole moment 120583119863119872 average polarizability120572 first static hyperpolarizability 120573 and anisotropy of polar-izability Δ120572 of Rubescin E were evaluated in both gas phaseand chloroform solution in order to define the nonlinearityof Rubescin E The finite-field approach was used for thispurpose Equations (2) (3) (4) and (5) were used to calculatethe polarizability dipole moment anisotropy of polarizabil-ity and first static hyperpolarizability respectively using thex 119910 119911 components obtained from Gaussian 09 W outputThe calculated parameters were presented in Table 5 at thethree levels with the 6-311++G(dp) basis set
The calculated values of polarizability and first static hyper-polarizability obtained from Gaussian output are in atomicunit These values were then converted into electrostatic unit(esu) for comparison purpose (for 120572 1 au = 01482 x 10minus24esu for 120573 1 au = 86393 x 10minus33 esu) [19ndash22] From a givingmolecule when these values (120583119863119872 and 120573) are greater thanthose of urea the molecule is said to have good active NLOproperties We observed from our results that the values of120572 120573 and 120583119863119872 are higher in solvent than their correspondingvalue in gas phase 120573 and 120583119863119872 of Rubescin E calculated at the6-311++G(dp) basis set using different methods were greaterthan those of urea These values calculated using the HF6-311D(dp)method (120583119863119872 = 52175Dand120573 = 17603169x10minus33esu) were also higher than those of urea (120583119863119872 = 38851D and120573 = 372811990910minus33esu) obtained using the same method and
12 Advances in Condensed Matter Physics
Table 5 Electric dipole moment polarizability anisotropy of polarization first-order hyperpolarizability and molar refractivity of RubescinE at the RHF B3LYP and B3PW91 levels with the 6-311G (d p) and 6-311++G (d p) basis sets
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
Table 6 Calculated values of polarization density (P) average electric field (E) electric susceptibility (120594) refractive index (120578) dielectricconstant (E) magnitude of the displacement (D) and molar refractivity (MR) of Rubescin E molecule obtained at the RHF B3LYP andB3PW91 levels with the 6-311++G(dp) basis set
Parameters RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
basis set [21] Hence Rubescin E can be considered to havegood active NLO properties and this is due to the delocalize electron on the furan ring
346 Optoelectronic Properties In order to recognize theoptoelectronic nature of Rubescin E for different devicesapplications some parameters such as electric field (E) elec-tric polarization (P) electric susceptibility (120594) permittivity(E) refractive index (120578) and electric displacement (D) werecalculated using equations given in the literature [23ndash25]We observed from Table 6 that the results of the calculatedparameters are slightly different when we move from onelevel to another and also when the medium changes Thevalue of electric field is greater in a solution of chloroformthan its corresponding value in gas phase This is because the
polarizability increases in presence of a solvent The valuesof electric susceptibility dielectric constant and refractiveindex are greater at B3LYP level compared to their corre-sponding value at the RHF All the calculated parametersof optoelectronic properties obtained at the B3LYP level aresimilar to those obtained at the B3PW91 level None of theseparameters have been determined before either theoreticallyor experimentally
One of the central goals of this study is to understandthe underlying structurendashproperty relationships whichmightform the basis for a ldquomolecular engineeringrdquo approachto electronics optoelectronics and photonics The molarrefractivity of our molecule known to be an importantparameter in quantitative structurendashproperty relationshipanalysis was calculated for this purpose The value of the
Advances in Condensed Matter Physics 13
Table 7 Experimental and calculated 1HNMR chemical shifts 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
molar refractivity was calculated at the three levels in bothgas and chloroform using the 6-311++G(dp) basis set TheLorenz-Lorentz equation was used for this calculation [2627] and its results are listed in Table 6
The high values of molar refractivity polarizabilityanisotropy of polarizability and first static hyperpolarizabil-ity of Rubescin E molecule show that the molecule has goodquantitative structurendashproperty relationship analysis andmight therefore form the basis for a ldquomolecular engineeringrdquoapproach to electronics optoelectronics and photonics
35 NMR Study of Rubescin E After the optimization ofthe Rubescin E molecule the 1H and 13C chemical shiftswere calculated at the RHF B3LYP and B3PW91 levels of thetheory using the 6-311++G(dp) basis set In order to comparethe calculated values of 1H and 13C chemical shifts withexperimental results we also need to calculate the absoluteshielding value of 1Hand 13C for the tetramethylsilane (TMS)using the same methods above The GIAO (Gauge InvariantAtomic Orbitals) approach known to provide satisfactorychemical shifts for different nuclei with larger molecules [28]was used for this purpose and the following equation
120575119894 (119901119901119898) = 119894119904119900119905119903119900119901119894119888 (119879119872119878119894) minus 119894119904119900119905119903119900119901119894119888 (119894) (6)
where 119894 is the atom type and was used to convert the chemicalshielding to chemical shifts
The experimental and calculated chemical shifts of 1Halong with their corresponding error are listed in Table 7From our results we observed that all the methods provideresults which are very close to experiment since the errorsbetween the experimental and calculated results are smaller
In order to compare experimental and theoretical resultsa linear correlation of 1H-NMR chemical shifts was estab-lished as shown in Figure 6 The regression line was plottedusing the following equations 120575119888119886119897 = 098880120575119890119909119901 minus 017198120575119888119886119897 = 097379120575119890119909119901 + 018796 and 120575119888119886119897 = 097069120575119890119909119901 +019387 respectively at the RHF B3PW91 and B3LYP levelsof the theory The theoretical results obtained from usingthe 6-311++G(dp) basis set show good correlation withexperiment since and the calculated R-square values arefound to be close to 1 at each level as shown by Figure 6
The calculated and experimental 13C chemical shifts ofour molecule are given in Table 8 and their comparison canbe found in Figure 7 The linear regression line plotted inFigure 7 shows that theoretical results are in good agreementwith experiment This is confirmed by the linear correlationcoefficient calculated here as R-square at the RHF B3PW91and B3LYP levels using the 6-311++G(dp) basis set
The following regression line plotted for each level usingthe general equation 120575119888119886119897 = 119886120575119890119909119901 + 119887 where a and b are givenin Figure 7 shows that the calculated 13C chemical shiftscorrelate very well with experiment The linear correlationcoefficient calculated as R-square found in Figure 7 alsoconfirms this
36 Vibrational Frequencies Analysis The vibrational fre-quencies of our molecule were computed by using B3LYP6-311G(dp) method in both gas phase and chloroform Theexperimental IR vibrational frequencies obtained for the twocarbonyl moiety present in our structure along with thecalculated scaled and unscaled vibrational frequencies IRand Raman frequencies with their approximate descriptions
14 Advances in Condensed Matter Physics
Table 8 Experimental and calculated 13C NMR chemical shift 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
y = +100x -0254 max dev150 r=0960 y = +0987x +0127 max dev104 r=0979
y = +0980x +0141 max dev103 r=0981
y = +100x -0254 max dev150 y = +0987x +0127 max dev104
y = +0980x +0141 max dev103
Figure 6 Comparison of experimental and theoretical 1H chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set in chloroform
Advances in Condensed Matter Physics 15
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3LYP6-311++G(dp)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3PW916-311++G(dp)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
minus250
255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
RHF6-311++G(dp)
y = +107x -517 max dev836 r=0994 y = +105x +238 max dev648 r=0998
y = +105x +354 max dev541 r=0998
y = +107x -517 max dev836 y = +105x +238 max dev648
y = +105x +354 max dev541
Figure 7 Comparison of experimental and theoretical 13C chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set
are given in Table 9 The rest of the vibrational parameterof Rubescin E molecule which is not described in Table 9can be obtained from Supplementary Material S2 The scalefactor was determined as the mean value of the scale factorthat matches correctly for the C=O stretching and the givenexperimental valueThe obtained scale factor was 09706 Noimaginary frequencies were found showing that structure ofthe molecule Rubescin E is stable in both gas and solventFigure 8 gives the representation of the scaled IR intensity andRaman scattering activity
The C=O double bond gives rise to a very intenseabsorption band in IR spectrum The position and intensityof this band range from 1870 cmminus1 to 1540 cmminus1 dependingon the physical state electronic andmass effects of neighbor-ing substituents intra- and intermolecular interactions andconjugations [29] The C=O double bond absorption spectra
were observed experimentally at 1720 cmminus1 and 1664 cmminus1[1] In this study the vibrational mode of C=O was found at172620 cmminus1 and 169057 cmminus1 gas phase and at 170101 cmminus1and 166759 cmminus1 in chloroform There is good agreementbetween the vibrational modes with experimental values
4 Conclusion
In this study the geometry optimization of Rubescin E hasbeen carried out using ab initio HF and density functionaltheoryDFT (B3LYP and B3PW91)methods in both gas phaseand chloroform solution with the 6-311++G(dp) basis setThe optimized parameters were compared to those of someexisting groups of compound present in our molecule sincenone of this have been done before for the title molecule andgood agreement was found In order to confirm the geometry
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
Applied Bionics and BiomechanicsHindawiwwwhindawicom Volume 2018
Advances inOptoElectronics
Hindawiwwwhindawicom
Volume 2018
Hindawiwwwhindawicom Volume 2018
Mathematical PhysicsAdvances in
Hindawiwwwhindawicom Volume 2018
ChemistryAdvances in
Hindawiwwwhindawicom Volume 2018
Journal of
Chemistry
Hindawiwwwhindawicom Volume 2018
Advances inPhysical Chemistry
International Journal of
RotatingMachinery
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom
Journal ofEngineeringVolume 2018
Submit your manuscripts atwwwhindawicom
12 Advances in Condensed Matter Physics
Table 5 Electric dipole moment polarizability anisotropy of polarization first-order hyperpolarizability and molar refractivity of RubescinE at the RHF B3LYP and B3PW91 levels with the 6-311G (d p) and 6-311++G (d p) basis sets
RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
Table 6 Calculated values of polarization density (P) average electric field (E) electric susceptibility (120594) refractive index (120578) dielectricconstant (E) magnitude of the displacement (D) and molar refractivity (MR) of Rubescin E molecule obtained at the RHF B3LYP andB3PW91 levels with the 6-311++G(dp) basis set
Parameters RHF B3LYP B3PW91Gas Chloroform Gas Chloroform Gas Chloroform
basis set [21] Hence Rubescin E can be considered to havegood active NLO properties and this is due to the delocalize electron on the furan ring
346 Optoelectronic Properties In order to recognize theoptoelectronic nature of Rubescin E for different devicesapplications some parameters such as electric field (E) elec-tric polarization (P) electric susceptibility (120594) permittivity(E) refractive index (120578) and electric displacement (D) werecalculated using equations given in the literature [23ndash25]We observed from Table 6 that the results of the calculatedparameters are slightly different when we move from onelevel to another and also when the medium changes Thevalue of electric field is greater in a solution of chloroformthan its corresponding value in gas phase This is because the
polarizability increases in presence of a solvent The valuesof electric susceptibility dielectric constant and refractiveindex are greater at B3LYP level compared to their corre-sponding value at the RHF All the calculated parametersof optoelectronic properties obtained at the B3LYP level aresimilar to those obtained at the B3PW91 level None of theseparameters have been determined before either theoreticallyor experimentally
One of the central goals of this study is to understandthe underlying structurendashproperty relationships whichmightform the basis for a ldquomolecular engineeringrdquo approachto electronics optoelectronics and photonics The molarrefractivity of our molecule known to be an importantparameter in quantitative structurendashproperty relationshipanalysis was calculated for this purpose The value of the
Advances in Condensed Matter Physics 13
Table 7 Experimental and calculated 1HNMR chemical shifts 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
molar refractivity was calculated at the three levels in bothgas and chloroform using the 6-311++G(dp) basis set TheLorenz-Lorentz equation was used for this calculation [2627] and its results are listed in Table 6
The high values of molar refractivity polarizabilityanisotropy of polarizability and first static hyperpolarizabil-ity of Rubescin E molecule show that the molecule has goodquantitative structurendashproperty relationship analysis andmight therefore form the basis for a ldquomolecular engineeringrdquoapproach to electronics optoelectronics and photonics
35 NMR Study of Rubescin E After the optimization ofthe Rubescin E molecule the 1H and 13C chemical shiftswere calculated at the RHF B3LYP and B3PW91 levels of thetheory using the 6-311++G(dp) basis set In order to comparethe calculated values of 1H and 13C chemical shifts withexperimental results we also need to calculate the absoluteshielding value of 1Hand 13C for the tetramethylsilane (TMS)using the same methods above The GIAO (Gauge InvariantAtomic Orbitals) approach known to provide satisfactorychemical shifts for different nuclei with larger molecules [28]was used for this purpose and the following equation
120575119894 (119901119901119898) = 119894119904119900119905119903119900119901119894119888 (119879119872119878119894) minus 119894119904119900119905119903119900119901119894119888 (119894) (6)
where 119894 is the atom type and was used to convert the chemicalshielding to chemical shifts
The experimental and calculated chemical shifts of 1Halong with their corresponding error are listed in Table 7From our results we observed that all the methods provideresults which are very close to experiment since the errorsbetween the experimental and calculated results are smaller
In order to compare experimental and theoretical resultsa linear correlation of 1H-NMR chemical shifts was estab-lished as shown in Figure 6 The regression line was plottedusing the following equations 120575119888119886119897 = 098880120575119890119909119901 minus 017198120575119888119886119897 = 097379120575119890119909119901 + 018796 and 120575119888119886119897 = 097069120575119890119909119901 +019387 respectively at the RHF B3PW91 and B3LYP levelsof the theory The theoretical results obtained from usingthe 6-311++G(dp) basis set show good correlation withexperiment since and the calculated R-square values arefound to be close to 1 at each level as shown by Figure 6
The calculated and experimental 13C chemical shifts ofour molecule are given in Table 8 and their comparison canbe found in Figure 7 The linear regression line plotted inFigure 7 shows that theoretical results are in good agreementwith experiment This is confirmed by the linear correlationcoefficient calculated here as R-square at the RHF B3PW91and B3LYP levels using the 6-311++G(dp) basis set
The following regression line plotted for each level usingthe general equation 120575119888119886119897 = 119886120575119890119909119901 + 119887 where a and b are givenin Figure 7 shows that the calculated 13C chemical shiftscorrelate very well with experiment The linear correlationcoefficient calculated as R-square found in Figure 7 alsoconfirms this
36 Vibrational Frequencies Analysis The vibrational fre-quencies of our molecule were computed by using B3LYP6-311G(dp) method in both gas phase and chloroform Theexperimental IR vibrational frequencies obtained for the twocarbonyl moiety present in our structure along with thecalculated scaled and unscaled vibrational frequencies IRand Raman frequencies with their approximate descriptions
14 Advances in Condensed Matter Physics
Table 8 Experimental and calculated 13C NMR chemical shift 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
y = +100x -0254 max dev150 r=0960 y = +0987x +0127 max dev104 r=0979
y = +0980x +0141 max dev103 r=0981
y = +100x -0254 max dev150 y = +0987x +0127 max dev104
y = +0980x +0141 max dev103
Figure 6 Comparison of experimental and theoretical 1H chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set in chloroform
Advances in Condensed Matter Physics 15
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3LYP6-311++G(dp)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3PW916-311++G(dp)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
minus250
255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
RHF6-311++G(dp)
y = +107x -517 max dev836 r=0994 y = +105x +238 max dev648 r=0998
y = +105x +354 max dev541 r=0998
y = +107x -517 max dev836 y = +105x +238 max dev648
y = +105x +354 max dev541
Figure 7 Comparison of experimental and theoretical 13C chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set
are given in Table 9 The rest of the vibrational parameterof Rubescin E molecule which is not described in Table 9can be obtained from Supplementary Material S2 The scalefactor was determined as the mean value of the scale factorthat matches correctly for the C=O stretching and the givenexperimental valueThe obtained scale factor was 09706 Noimaginary frequencies were found showing that structure ofthe molecule Rubescin E is stable in both gas and solventFigure 8 gives the representation of the scaled IR intensity andRaman scattering activity
The C=O double bond gives rise to a very intenseabsorption band in IR spectrum The position and intensityof this band range from 1870 cmminus1 to 1540 cmminus1 dependingon the physical state electronic andmass effects of neighbor-ing substituents intra- and intermolecular interactions andconjugations [29] The C=O double bond absorption spectra
were observed experimentally at 1720 cmminus1 and 1664 cmminus1[1] In this study the vibrational mode of C=O was found at172620 cmminus1 and 169057 cmminus1 gas phase and at 170101 cmminus1and 166759 cmminus1 in chloroform There is good agreementbetween the vibrational modes with experimental values
4 Conclusion
In this study the geometry optimization of Rubescin E hasbeen carried out using ab initio HF and density functionaltheoryDFT (B3LYP and B3PW91)methods in both gas phaseand chloroform solution with the 6-311++G(dp) basis setThe optimized parameters were compared to those of someexisting groups of compound present in our molecule sincenone of this have been done before for the title molecule andgood agreement was found In order to confirm the geometry
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
Applied Bionics and BiomechanicsHindawiwwwhindawicom Volume 2018
Advances inOptoElectronics
Hindawiwwwhindawicom
Volume 2018
Hindawiwwwhindawicom Volume 2018
Mathematical PhysicsAdvances in
Hindawiwwwhindawicom Volume 2018
ChemistryAdvances in
Hindawiwwwhindawicom Volume 2018
Journal of
Chemistry
Hindawiwwwhindawicom Volume 2018
Advances inPhysical Chemistry
International Journal of
RotatingMachinery
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom
Journal ofEngineeringVolume 2018
Submit your manuscripts atwwwhindawicom
Advances in Condensed Matter Physics 13
Table 7 Experimental and calculated 1HNMR chemical shifts 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
molar refractivity was calculated at the three levels in bothgas and chloroform using the 6-311++G(dp) basis set TheLorenz-Lorentz equation was used for this calculation [2627] and its results are listed in Table 6
The high values of molar refractivity polarizabilityanisotropy of polarizability and first static hyperpolarizabil-ity of Rubescin E molecule show that the molecule has goodquantitative structurendashproperty relationship analysis andmight therefore form the basis for a ldquomolecular engineeringrdquoapproach to electronics optoelectronics and photonics
35 NMR Study of Rubescin E After the optimization ofthe Rubescin E molecule the 1H and 13C chemical shiftswere calculated at the RHF B3LYP and B3PW91 levels of thetheory using the 6-311++G(dp) basis set In order to comparethe calculated values of 1H and 13C chemical shifts withexperimental results we also need to calculate the absoluteshielding value of 1Hand 13C for the tetramethylsilane (TMS)using the same methods above The GIAO (Gauge InvariantAtomic Orbitals) approach known to provide satisfactorychemical shifts for different nuclei with larger molecules [28]was used for this purpose and the following equation
120575119894 (119901119901119898) = 119894119904119900119905119903119900119901119894119888 (119879119872119878119894) minus 119894119904119900119905119903119900119901119894119888 (119894) (6)
where 119894 is the atom type and was used to convert the chemicalshielding to chemical shifts
The experimental and calculated chemical shifts of 1Halong with their corresponding error are listed in Table 7From our results we observed that all the methods provideresults which are very close to experiment since the errorsbetween the experimental and calculated results are smaller
In order to compare experimental and theoretical resultsa linear correlation of 1H-NMR chemical shifts was estab-lished as shown in Figure 6 The regression line was plottedusing the following equations 120575119888119886119897 = 098880120575119890119909119901 minus 017198120575119888119886119897 = 097379120575119890119909119901 + 018796 and 120575119888119886119897 = 097069120575119890119909119901 +019387 respectively at the RHF B3PW91 and B3LYP levelsof the theory The theoretical results obtained from usingthe 6-311++G(dp) basis set show good correlation withexperiment since and the calculated R-square values arefound to be close to 1 at each level as shown by Figure 6
The calculated and experimental 13C chemical shifts ofour molecule are given in Table 8 and their comparison canbe found in Figure 7 The linear regression line plotted inFigure 7 shows that theoretical results are in good agreementwith experiment This is confirmed by the linear correlationcoefficient calculated here as R-square at the RHF B3PW91and B3LYP levels using the 6-311++G(dp) basis set
The following regression line plotted for each level usingthe general equation 120575119888119886119897 = 119886120575119890119909119901 + 119887 where a and b are givenin Figure 7 shows that the calculated 13C chemical shiftscorrelate very well with experiment The linear correlationcoefficient calculated as R-square found in Figure 7 alsoconfirms this
36 Vibrational Frequencies Analysis The vibrational fre-quencies of our molecule were computed by using B3LYP6-311G(dp) method in both gas phase and chloroform Theexperimental IR vibrational frequencies obtained for the twocarbonyl moiety present in our structure along with thecalculated scaled and unscaled vibrational frequencies IRand Raman frequencies with their approximate descriptions
14 Advances in Condensed Matter Physics
Table 8 Experimental and calculated 13C NMR chemical shift 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
y = +100x -0254 max dev150 r=0960 y = +0987x +0127 max dev104 r=0979
y = +0980x +0141 max dev103 r=0981
y = +100x -0254 max dev150 y = +0987x +0127 max dev104
y = +0980x +0141 max dev103
Figure 6 Comparison of experimental and theoretical 1H chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set in chloroform
Advances in Condensed Matter Physics 15
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3LYP6-311++G(dp)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3PW916-311++G(dp)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
minus250
255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
RHF6-311++G(dp)
y = +107x -517 max dev836 r=0994 y = +105x +238 max dev648 r=0998
y = +105x +354 max dev541 r=0998
y = +107x -517 max dev836 y = +105x +238 max dev648
y = +105x +354 max dev541
Figure 7 Comparison of experimental and theoretical 13C chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set
are given in Table 9 The rest of the vibrational parameterof Rubescin E molecule which is not described in Table 9can be obtained from Supplementary Material S2 The scalefactor was determined as the mean value of the scale factorthat matches correctly for the C=O stretching and the givenexperimental valueThe obtained scale factor was 09706 Noimaginary frequencies were found showing that structure ofthe molecule Rubescin E is stable in both gas and solventFigure 8 gives the representation of the scaled IR intensity andRaman scattering activity
The C=O double bond gives rise to a very intenseabsorption band in IR spectrum The position and intensityof this band range from 1870 cmminus1 to 1540 cmminus1 dependingon the physical state electronic andmass effects of neighbor-ing substituents intra- and intermolecular interactions andconjugations [29] The C=O double bond absorption spectra
were observed experimentally at 1720 cmminus1 and 1664 cmminus1[1] In this study the vibrational mode of C=O was found at172620 cmminus1 and 169057 cmminus1 gas phase and at 170101 cmminus1and 166759 cmminus1 in chloroform There is good agreementbetween the vibrational modes with experimental values
4 Conclusion
In this study the geometry optimization of Rubescin E hasbeen carried out using ab initio HF and density functionaltheoryDFT (B3LYP and B3PW91)methods in both gas phaseand chloroform solution with the 6-311++G(dp) basis setThe optimized parameters were compared to those of someexisting groups of compound present in our molecule sincenone of this have been done before for the title molecule andgood agreement was found In order to confirm the geometry
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
Applied Bionics and BiomechanicsHindawiwwwhindawicom Volume 2018
Advances inOptoElectronics
Hindawiwwwhindawicom
Volume 2018
Hindawiwwwhindawicom Volume 2018
Mathematical PhysicsAdvances in
Hindawiwwwhindawicom Volume 2018
ChemistryAdvances in
Hindawiwwwhindawicom Volume 2018
Journal of
Chemistry
Hindawiwwwhindawicom Volume 2018
Advances inPhysical Chemistry
International Journal of
RotatingMachinery
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom
Journal ofEngineeringVolume 2018
Submit your manuscripts atwwwhindawicom
14 Advances in Condensed Matter Physics
Table 8 Experimental and calculated 13C NMR chemical shift 120575 (ppm) of Rubescin E at the RHF B3LYP and B3PW91 levels in chloroformsolution using the 6-311++G(dp) basis set
y = +100x -0254 max dev150 r=0960 y = +0987x +0127 max dev104 r=0979
y = +0980x +0141 max dev103 r=0981
y = +100x -0254 max dev150 y = +0987x +0127 max dev104
y = +0980x +0141 max dev103
Figure 6 Comparison of experimental and theoretical 1H chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set in chloroform
Advances in Condensed Matter Physics 15
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3LYP6-311++G(dp)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3PW916-311++G(dp)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
minus250
255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
RHF6-311++G(dp)
y = +107x -517 max dev836 r=0994 y = +105x +238 max dev648 r=0998
y = +105x +354 max dev541 r=0998
y = +107x -517 max dev836 y = +105x +238 max dev648
y = +105x +354 max dev541
Figure 7 Comparison of experimental and theoretical 13C chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set
are given in Table 9 The rest of the vibrational parameterof Rubescin E molecule which is not described in Table 9can be obtained from Supplementary Material S2 The scalefactor was determined as the mean value of the scale factorthat matches correctly for the C=O stretching and the givenexperimental valueThe obtained scale factor was 09706 Noimaginary frequencies were found showing that structure ofthe molecule Rubescin E is stable in both gas and solventFigure 8 gives the representation of the scaled IR intensity andRaman scattering activity
The C=O double bond gives rise to a very intenseabsorption band in IR spectrum The position and intensityof this band range from 1870 cmminus1 to 1540 cmminus1 dependingon the physical state electronic andmass effects of neighbor-ing substituents intra- and intermolecular interactions andconjugations [29] The C=O double bond absorption spectra
were observed experimentally at 1720 cmminus1 and 1664 cmminus1[1] In this study the vibrational mode of C=O was found at172620 cmminus1 and 169057 cmminus1 gas phase and at 170101 cmminus1and 166759 cmminus1 in chloroform There is good agreementbetween the vibrational modes with experimental values
4 Conclusion
In this study the geometry optimization of Rubescin E hasbeen carried out using ab initio HF and density functionaltheoryDFT (B3LYP and B3PW91)methods in both gas phaseand chloroform solution with the 6-311++G(dp) basis setThe optimized parameters were compared to those of someexisting groups of compound present in our molecule sincenone of this have been done before for the title molecule andgood agreement was found In order to confirm the geometry
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
Applied Bionics and BiomechanicsHindawiwwwhindawicom Volume 2018
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Volume 2018
Hindawiwwwhindawicom Volume 2018
Mathematical PhysicsAdvances in
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Journal ofEngineeringVolume 2018
Submit your manuscripts atwwwhindawicom
Advances in Condensed Matter Physics 15
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
Experimental 13C NMR (ppm)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3LYP6-311++G(dp)
0255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
B3PW916-311++G(dp)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
Cal
cula
ted
13C
NM
R (p
pm)
minus250
255075
100125150175200225250275
0 25 50 75 100 125 150 175 200 225 250
RHF6-311++G(dp)
y = +107x -517 max dev836 r=0994 y = +105x +238 max dev648 r=0998
y = +105x +354 max dev541 r=0998
y = +107x -517 max dev836 y = +105x +238 max dev648
y = +105x +354 max dev541
Figure 7 Comparison of experimental and theoretical 13C chemical shifts of Rubescin E calculated at the RHF B3PW91 and B3LYP usingthe 6-311++G(dp) basis set
are given in Table 9 The rest of the vibrational parameterof Rubescin E molecule which is not described in Table 9can be obtained from Supplementary Material S2 The scalefactor was determined as the mean value of the scale factorthat matches correctly for the C=O stretching and the givenexperimental valueThe obtained scale factor was 09706 Noimaginary frequencies were found showing that structure ofthe molecule Rubescin E is stable in both gas and solventFigure 8 gives the representation of the scaled IR intensity andRaman scattering activity
The C=O double bond gives rise to a very intenseabsorption band in IR spectrum The position and intensityof this band range from 1870 cmminus1 to 1540 cmminus1 dependingon the physical state electronic andmass effects of neighbor-ing substituents intra- and intermolecular interactions andconjugations [29] The C=O double bond absorption spectra
were observed experimentally at 1720 cmminus1 and 1664 cmminus1[1] In this study the vibrational mode of C=O was found at172620 cmminus1 and 169057 cmminus1 gas phase and at 170101 cmminus1and 166759 cmminus1 in chloroform There is good agreementbetween the vibrational modes with experimental values
4 Conclusion
In this study the geometry optimization of Rubescin E hasbeen carried out using ab initio HF and density functionaltheoryDFT (B3LYP and B3PW91)methods in both gas phaseand chloroform solution with the 6-311++G(dp) basis setThe optimized parameters were compared to those of someexisting groups of compound present in our molecule sincenone of this have been done before for the title molecule andgood agreement was found In order to confirm the geometry
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
Figure 8 IR spectra (blue) and Raman spectra (red) of Rubescin E in both gas phase (top) and chloroform solution (bottom) using B3LYP6-311G(dp)
of our molecule the 3119869119867-119867 proton-proton coupling constantwas evaluated and the results compared to experiment weresimilar The calculated results have showed that RubescinE possesses a HOMO-LUMO energy gap greater than 4which indicate a hard molecule that can be used as aninsulator in many electronic devices We can also concludefrom the HOMO-LUMO analysis that the electron caneasily be transferred from the furan to tetrahydrofuran ringThe charge analysis performed using Mulliken populationCHepG and NBO methods showed positive charge for allhydrogen atoms it was observed that the most positive(respectively negative) charge atoms were directly linkedto the most negative (respectively positive) charge atomsand also that all the carbon atoms linked to hydrogen wereall negatively charged The calculated first static hyperpo-larizability was found to be more than four times greaterthan the reported value found in the literature for urealeading us to the conclusion that Rubescin E has very goodNLO properties The calculated optoelectronic propertiesshow large values of refractive index dielectric constant
and electrical susceptibility leading us to the conclusionthat Rubescin E has strong optical and phonon applicationGood agreement was found between the calculated andexperimental UV spectrumThe theoretical proton (1H) andcarbon (13C) chemical shift values (with respect to TMS)werereported and compared with experimental data showinga very good agreement for both 1H and 13C NMR Thecalculated vibrational frequencies done using the B3LYP6-311G(dp) functional in both gas and chloroform solutionswere all positive leading us to the conclusion that RubescinE was stable Approximate descriptions of the vibrationalassignments were done in order to take out the differentmotions of atoms in the title molecule
Data Availability
Most of data are already provided in themanuscriptThe data[Figures 2 and 4] used to support the findings of this study areavailable from the corresponding author upon request
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
Applied Bionics and BiomechanicsHindawiwwwhindawicom Volume 2018
Advances inOptoElectronics
Hindawiwwwhindawicom
Volume 2018
Hindawiwwwhindawicom Volume 2018
Mathematical PhysicsAdvances in
Hindawiwwwhindawicom Volume 2018
ChemistryAdvances in
Hindawiwwwhindawicom Volume 2018
Journal of
Chemistry
Hindawiwwwhindawicom Volume 2018
Advances inPhysical Chemistry
International Journal of
RotatingMachinery
Hindawiwwwhindawicom Volume 2018
Hindawiwwwhindawicom
Journal ofEngineeringVolume 2018
Submit your manuscripts atwwwhindawicom
Advances in Condensed Matter Physics 21
Conflicts of Interest
The authors declare that they have no conflicts of interest
Acknowledgments
We are thankful to the Council of Scientific and Indus-trial Research (CSIR) India for financial support throughEmeritus Professor Scheme (Grant No 21(0582)03EMR-II) to Prof AN Singh of the Physics Department BahamasHindu University India which enabled him to purchase theGaussian Software We are most grateful to Emeritus ProfAN Singh for donating this software toDr GehWilson EjuhUniversity of Dschang IUT-FV Bandjoun Cameroon
Supplementary Materials
The optimized geometry parameters of the Rubescin Emolecule such as bonds length bonds angles and dihedralangle obtained at the three levels RHF B3PW91 and B3LYPusing the 6-311++G(dp) basis set in gas phase and in asolution of chloroform are listed in Supplementary Material1 The vibrational frequencies of the title molecules alongwith the IR intensity and Raman scattering activity of eachvibrational mode obtained at the B3LYP6-311G(dp) basisset in both gas phase and a chloroform solution are listedin SupplementaryMaterial 2 associated with this manuscript(Supplementary Materials)
References
[1] T T Armelle N K Pamela M Pierre et al ldquoAntiplasmodiallimonoids from Trichilia rubescens (Meliaceae)rdquo MedicinalChemistry vol 12 no 7 pp 655ndash661 2016
[2] Y Zhang Z Guo and X-Z You ldquoHydrolysis theory forcisplatin and its analogues based on density functional studiesrdquoJournal of the American Chemical Society vol 123 no 38 pp9378ndash9387 2001
[3] H Tanak F Ersahin Y Koysal E Agar S Isik and MYavuz ldquoTheoretical modeling and experimental studies on N-n-Decyl-2-oxo-5-nitro-1-benzylidene-methylaminerdquo Journal ofMolecular Modeling vol 15 no 10 pp 1281ndash1290 2009
[4] Y B Alpaslan N Suleymanoglu E Oztekin F Ersahin E Agarand S IsIk ldquoExperimental and semi-empirical and DFT calcu-lational studies on (E)-2-[(24-Dichlorophenylimino) methyl]-p-cresolrdquo Journal of Chemical Crystallography vol 40 no 11 pp950ndash956 2010
[5] M Szafran A Komasa and Z Dega-Szafran ldquoSpectro-scopic and theoretical studies of bis(dimethylphenyl betaine)hydrochloride monohydraterdquo Vibrational Spectroscopy vol 79pp 16ndash23 2015
[6] S Difley L-P Wang S Yeganeh S R Yost and T V VoorhisldquoElectronic properties of disordered organic semiconductorsvia QMMM simulationsrdquo Accounts of Chemical Research vol43 no 7 pp 995ndash1004 2010
[7] G-J Linker P H M V Loosdrecht P V Duijnen and R BroerldquoComparison of ab initio molecular properties of EDO-TTFwith the properties of the (EDO-TTF)2PF6 crystalrdquo ChemicalPhysics Letters vol 487 no 4-6 pp 220ndash225 2010
[8] G W Ejuh F T Nya R A Y Kamsi and J M B NdjakaldquoInvestigation of the electronic optoelectronics and linearand nonlinear optical properties of the molecules heptacene([7]acene) (C30H18) and [7]acene doped with potassium atom(C30H9K9)rdquo Polymer Bulletin pp 1ndash16 2017
[9] M Frisch G W Trucks H B Schlegel et al Gaussian 09Revision A02 Gaussian Inc Wallingford UK 2009
[10] H J Reich Vicinal Proton-Proton Coupling 3JHH vol 14University of Wisconsin Chemistry 2010
[11] K BWiberg and YWang ldquoA comparison of some properties ofC=O and C=S bondsrdquo Arkivoc vol 2011 no 5 pp 45ndash56 2011
[12] P B Liescheski and D W H Rankin ldquoMolecular structure offuran determined by combined analyses of data obtained byelectron diffraction rotational spectroscopy and liquid crystalNMR spectroscopyrdquo Journal of Molecular Structure vol 196 noC pp 1ndash19 1989
[13] R Siegfried and M Dieter ldquoEthylene Oxiderdquo Journal of Molec-ular Structure vol 13 pp 547ndash572 2012
[14] H J Geise W J Adams and L S Bartell ldquoElectron diffractionstudy of gaseous tetrahydrofuranrdquo Tetrahedron vol 25 no 15pp 3045ndash3052 1969
[15] I FlemingMolecular Orbitals and Organic Chemical ReactionsJohn Wiley amp Sons Ltd Chichester UK 2009
[16] S Xavier S Ramalingam and S Periandy ldquoExperimental [FT-IR and FT-Raman] analysis and theoretical [IR Raman NMRand UVndashVisible] investigation on propylbenzenerdquo Journal ofTheoretical and Computational Science vol 109 pp 1ndash12 2014
[17] D Zeynep A K Cigdem and B Orhan ldquoTheoreticalanalysis (NBO NPA Mulliken Population Method) andmolecular orbital studies (hardness chemical potential elec-trophilicity and Fukui function analysis) of (E)-2-((4-hydroxy-2- methylphenylimino)methyl)-3methoxyphenolrdquo Journal ofMolecular structure vol 1091 pp 183ndash195 2015
[18] N M OrsquoBoyle A L Tenderholt and K M Langner ldquoSoftwarenews and updates cclib a library for package-independentcomputational chemistry algorithmsrdquo Journal of ComputationalChemistry vol 29 no 5 pp 839ndash845 2008
[19] J B Foresman and A Frisch Exploring Chemistry with Elec-tronic Structure methods Gaussian Inc Pittsburgh Pa USA1996
[20] H Reis M Papadopoulos P Calaminici K Jug and AKoster ldquoCalculation of macroscopic linear and nonlinear opti-cal susceptibilities for the naphthalene anthracene and meta-nitroaniline crystalsrdquo Chemical Physics vol 261 no 3 pp 359ndash371 2000
[21] M Govindarajan and M Karabacak ldquoFT-IR FT-Ramanand UV spectral investigation Computed frequency esti-mation analysis and electronic structure calculations on 4-hydroxypteridinerdquo Journal of Molecular Structure vol 1038 pp114ndash125 2013
[22] O Tamer ldquoA unique manganese (II) complex of 4-methoxy-pyridine-2-carboxylate Synthesis crystal structure FT-IR andUVndashVis spectra and DFT calculationsrdquo Journal of MolecularStructure vol 1144 pp 370ndash378 2017
[23] D Freude ldquoChapter Radiationrdquo Journal of Spectroscopy pp 1ndash21 2006
[24] G W Ejuh S Nouemo and J M B Ndjaka ldquoTchangnwaNya Modeling of the electronic optoelectronics photonic andthermodynamics properties of 14 bis(3 carboxyl 3 oxo prop 1enyl) benzene moleculerdquo Iranian Chemical Society 2016
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017
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Submit your manuscripts atwwwhindawicom
22 Advances in Condensed Matter Physics
[25] A Spott A Jaron-Becker and A Becker ldquoAb initio andperturbative calculations of the electric susceptibility of atomichydrogenrdquo Physical Review A Atomic Molecular and OpticalPhysics vol 90 pp 1ndash6 2014
[26] R Carrasco J Padron and J Galvez ldquoDefinition of a novelatomic index for QSAR the refractopological staterdquo Journal ofPharmaceutical Science vol 7 pp 19ndash26 2004
[27] J A Padron R Carasco and R F Pellon ldquoMolecular descriptorbased on a molar refractivity partition using Randic-typegraph-theoretical invariantrdquo Journal of Pharmaceutical Sciencesvol 5 pp 258ndash265 2002
[28] I Cakmak ldquoGIAO calculations of chemical shifts in enantio-metrically pure 1-trifluoromethyl tetrahydroisoquinoline alka-loidsrdquo Journal ofMolecular Structure THEOCHEM vol 716 no1-3 pp 143ndash148 2005
[29] E Temel C Alasalvar H Eserci and E Agar ldquoExperimental(X-ray IR and UVndashvis) and DFT studies on cocrystallizationof two tautomers of a novel Schiff base compoundrdquo Journal ofMolecular Structure vol 1128 pp 5ndash12 2017