Page 1 Molecular orbital theory We would like a theory of bonding that can be visualized and is at least semiquantitative. We have a picture of atoms with an electronic structure described by orbitals. Why not do the same thing for molecules ? Employ the orbital approximation Ψ(r 1 ,r 2 ,r 3 ,....) = ψ(r 1 )ψ(r 2 )ψ(r 3 )....... How do we arrive at an approximation to the orbitals ? The electron density distribution for an electron in the vicinity of a nucleus in a molecule should be similar to that found in the free atom. Use the idea of Linear Combination of Atomic Orbitals (LCAO). What orbitals do we combine ? Start with a minimal basis (just the valence orbitals).
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1Page 1
Molecular orbital theory
We would like a theory of bonding that can be visualized and is at least semiquantitative.We have a picture of atoms with an electronic structure described by orbitals. Why not do the same thing for molecules ?Employ the orbital approximation
Ψ(r1,r2,r3,....) = ψ(r1)ψ(r2)ψ(r3).......
How do we arrive at an approximation to the orbitals ?
The electron density distribution for an electron in the vicinity of a nucleus in a molecule should be similar to that found in the free atom.Use the idea of Linear Combination of Atomic Orbitals (LCAO).What orbitals do we combine ?Start with a minimal basis (just the valence orbitals).
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Bonding in H2
Take two 1s orbitals as the basisGet two MO’s
ψ+ = φ1s(A) + φ1s(B)ψ- = φ1s(A) - φ1s(B)
One electron in BO gives 2.6 eV bond energy but two electrons give only 4.5 eV. Why?
What holds the molecule together?
There is nothing magic about the molecule being bonded– Electrons preferentially spend time between the
two nuclei. They act as electrostatic “glue”
– ψ+2 = [φ1s(A)]2 + [φ1s(B)]2 +
φ1s(A)φ1s(B) + φ1s(B)φ1s(A) » First two terms are electron density on original atoms,
other terms correspond to density between atoms
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Interatomic potentials
Molecular potential energy curve– the equilibrium bond
length corresponds to the minimum energy bond length
– De is the depth of the potential well
UV - PES
How do we know if the energy level diagrams have any meaning ?We can compare to experiments that directly measure the orbital energiesIlluminate a sample with high energy radiation (usually 21.2 eV - in the UV) and measure the kinetic energies of the ejected electrons.– Ek = hν - I
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The PES experiment
The PES spectrum of N2
Note nitrogen atoms have a first ionization energy of 14.5 eV
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Construction of MO diagrams for other diatomics
We need to select a basis set– usually use valence orbitals
We need to categorize the basis orbitalsaccording to their symmetry– only orbitals with the same symmetry have nonzero
overlapFigure out the relative energies of the orbitals– this may require help from spectroscopic data
Classifying orbitals by symmetry
Orbitals in diatomics can be classified according to their rotational symmetry characteristics as σ, π or δ. These classifications are strictly only valid for diatomics, but we also use them to describe bonds between pairs of atoms in polyatomic molecules.
σ orbitals π orbitals δ orbitalsFound in quadruply bonded species such as [Re2Cl8]2-
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MOs in first row diatomics
Ungerade or gerade ?MOs in molecules that are centrosymmetric can be classified as (g) or (u)– Useful for predicting spectroscopic transitions etc.– (g) implies that the wavefunction does not change sign
on inversion through the center of the molecule. (u) means that it does change sign
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Experimental MO energies
Determining electron configurations
The filling rules are essentially the same as those for atoms– Two electrons per orbital– Fill from the lowest energy up– If orbitals are degenerate go for the electron
configuration with the highest spin (Hund’s rule)Consider O2– 1σg
2 2σu2 3σg
2 1πu4 2πg
2
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Hetronuclear diatomics
The contributions to the MO from each of the atoms is unequal– ψ = cAφ(A) + cBφ(B) +.......
The more electronegative atom contributes strongly to the bonding orbitalThe less electronegative atom contributes strongly to the anti-bonding orbital– gives rise to polarity
Orbital mixing
The difference in energy between orbitals on different atoms leads to reduced mixing– The reduced mixing does
not imply weaker bonding
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Hydrogen fluoride
Carbon monoxide
Note that the HOMO and LUMO are largely on C. Important for metal carbonyl formation
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ICl an interhalogen compound
Bond order
B.O. = 1/2 x (No. bonding e - No. anti-bonding e)
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Bond strength / bond length
H3+
This species is postulated as an intermediate in some reactions– It is the simplest triatomic molecule
There is a relationship between the orbitals in the linear and triangular species. This relationship (how the orbital energies evolve on bending from linear to triangular) is shown on a Walsh or correlation diagram.
Three center two electron bonds
The orbitals in H3 are delocalized over the entire moleculeIn H3
+ 2 electrons hold the molecule together– this is an example of a three center two electron
bond
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MO s for Polyatomic chains
Constructing MOs for polyatomic chains
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MOs for rings
Orbitals in more complex molecules
In general, we form MOs from linear combinations of AOs with the correct symmetry propertiesThe energy of the MOs increases as the number of nodes increasesMOs made up from low energy AOs also have low energies
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MOs for NH3
The basis set consists of 3 H1s orbitals and the N 2s and 2p orbitalsThe molecule is known to have three fold symmetryThe N 2s and 2pz orbitals have cylindrical symmetry (also have three fold symmetry)The linear combination H 1s(A) + 1s(B) + 1s(C) has three fold symmetry
a1 MOs for NH3
Combine orbitals/LCAOS with cylindrical symmetry to form MOs
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e MOs for NH3
A combination of N 2px and 2py orbitals and linear combinations of H1s orbitals have e symmetry
Composition of NH3 MOs
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MO diagram + PES for NH3
SF6 and hypervalence
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Diborane and electron deficient compounds
B2H6 is a compound that you can not draw a reasonable Lewis structure for !
Electron deficient as the three atoms forming the B-H-B bridge are held together using only two electrons
XeF2 and electron excess compounds
The electronic structure of XeF2 and it’s stability can be rationalized by invoking a 3 center 4 electron bond