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 basis
‹ Get 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 energies
‹ Illuminate 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 orbitals
according to their symmetry
– only orbitals with the same symmetry have nonzero
overlap
‹ Figure 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.

δ orbitals
σ orbitals π orbitals
Found 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

‹ Thefilling 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
– 1σg2 2σu2 3σg2 1πu4 2πg2

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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 orbital
‹ The 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

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Linear H3

1σ = φ1s(A) + 21/2φ1s(B) + φ1s(C)

2σ = φ1s(A) - φ1s(C)
3σ = φ1s(A) - 21/2φ1s(B) + φ1s(C)

Triangular

a1 = φ1s(A) + φ1s(B) + φ1s(C)

φ1s(A) - φ1s(C)
e{
φ1s(A) - 2φ1s(B) + φ1s(C)

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Correlation diagram / Walsh diagrams
‹ 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 molecule
‹ In 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
properties
‹ The energy of the MOs increases as the number
of nodes increases
‹ MOs 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 orbitals
‹ The molecule is known to have three fold
symmetry
‹ The 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

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