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27. Molecular Orbital Theory

Date: 4 November 2001 Suggested Reading: Chapters 9-7 to 9-16 of the text.

Introduction
We will construct sets of molecular orbitals for diatomic molecules by combining pairs of atomic orbitals, one from each atom.

Labelling of the Molecular Orbitals

If the resulting molecular orbital is symmetric about the internuclear axis, then the MO s called a (sigma) orbital. For example,

Figure 27-1: Sketch of two 1s atomic orbitals forming a molecular orbital.

Scott Kirkby Last revised: 04 November 2002

Introduction to Quantum Chemistry

Lecture # 27

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There are many combinations of atomic orbitals that will lead to orbitals. thus we add on the label for the originating atomic orbital, that is
1s A + 1s B 1s

(27-1)

An antibonding orbital is designated with a * superscript.

1s A 1s B 1s

(27-2)

orbitals may be alternately designated by their symmetry with respect to a center of inversion at the center of the molecule. If the orbital does not change sign with inversion, it is labelled with a g for the German word for even (gerade). If it changes sign, it is labelled u for ungerade. (not even, that is odd).
1 1s = ------------------------ ( 1s A + 1s B ) 2(1 + S) = g 1s 1 1s = ----------------------- ( 1s A 1s B ) 2(1 S) = u 1s
(27-4) (27-3)

Note: It is possible for an orbital to be g and antibonding and u and bonding as we shall see. Only atomic orbitals of similar energies are combined in this fashion to give molecular orbitals. (Large differences in energy lead to little overlap.)

Scott Kirkby

Last revised: 04 November 2002

Introduction to Quantum Chemistry

Lecture # 27

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2s A + 2s B g 2s 2s A 2s B u 2s 2p zA + 2p zB g 2p z 2p zA 2p zB u 2p z
(27-5)

What if we combine 2px and 2pz?

2p xA + 2p zB No net overlap 2p xA 2p zB No net overlap
(27-6)

Figure 27-2: Pictorial representation of the combination of the 2px and 2pz orbitals.

Scott Kirkby

Last revised: 04 November 2002

Introduction to Quantum Chemistry

Lecture # 27

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Symmetry plays a role in combining orbitals in useful ways.

Figure 27-3: Pictorial representation of the combination of the 2pxA and 2pxB orbitals.

The 2pxA + 2pxB molecular orbital has a nodal plane in the yz plane (by convention, the z direction is the line joining the two nuclei) running through the internuclear axis. Molecular orbitals that have a nodal plane colinear with the internuclear axis are called orbitals.
2p xA + 2p xB u 2p x 2p xA 2p xB g 2p x
(27-7)

Here the gerade molecular orbital is antibonding. The same happens for 2py
2p yA + 2p yB u 2p y 2p yA 2p yB g 2p y
(27-8)

Scott Kirkby

Last revised: 04 November 2002

Introduction to Quantum Chemistry

Lecture # 27

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Ordering of Energies

Figure 27-4: Ordering of the molecular orbitals for diatomic molecules. Note figure is not to scale. For molecules N2 and lighter g2pz is higher in energy that u2px and u2py. For O2 and heavier, the ordering is reversed.

Suggested Reading for Next Lecture: Chapter 10 of the text.

Scott Kirkby

Last revised: 04 November 2002