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MolecularOrbitalTheory
Molecular Orbital Theory
Molecular orbital theory describes bonding in terms of orbitals which encompass
the entire molecule. These orbitals are viewed as resulting from the constructive or
destructive interaction of atomic orbitals of the atoms in the molecule. In a simple
diatomic molecule, molecular orbitals can be viewed as overlap between the atomic
orbitals on each atom. For overlap to occur, the atomic orbitals must be of similar
energy, and must have the proper symmetry. If the overlap is constructive,
electron density will increase in the region between the two nuclei, and a bonding
orbital results. That is, the system is stabilized relative to two separate atoms. If
the interaction of the two atomic orbitals is destructive, nodal planes result
between the nuclei, resulting in a destabilizing, or antibonding orbital.
Atomic orbitals can overlap in a variety of ways. Endonend overlap, which
results in electron density along the internuclear axis (usually specified as the z
axis) results in a (sigma) bond. This type of overlap is possible between two
neighboring s orbitals, between an s orbital and a pz orbital, or between two
neighboring pz orbitals. The shapes of the bonding orbitals are illustrated below.

Adjacent atomic orbitals can also overlap sidebyside. This type of constructive
overlap results in electron density above and below the internuclear axis, and is
called a bond. Neighboring px or neighboring py orbitals can overlap in this way.
A nodal plane which passes through the internuclear axis results.

Atomic orbitals on neighboring atoms can also overlap facetoface. This occurs
between d orbitals, and is seen in transition metal compounds. The bond, which is
called a bond, results in two nodal planes which intersect along the internuclear
axis.

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Energy level diagrams can be created for molecular orbitals, and they are similar
to atomic energy level diagrams. Bonding orbitals (constructive overlap) are always
lower in energy than their antibonding (destructive overlap) counterparts. Each
level is designated by its number, type (, and its symmetry with relation to
inversion through the center of the molecule. If a molecular orbital is symmetrical
with respect to inversion, it has a subscript g (gerade, for even). If it is
asymmetrical with respect to inversion, it is given a subscript u (ungerade, for
uneven). The molecular orbitals for the combination of s orbitals on neighboring
atoms are drawn below. The bonding orbital is given the designation g, and will
be lower in energy. The antibonding orbital, which will be higher in energy, is given
the designation u, because the sign of the orbital changes upon inversion through
the center.

The possible combinations between neighboring p orbitals are shown below. The
orbitals can combine endtoend to form bonding and antibonding orbitals, or
sidebyside to produce bonding and antibonding orbitals. It is important to note
that the notations of gerade and ungerade are unrelated to the bonding or
antibonding nature of the resulting molecular orbital. Each type of orbital and its
symmetry must be considered separately.

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 The above molecular orbitals differ in energy, and an energy level diagrams can be
constructed for simple diatomic molecules. The simplest diagram, which assumes
no interaction between s orbitals on one atom and p orbitals on the other has the
following form: (Please note that the numerical prefixes for the orbitals are not
correct. The lowest orbital should be 1g, and the orbitals in the upper section
should both have the prefix 1 see figure 3.14 of the text

The lower orbitals represent the sigma bonding and antibonding orbitals. The
upper section shows the sigma (endtoend) bonding orbital between two pz orbitals
(lowest in energy), then the two degenerate bonding orbitals. Next in energy are
the two degenerate antibonding orbitals, and highest in energy, the antibonding
orbital. This type of diagram, which assumes that the 2p orbitals are high enough
in energy so that they do not interact with the 2s orbitals, is appropriate for the
diatomic molecules O2 and F2. For the diatomic molecules Li2 through N2, there is
evidence for significant interaction between the 2p and the 2s orbitals. The energy
diagram will be altered as follows: (Please note that the numbering is again
incorrect. Your text contains the correct numbering for the orbitals see figure
3.18)

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Molecular orbital diagrams can also be developed for heteronuclear diatomic

molecules. For these molecules, the overlap is often less, since the energy levels of
the orbitals on each atom usually differ. The simplest case is for a molecule such
as HF, where only the 1s orbital of hydrogen need be considered. It can overlap
with both the 2s and 2pz orbitals on fluorine to produce the following MO diagram.

Note that the notation gerade and ungerade are no longer used, as the molecule
no longer has a center of inversion. Since the orbitals on fluorine are lower in
energy than those of hydrogen, the bonding orbitals reside mostly on fluorine. This
is consistent with the high electronegativity of fluorine. The molecular orbitals
are nonbonding, and represent the lone pairs of electrons in the px and py orbitals
of fluorine. The molecule can be viewed as having bonds resulting from the overlap
of the hydrogen 1s orbital with both the 2s and 2p orbitals of fluorine, or with sp
hybrid orbitals on fluorine. The 3 molecular orbital, which is antibonding, resides
predominantly on hydrogen, because it is closer in energy to the orbitals on the
hydrogen atom.
A similar treatment for the bonding in carbon monoxide is significant, as CO
serves a ligand in many transition metal complexes. Here, the energies of the
orbitals in carbon and oxygen are a bit closer, so more interaction is possible.

 In considering bonding of CO to transiton metals, the highest occupied

molecular orbital (2) and the lowest unoccupied molecular orbital (3) are key.
The HOMO is essentially the lone pair of electrons on carbon, and the LUMO are
the 2 antibonding orbitals which are also skewed more towards the carbon atom.
Depictions of the electron density of each orbital follows. Note that the lower energy
orbitals will tend to reside more on the oxygen atom, and the higher energy orbitals
will reside more on the carbon atom.

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