The molecular orbital (MO) theory is a way of looking at the structure of

a molecule by using molecular orbitals that belong to the molecule as a whole

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Figure 1. Combination of two 1s atomic orbitals to form a sigma bonding orbital or a

sigma-starred antibonding orbital.

rather than to the individual atoms. When simple bonding occurs between two
atoms, the pair of electrons forming the bond occupies an MO that is
a mathematical combination of the wave functions of the atomic orbitals of the two
atoms involved. The MO method originated in the work of Friedrich Hund and
Robert S. Mulliken.

When atoms combine to form a molecule, the number of orbitals in the molecule
equals the number of orbitals in the combining atoms. When two very simple atoms,
each with one atomic orbital, are combined, two molecular orbitals are formed. One
is a bonding orbital, lower in energy than the atomic orbitals, and derived from their
sum. It is called sigma. The other is an antibonding orbital, higher in energy than the
atomic orbitals, and resulting from their difference. It is called sigma-starred ( *).
(See the diagram in Figure 1.)
The basic idea might best be illustrated by considering diatomic molecules of
hydrogen and helium. The energy diagrams are shown in Figure 2. Each hydrogen
atom has one 1 s electron. In the H 2 molecule the two hydrogen electrons go into the
lowest energy MO available, the sigma orbital. In the case of helium, each helium
atom has two electrons, so the He 2 molecule would have four. Two would go into the
lower energy bonding orbital, but the other two would have to go into the higher
energy sigma-starred orbital.

Figure 2. Molecular orbital energy diagrams for (a) H 2 showing both electrons in the
bonding sigma MO; and (b) He 2 in which two of the electrons are in the antibonding
sigma-starred MO
Figure 3. Combination of p atomic orbitals to form (a) sigma MOs by end-to-end
interactions or (b) pi MOs by sideways interaction.

Bond Order

The bond order for a molecule can be determined as follows: bond order =
(bonding electrons antibonding electrons). Therefore, the H 2 molecule has a bond
order of (2 0) = 1. In other words, there is a single bond connecting the two H
atoms in the H 2 molecule. In the case of He 2 , on the other hand, the bond order is
(2 2) = 0. This means that He 2 is not a stable molecule.
Multiple Bonds

Double or triple bonds involve two or three pairs of bonding electrons. Single bonds
are always sigma bonds, but in multiple bonds the first bond is sigma, while any
second or third bonds are pi bonds. The overlap of p orbitals can yield either pi or
sigma MOs, as shown in Figure 3. When they overlap end to end, they form sigma
orbitals, but when they overlap side to side, they form pi orbitals.

Consider now the oxygen molecule. The Lewis structure for oxygen is :::: The
double bond is necessary in order to satisfy the octet rule for both oxygen atoms. The
measured bond length for oxygen supports the presence of a double bond. Yet we
know that this Lewis formula cannot be the correct structure for oxygen because
oxygen is paramagnetic, which means that the oxygen molecule must have unpaired
electrons.

Look now at the MO diagram for oxygen, which is shown in Figure 4. It still indicates
a bond order of 2 [(10 6) = 2], but it also shows two unpaired electrons.
Figure 4. MO energy diagram for O 2 . Eight electrons from each oxygen atom add up
to 16 electrons in the O 2 molecule. They combine to form the molecular orbitals
indicated above.

The MO theory also works well for larger molecules such as N 2 O, CO 2 , and BF 3 and
for ions such as NO 3 and CO 3 2 , in which the bonding MOs are delocalized,
involving three or more atoms. It is especially useful for aromatic matic molecules
such as benzene. In this case all six C atoms in the ring are equally involved in a
delocalized pi electron cloud that envelops the entire molecule. The MO theory can
even be extended to complex ions and to solids, including materials such as
superconductors and semiconductors.
The valence bond (VB) theory of bonding was mainly developed by Walter Heitler
and Fritz London in 1927, and later modified by Linus Pauling to take bond direction
into account. The VB approach concentrates on forming bonds in localized orbitals
between pairs of atoms, and hence retains the simple idea of Lewis structures and
electron pairs. The wave function for the bonding electrons is described as the
overlap of atomic orbitals. Thus, in the H 2 molecule, the spherical s orbitals of the
two H atoms simply overlap, so that the electrons in the bond sense the nuclei of
both atoms. This method also works well for simple molecules like H 2 O, CH 4 , and
NH 3 . First the appropriate hybrid orbitals are constructed on the central atom to
give the correct molecular geometry (e.g., four sp 3 tetrahedral orbitals on the C atom
in CH 4 ). The bonding picture is then constructed by simple overlap of the atomic
orbitals, (e.g., one 1s orbital of a H atom with each sp 3 lobe of the C atom in CH 4 to
give four CH bonds).

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Figure 1. The bonding in the BF 3 molecule: Three sp 2 hybrid orbitals on

the boron atom overlap a p orbital from each of the three fluorine atoms.
Bonding in BF 3

The electron configuration of the boron atom is 2s 2 2p 1 , with one unpaired electron.
This electron is excited to the higher energy configuration 2s 1 2p 2 , with three
unpaired electrons. These three orbitals are now hybridised to give three equivalent
sp 2 hybrid orbitals, coplanar, and lying 120 apart, each containing one electron.
These hybrid orbitals then overlap the half-filled p orbitals of the three fluorine
atoms, thus forming three coplanar BF electron-pair bonds. (See Figure 1.)

All seems well, except that the boron atom does not have an octet:
One perpendicular 2p orbital remains empty. This orbital can accept electron density
from the F atoms to a maximum of one electron pair. On average, each F atom
donates one-third of an electron pair to the empty p orbital on boron. One model for
BF 3 is a resonance hybrid of three structures, each having one double bond and two
single bonds. The BF bond is said to have a bond order of 1.

Some Shortcomings

The valence bond approach is especially useful in organic chemistry where so many
molecules are built of tetrahedral C atoms, sp 3 hybridised. The concept of hybrids is
intuitively very satisfying because they fit visually with our perceived picture of the
shape of a molecule with its directed bonds between pairs of atoms. Unfortunately,
the VB approach is not satisfactory for species like CO 3 = , NO 3 ,
and benzene because the VB picture does not reflect the known chemical structure. A
new concept of resonance hybrids must be introduced, and CO 3 = must now be
represented by a combination of three Lewis-octet structures. Worse still, the VB
approach cannot easily give a satisfactory bonding picture for either of the important
molecules O 2 or CO.
In cases where the VB approach does not work well, the molecular orbital (MO)
method is often more successful. The situation is best summarized by using the
strengths of the VB approach where they are appropriate, as in CH 4 , and using the
MO approach where it is best suited, as in O 2 and benzene. After all, each approach is
an approximation, incomplete and imperfect.