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Molecular Orbital Theory

Unlike hybrid orbitals that are constructed from the orbital set of a single atom, molecular
orbitals are Linear Combinations of Atomic Orbitals that are distributed over the entire
molecule.
Molecular orbitals have associated with them a set of energy levels that follow the
Aufbau Principle and also satisfy the Pauli Exclusion Principle. Remember that for the
construction of hybrid orbitals, the number of hybrid orbitals equals the number of atomic
orbitals from which they are constructed. The same is true for MOs.
Number of molecular orbitals = number of atomic orbitals from which they are
constructed

MOs based on 1s orbitals

We start by taking a linear combination of 1s
atomic orbitals on two distinct hydrogen
atoms. Remember that the increased
electron density between bonding atoms
results in a lowering of energy. We also use
the language of waves to think of this
increase in electron density as complete
constructive interference. We call the
bonding molecular orbital the 1s MO.
Following the Pauli Exclusion Principle, we
place two electrons in the MO with electron
spins paired, as shown on the left.
Mathematically, we would say:
MO, bonding (1sA) + (1sB)

Since we used two 1s wavefunctions, one on each atom, we must also have a second
molecular orbital. The second MO is equivalent to complete destructive interference of
the matter wave amplitude between the atoms. The energy of this antibonding MO lies
above that of the separated atoms and is denoted *1s.
Matematically, we write MO, antibonding (1sA) - (1sB)

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We can visualize the electron density distributions for the bonding and antibonding MOs
from the following diagrams:

Note that the antibonding MO changes sign between the lobes, so there is a nodal plane
perpendicular to the bond axis. Remember that the orbitals are probability
amplitudes, and can be positive or negative. The square of the amplitude is always
positive, and represents the true probability of finding a particle in a region of
space.
We can place the number of electrons from the constituent atoms in the orbitals to
understand electron configurations in molecules.
For H2, we write the electron figuration as (1s)2. If we remove a single electron, we
make the H2+ molecular ion, and its electron configuration is (1s)1. The H2+ molecular
ion is well known in mass spectrometry.
Bond energy for H2 = 432 kJ/mol
Bond energy for H2+ = 255 kJ/mol
We can construct the electron
configurations for two helium atoms
in like manner, using the fact that
each He atom contributes two
electrons to the bonding scheme.
Note that the third and fourth
electrons go into the antibonding
orbital.

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We define the bond order (BO) as (number of bonding electrons number of

antibonding electrons)
According to this definition, the BO for H2 is 1, that for H2+ is 0.5, and for He2, the BO is
zero. The bond energies for H2 and H2+ indicated above are in semiquantitative
agreement with the concept of BO. A bond order of zero means that there is no covalent
bonding (which involves the sharing of electrons), but only the weak van der Waals
force. The binding energy of He2, which comes entirely from vdW forces, is about 0.1
kJ/mol.
We can also add and remove electrons
to examine electron configurations of
various molecular ions. If we remove
a single antibonding electron to make
He2+, the BO is calculated to be 0.5,
and the bond energy of this species
has been measured to be ~230 kJ/mol.
So, its bond strength is about half that
of H2.
In contrast, H2-, which also has a BO
of 0.5 is known to be unstable.
Negative ions in general are peculiar entities, and it is difficult to predict a priori
whether a given species is stable or not.
MOs of molecules comprised of second row atoms
The first species we encounter in the second
row is Li2. When we look at the electron
distributions in the atomic orbitals of Li, we
see that there is negligible overlap of the
electrons in the 1s orbitals. MOs are formed
from the valence electrons. There is
significant overlap of the electrons in the 2s
orbitals.
We can construct bonding and antibonding MOs form the 2s orbital set on each Li atom,
and the MO energies look qualitatively the same as those made from 1s orbitals. The
electron configuration for Li2 is (2s)2.

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We can also make the molecular ions Li2+ and Li2-. Both of these species exist (unlike
the corresponding cases with hydrogen).
For your cultural enrichment, the bond strength in Li2 is ~101 kJ/mol, while in Li2+
(with one fewer bonding electron), the bond energy is 139 kJ/mol. Devotees of
simple MO theory hate this example. There is no simple explanation. This wont be
on the test.

MOs involving 2p-orbitals

When the 2p orbitals on each atom interact, two distinct kinds of interactions can occur.
The first homonuclear diatomic molecule in which the 2p orbitals can interact is
constructed from two boron atoms. Figure (a) below shows the orbitals orientations that
can arise from the interaction of two boron atoms.

Panel (d) in the above figure shows that only one of the 2p orbitals on each atom lies
along the bond axis. Those two orbitals overlap to give an electron density distribution
that is cylindrically symmetric about the bond axis (See the figure). The remaining four
orbitals, two per atom, generate MOs that are fundamentally different in shape. The
axes defining the directions (orientations) of the p orbitals are parallel to one another
when electron overlap occurs. The electron density distribution is no longer
cylindrically symmetric. Panels (b) and (c) show how the orbitals interact to form -type
MOs. Note also that the two -type interactions differ only by a rotation of 90 about
the bond axis, i.e., they are degenerate.

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When we construct MOs we always have a symmetric and an antisymmetric

combination of orbitals, corresponding to constructive and destructive interference
respectively, of amplitude between the bonding atoms. The figure below shows how
these combinations occur. We have one 2p (bonding) and one *2p (antibonding) MO.
Note that the electron density is enhanced along the bond axis for the 2p (bonding)
orbital, and there is a node for the *2p (antibonding) orbital. The upper two orbitals in
the figure below show those orbitals.
We can also construct bonding and antibonding MOs from the -type orbital set. These
MOs are not cylindrically symmetric about the bond axis. The 2p MOs are bonding,

with increased electron density (remember that the electron density is proportional to the
square of the wavefunction) between the atoms. In contrast, the *2p antibonding orbitals
have a nodal plane between the atoms.
Energy Ordering the MOs
Of course, the bonding MOs are lower in energy than the energies of the isolated atoms.
But, we have no a priori way to determine whether the or orbitals are lower. The
next two diagrams illustrate the possibilities.

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One possibility:
The figure shows that if the MO is the lowest in energy, then the two 2p electrons from
the boron atoms should have
paired electron spins in B2. This
would make B2 diamagnetic, i.e.,
weakly repelled by an external
magnetic field.
In fact, B2 is strongly attracted
by an external magnetic field.

This indicates that B2 has

unpaired electrons, and the
correct picture of the orbitals is
that shown in the lower figure.
Hunds Rule states that we must
place electrons in distinct,
degenerate orbitals (the two 2p
orbitals) with the same spin.

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For the first three elements in the 2p series (B, C, N), the 2p orbitals lie below the 2p
orbitals. For the atoms in the last half of the series (O, F, Ne), the order is reversed.
The figure below shows the electron configurations for these species. One important
consequence of this ordering is the fact that molecular oxygen, O2,is paramagnetic, a fact
that has important consequences in many chemical applications, especially in
photochemistry and atmospheric chemistry.

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Heteronuclear diatomics
There are many examples of such species. As a simple example, consider HF. The MO
diagram is shown below. Note that the positions of the atomic orbitals are asymmetric,
with the ionization potential of the atom determining its position:

Ionization limit

Hydrogen ionization energy

= 1312 kJ/mol

Fluorine ionization energy

= 1681 kJ/mol

The larger ionization energy of fluorine makes its valence orbital lie below that of the 1s
orbital in hydrogen.

Comment on the NO molecule. Although NO has one atom with a p2 configuration and
one with a p4 configuration, the correct MO diagram for NO has the orbitals below the
orbitals, just like in O2.