Unit I

Chemical Bonding

Module 1.2

Molecular Orbital Theory

In discussing valence bond theory, the student has learnt a general

principle of quantum mechanics. If there are several possible equal out
comes, then we add together the wave functions that represent the
different outcomes. For example in the hydrogen molecule

= c1A + c2B where c1 and c2 are numerical coefficients. This wave

function is known as the linear combination of atomic orbitals (LCAO).
and indicate the extent of the contribution of the atomic orbitals to the
molecular orbital. In a homonuclear diatomic molecule like H2, .
This is because in such molecules the electron can be found with equal
probability in the atomic orbital of A or in orbital B. also we noted that
and hence c2 = 1. Then the two possible wave functions are written
as

I = [A + B] and II = [A B] .

I and II stand for the wave function of a molecular orbital. A molecular

orbital is a one electron wave function for an electron that spreads
throughout the molecule. The mathematical forms of such orbitals are
highly complicated even for a system like . And such relations are
unknown in general. Therefore a true molecular orbital is built by the
models based on the linear combination of the atomic orbitals on the atoms
in the molecule.

Now let us consider the molecular orbital I. This form of the orbital has the
lower energy than either of the two AOs (AO stands for atomic orbital) this
molecular orbital is known as orbital because it resembles an s orbital
when viewed along the internuclear axis. The orbital of lowest energy is
labeled as 1. Similarly the other orbital are represented as 2, 3 . An
electron that occupies a orbital is called a electron. In the ground state
of an electron in hydrogen molecule ion, , there is a single 1 electron.
Then the ground state configuration of is reported as 11.

ORIGIN OF LOWERING OF ENERGY Formation of bonding orbital

The two AOs are like waves originating from the two interacting nuclei. The
amplitudes of these waves interfere constructively in the internulear region.
The wave function has an enhanced amplitude. This is depicted in the
figure below.
Because of the increased amplitude, there is an increased probability of
finding the electron between the two nuclei. The electron can interact
strongly with either of the nuclei. Hence the energy of the molecule
becomes lower than that of separate atoms. In an atom the electron
interacts strongly only with one nucleus. According to molecular orbital
theory, the constructive interference of the contributing AOs in the
internuclear region results in the bonding effect of an electron. The
molecular orbital is referred as bonding orbital. Therefore orbital has a
cylindrical symmetry about the internuclear axis. When it is occupied by two
paired electrons we have a bond. Then the configuration is written as 2.

Antibonding orbitals:-

Now let us consider relation II = [A B]. This wave function is also

cylindrically symmetrical around the internuclear axis. Therefore this also is
a orbital. It is denoted by *. This has a higher energy than the
bonding orbital or even the atomic orbitals. This conclusion can be drawn
from the Schrodingers equation. These *- orbitals are known as
antibonding orbitals. The anti bonding orbitals are formed when the wave
functions of the AOs have opposite signs. The waves functions have a
distructive interference. As a result they give rise to decreased amplitude in
the internuclear region. There is a nodal plane exactly half way between
the nuclei. On this nodal plane any electrons that occupy the orbitals will
not be found. This plane cuts through the internuclear axis. The two wave
function of the two atoms cancel each other on this plane as a result of
their destructive interference. The high energy of the * orbital is due to the
existence of this nodal plane. The anti bonding orbital, if occupied by
electrons, decreases the strength of a bond between the two atoms. This
antibonding nature of the * orbital may be because the electron not in the
internuclear region. Secondly the electron in the outside space pulls the
nuclei apart rather than binding them as in the case of a orbital.

Gerade and Ungerade symmetry:

This notation is helpful to identify the inversion symmetry of a molecular
orbital. This is particularly applicable when discussing the electronic
transitions by inversion symmetry is meant the behavior of a wave
function when it is inverted through the centre of the molecule.

Consider any point of a bonding orbital. Project it through the centre of

the molecule through an equal distance on the opposite side. If the wave
function value and sign do not change, then it is referred as having gerade
symmetry. (from

German word for even.) This is denoted by the subscript g.

When the same procedure is applied to the antibonding * orbital, the wave
function value remains the same but the sign changes. Then it is referred
as ungerade symmetry. (meaning odd symmetry). This is denoted by the
subscript u.
This inversion symmetry does not apply to heteronuclear diatomic
molecules like HCl; CO: NO: as they do not have a centre of symmetry.

Why only pz orbital forms a orbital with s orbital?

One important feature of molecular orbital theory can be seen from the
overlap of s and p orbitals. let us suppose s and pz orbitals are
overlapping. They contribute to the formation of a orbital (the
internuclear axis is taken as z axis)

The s orbital has a cylindrical symmetry around the internuclear axis i.e. z
axis. While building the molecular orbitals, we need to consider linear
combinations only of atomic orbitals of the same symmetry with respect to
the internuclear axis. pz also has a cylindrical symmetry about the z axis.
But a px or py orbital does not. The atomic orbitals cannot contribute to form
a molecular orbital. The reason for this can be understood by considering
the interference (or overlap) between an s orbital and a px orbital.
Although there

is a constructive interference between the two orbitals on one side of the

axis (shaded part), there is exactly equivalent amount of destructive
interference on the other side of the axis. Therefore the net boding effect is
zero.

A similar explanation can be given for the overlap of an s orbital and a py

orbital

Why H2 molecule is formed while He2 is not?

The simplest of the diatomic molecules is H2. To build the molecular

orbitals in H2 molecule the following arguments hold good.

Each H atom of H2 contributes a 1s orbital to orbital interaction. One can

form the 1 and 1* bonding and antibonding orbitals from them. The
molecular orbital energy level diagram or the orbitals constructed from the
1s 1s overlap and the separation of the energy levels can be represented
as shown in the diagram.
There are two electrons to be
accommodated. Both these electrons enter
into the 1 orbital. These two electrons
bond the two nuclei more strongly and
closely than the single electron in a ion.
Then the internuclear distance, at
equilibrium, would be 0.74 A0. The wave functions interfere constructively.
As a result the electron distribution between the two atoms joined by the
covalent bond (i.e. electron pair) gives an enhanced amplitude of wave
function. So a strong bond is formed. In other words H2 is formed and is
stable. We can conclude that normally electrons do not want to get paired.
But in the molecules they get paired because in that way they are able to
occupy a lower energy orbital.

Now consider a hypothetical He2 molecule. Each He atom contributes a 1s

orbital to the formation of molecular orbitals. So one can construct 1 and
1* molecular orbitals. For all qualitative purposes one can use the same
molecular orbital energy level diagram as that of H2 molecule.

Each He atom contributes two electrons

towards bond formation. Totally there are
four electrons to be accommodated in the
molecular orbitals. Two electrons can enter the 1 orbital. But as full as it
follows Pauls exclusion principle. The next two electrons, then, must enter
the anti bonding 1* molecular orbital. That means the ground state
electronic configuration of He2 is 12, 1*2. Now it is known that the anti
bonding orbitals are slightly more anti bonding than the bonding orbital is
bonding. This implies that He2 molecule has a higher energy than the
isolated atoms. So He2 is unstable. Hence two ground state He atoms do
not form bonds to each other and He2 does not exist. Moreover Helium gas
occurs as a monoatomic gas for the same reason.

Molecular orbital energy level diagrams of heterogeneous diatomic

molecules/ ion.

MO energy level diagram for CO molecule

CO In CO C is in sp hybridized state.

Molecular orbital configuration of CO is , , =

, , = ,

Electronegativity of oxygen is greater than that of carbon, the 2s and sp

orbitals of oxygen have been placed lower than the 2s and 2p orbitals of
carbon
Electron pair in (sp)C hybrid orbitals of C and 2s atomic orbital of oxygen
are not involved in bonding and are called non bonding electron
pairs
In C atom (sp)C hybrid orbital containing lone pair of electrons is more
energetic than (sp)C hybrid orbital containing single electron. But in O
 atom 2s orbital containing lone pair of electrons is less energetic than 2p
orbital containing single electron
Now we have sp hybrid orbitals (sp)C and (sp)O containing single
electron and two 2p atomic orbitals (2px and 2py) on both the atoms.
They (C and O) undergo overlapping as follows.
(sp)C + (sp)O give and molecular orbitals
2px atomic orbital on carbon atom and 2px atomic orbital on oxygen
atom give and molecular orbitals; Similarly 2py atomic orbital on
carbon atom and 2py atomic orbital on oxygen atom give
molecular orbitals.
NO Molecular Orbital energy level diagram

Electronegativity of oxygen is greater than that of nitrogen, the 2s and

2p orbitals of oxygen have been placed lower than the 2s and 2p orbitals
of nitrogen.
 The 2s orbital of nitrogen atom and that of oxygen atom interact to give
2s and *2s bonding and anti-bonding 2s orbitals cancel, and a bond
is formed by the filled orbital.
bonds are formed by the filled orbitals.

molecular orbital contains one electron. This imparts paramagnetic

nature to NO.
NO is paramagnetic species due to unpaired electron.

Molecular orbital energy level diagram of CN

 Electronegativity of nitrogen is greater than that of carbon, the 2s and 2p
orbitals of nitrogen have been placed lower than the 2s and 2p orbitals
of carbon.
From the MOED all the electrons are completely paired. Hence CN is
diamagnetic

Assignment questions
1. What do you understand by the bonding and antibonding orbitals? Write
a few lines on the g and u inversion symmetry.
2. A true molecular orbital is built by the models based on the linear
combination of atomic orbitals. Comment on it.
3. According molecular orbital theory, explain the consequences of the
interference of the wave functions of atomic orbitals.
4. Write a note on the notation to identify the inversion symmetry of
molecular orbitals.
5. All the p orbitals have identical shapes and energies. But only p z
orbital forms a molecular orbital with s orbital. Other p orbitals do
not. Why?
6. Explain why hydrogen molecule is written as H2 but helium molecule is
written as He.