The Molecular Orbital Theory

Application of the Molecular Orbital Theory: Bonding in Homonuclear Diatomic Molecules

Molecular orbitals are formed by the linear combination of atomic orbitals (LCAO). When orbitals of the same atom combine, we saw
how we got the concept of hybridization. When atomic orbitals of neighbouring atoms combine, we get molecular orbitals.
1. Bonding and Anti-Bonding molecular orbitals
When two atomic orbitals combine they may be added to each other as

If the signs of the amplitudes of

and
are the same, the resultant amplitude of the combination would increase in the region of
their overlap between the two nuclei. Having electrons in such an orbital would mean an increase in electron density between the
nuclei. Since this would lead to bonding, such molecular orbitals are called bonding molecular orbitals (BMO).
If the amplitude signs of the two atomic orbitals are opposite in the region of their overlap, the resultant amplitude of the molecular
orbital becomes zero. If electrons are present in such an orbital, the electron density between the nuclei will be drastically reduced,
since a node is formed. The effect would be just the opposite of bonding. Such orbitals are called antibonding molecular orbitals
(ABMO).
The molecular orbitals formed are labeled as or (for bonding molecular orbitals) and as *or * (for anti-bonding molecular
orbitals), depending on whether it has an axis of symmetry (along the internuclear axis), or a plane of symmetry.
The different types of combinations for s and p orbitals and the labels used are as follows:

Fig1: Types of molecular orbitals formed by various combinations of atomic orbitals.

2. Energies of molecular orbitals
A bonding molecular orbital has a lower energy than the constituent atomic orbitals, whereas an anti-bonding molecular orbital has a
higher energy.
The different types of and molecular orbitals formed by the combination of atomic orbitals of elements of 1st and the 2nd period,

and their relative order of energies are given in the figure 2 (a)-(b)
(a)

(b)

Fig.2 Correlation diagram showing energies of atomic orbitals and the relative order of energies of molecular orbitals formed by linear
combination of atomic orbitals (LCAO) for
(a) period 1 elements
(b) period 2 elements
3. Filling up of the Molecular Orbitals
Given the molecular orbital energies, the electronic configuration of the molecule may be determined, using Aufbau's principle. The
order of filling up of molecular orbitals is from lower energy upwards as shown in figure 2 and may be written as

Actually the order of energies of molecular orbitals changes, such that

atomic number greater than 7. But that does not change the final configuration.

for molecules of atoms having

4. Electronic Configuration of Molecules: Bond order and Paramagnetism

Bond order is defined as

If the molecule has unpaired electrons, it will be paramagnetic.

If the bond order is zero or negative, bond formation will not take place, as it increases the energy of molecule as compared to that of
the isolated atom. If the bond order is positive, it means that the energy of the atoms in combined form of molecules is lower and such

a molecule should be formed, whether the octet is complete or incomplete. The bond order of 1, 2 or 3 corresponds to a single, double
or triple bond respectively. The greater the bond order, the greater will be the bond dissociation energy and lesser will be the bond
length. Bond order may be fractional also.
Bond order and molecular orbital configuration of some simple molecules is given below.
a) Hydrogen molecule (H2)
Total number of electrons in 2H atom = 2
Molecular orbital configuration of H2 molecule = 1s2
.
Bond order
It will exist and will be diamagnetic.
b) Hydrogen molecule ion (

Total number of electrons in

=1
1s1

Molecular orbital configuration of

Bond order
.
The molecule will exist and will be paramagnetic.
c) Helium molecule (He2)
Total number of electrons in He2 = 4
Molecular orbital configuration of He2 =
Bond order
The molecule will not exist.

d) Helium molecule ion (

Total number of electrons in

=3
=

Molecular orbital configuration of

.
Bond order
The molecule will exist and will be paramagnetic.
e)
Total number of electrons in
Molecular orbital configuration of

=2
=

.
Bond order
The molecule will exist and will be diamagnetic.
f) Beryllium molecule (Be2)
Total number of electrons in two Be atoms = 8
Molecular orbital configuration =
.
Bond order
The molecule will not exist.
g) Boron molecule (B2)
Total number of electrons in two B atoms = 10
Molecular orbital configuration =
Note that degenerate orbitals such as
of these orbitals.

2py and

2pz will obey Hund's rule and hence there cannot be pairing of electrons in any one

Bond order
.
The molecule will exist and will be paramagnetic.
h) Carbon molecule (C2)
Total number of electrons in two C atoms = 12
Molecular orbital configuration =
Bond order
.
The molecule will exist and will be diamagnetic.
i) Nitrogen molecule (N2)
Total number of electrons in two N atoms = 14.
Molecular orbital configuration
.
Bond order
The molecule will exist and will be diamagnetic.
j) Oxygen molecule (O2)
Total number of electrons in two O atoms = 16
Molecular orbital configuration =
(Note: Application of Hund's Rule while filling of

orbitals)

Bond order
.
The molecule will exist and will be paramagnetic.
k) Carbon monoxide molecule (CO)
Total number of electrons = 14
Molecular orbital configuration =
Bond order
The molecule will exist and will be diamagnetic
l) Nitrogen monoxide (NO)
Total number of electrons = 15
Molecular orbital configuration =
.
Bond order
The molecule will exist and will be paramagnetic.
On the basis of bond order, the stability of a molecule, the bond strength, the bond length and the magnetic properties of any species
can be predicted. For example, amongst
1.5),

(Bond order = 3),

(Bond order = 2.5), O2 (Bond order = 2),

(Bond order =

(Bond order = 1), it may be predicted that with decrease in bond order, stability and bond strength decreases while bond

length increases. The species

, O2 and

should be paramagnetic while

and

should be diamagnetic.

The Forces between Molecules and Properties of Substances

Van der Waals' forces (except for the ion - ion forces) are weaker than the bonding forces.
The table below gives a general idea about the relative magnitudes of the interionic and intermolecular forces, at an average distance
of 500 pm.
Table 1: Interionic and intermolecular forces
Type of interaction

Typical energy
-1

Interacting species

1. ion-ion

250 kJ mol

ion only

2. ion-dipole

15 kJ mol-1

ions and polar molecules

3. dipole-dipole

2 kJ mol

-1

stationary polar molecules

0.3 kJ mol-1

rotating polar molecules

4. London or dispersion forces:

dipole-induced dipole
and
induced dipole-induced dipole

2 kJ mol-1

all types of molecules

5. hydrogen bonding

20 kJ mol-1

N, O, F: The link in a shared H atom

The most significant of these forces is the ion-ion force (related to lattice energies), ion-dipole (related to hydration or solvation
energies) and hydrogen bonding forces.
HYDROGEN BONDING
Let us consider the water molecule. Since oxygen is much more electronegative than hydrogen, oxygen will attract the electrons in the
O - H bond towards itself, thus creating a dipole. If we look at the predicament of hydrogen we find that its nucleus, a proton, is left
highly exposed on the side opposite to the O - H bond. There is another water molecule with its electronegative oxygen atom (hence,
carrying a charge) with a lone pair of electrons, it will tend to donate these electrons to the exposed side of the proton. Thus, the two
molecules will be strongly associated with each other. This type of association is called a hydrogen bond.

In general, a group X - H (X is electronegative) and a group Y (Y is electron rich and has lone pairs) may associate as X - H ..... Y to
form a hydrogen bond. If the groups belong to the same molecule, we have intramolecular hydrogen bonding. If the groups belong
to different molecules, we have intermolecular hydrogen bonding.
Since the electron rich and the lone pair possessing atoms are all placed on the right hand side of the periodic table, both X and Y
should be electronegative. However, since X will act as an acceptor atom and Y will be a donor atom, the requirements are slightly
different. For Y, for example, large size and hence, high polarizability should have advantages.
Usually we have X = F, O or N and Y = F, O, N or Cl for the formation of significant hydrogen bonds.
Intermolecular Hydrogen Bonding
The intermolecular association through hydrogen bonds results in unusually high boiling points of liquids. Thus, the high boiling
points of water, alcohols, amines and acids as compared to the monomeric molecules of comparable molecular masses can be
explained on the basis of H-bonding.
Amongst the isomeric compounds, ethyl alcohol i.e. C2H5OH (boiling point 78oC) is a liquid, while dimethyl ether (boiling point 25oC) is a gas. All these and many other anomalies have been explained on the basis of association of a large number of molecules
through hydrogen bonding.
Amongst the hydrides of the group 16, only water is a liquid with a high boiling point. Similarly, in the hydrides of the 15 group, only
ammonia is water soluble, and amongst the hydrides of the 17 group, only hydrogen fluoride is a liquid.
A significant effect of the intermolecular hydrogen bonding is observed in terms of the unusually high bonding and melting points of
HF, H2O and NH3 as compared to the other hydrides of their respective groups. As a result of the absence of hydrogen bonding, CH4
does not show such an anomaly.
The plot of the boiling points of the hydrides of different groups against their periods given below in Figure 2 illustrates the point.

Some examples of intermolecular hydrogen bonding are given below.

bonds.
Note: The last type is very important in biological systems. Proteins have
Much of the properties (structure, shape and reactivity) are due to such hydrogen bonding. Hydrogen bonding is also important for the
double helix structure of DNA.
Intramolecular Hydrogen Bonding.
In some compounds, the H-bonding may occur within the molecule itself. Ethyl acetoacetate, salicyaldehyde and o-nitrophenol are
examples of this type.

This type of H-bonding prevents the association of such molecules. Amongst o-nitrophenol and p-nitrophenol, the o-isomer is almost
insoluble in water, and has a lower boiling point and a lesser acid strength, due to the intramolecular H-bonding, while the p-isomer
which can undergo intermolecular H-bonding is soluble in H2O, has a higher boiling point and a greater acid strength. Similarly, the
enolic contents in a keto-enol tautomer increases if the intramolecular H-bonding stabilises the enolic form, as in ethyl acetoacetate
and acetyl acetone.

Usually the intramolecular H-bonding occurs in cases where a six-membered ring can be formed easily through H-bonding. However,
the 5 and 7 membered ring formations involving intramolecular hydrogen bonding are also known.
Applications of Hydrogen Bonding - a Summary
1. Intermolecular H-bonding raises the boiling point and melting point of a large number of compounds including water, alcohol,
amines, acids, etc.
2. The solubility of certain organic compounds in hydroxylic solvents is explained because of the formation of H bonds between the
solute and solvent.
3. H-bonding explains the lack of ideality of gases, solutions and ionisation constants of acids.
4. It has a strong influence on the configuration of a molecule in space, and can prevent the inter-conversion of isomers.
5. It explains the adsorption of dyes etc. by textile fibres like cellulose (contains - OH groups) and proteins (contains > NH groups).
6. Lack of chemical reactivity of the > C = O group in certain compounds like -keto succinamic acid is because of H-bonding.

7. The H bond serves as a useful bonding force in biological systems. The structures of proteins and nucleic acids show that H bonds
play an important role in retaining the helix configuration.
van der Waals' Forces
van der Waals' forces increase with an increase in the surface areas of the molecules, since such forces are related to the induced
polarisation of surface electrons. Thus, there is greater van der Waals' force of attraction between straight chain organic molecules
compared to branched chain molecules having less surface area. The resultant effect is observed in terms of lower boiling points of the
branched chain hydrocarbons, as compared to the corresponding isomeric normal chain molecules. Thus, the boiling point order is
(CH3)3CH < (CH3)2CHCH3 < CH3CH2CH2CH3
PROPERTIES OF SUBSTANCES
The bonding interactions determine the properties of molecules. The properties of molecules determine the properties of substances
through the intermediacy of intermolecular forces. Both bonding as well as non-bonding forces are taken together and are referred to
as structure and bonding factors.