Aryan Kumar 11B Student ID - 20230402193

Molecular
Orbital

Molecular orbital (MO) theory was developed by F. Hund and

R.S. Mulliken in 1932. The salient features of this theory are:
(i) The electrons in a molecule are present in the various
molecular orbitals as the electrons of atoms are
present in the various atomic orbitals.
(ii) The atomic orbitals of comparable energies and proper
symmetry combine to form molecular orbitals.
(iii) While an electron in an atomic orbital is influenced by
one nucleus, in a molecular orbital it is influenced by
two or more nuclei depending upon the number of
atoms in the molecule. Thus, an atomic orbital is
monocentric while a molecular orbital is polycentric.
(iv) The number of molecular orbitals formed is equal to
the number of combining atomic orbitals. When two
atomic orbitals combine, two molecular orbitals are
formed. One is known as bonding molecular orbital
while the other is called antibonding molecular orbital.
(v) The bonding molecular orbital has lower energy and
hence greater stability than the corresponding
antibonding molecular orbital.
Aryan Kumar 11B Student ID - 20230402193

(vi) Just as the electron probability distribution around a

nucleus in an atom is given by an atomic orbital, the
electron probability distribution around a group of
nuclei in a molecule is given by a molecular orbital.
(vii) The molecular orbitals like atomic orbitals are filled in
accordance with the Aufbau principle obeying the
Pauli’s exclusion principle and the Hund’s rule.

Formation of Molecular Orbital (LCAO)

1. According to wave mechanics, the atomic orbitals can be

expressed by wave functions (Ψ’s) which represent the
amplitude of the electron waves. These are obtained from
the solution of Schrödinger wave equation. However, since
it cannot be solved. To overcome this problem, an
approximate method known as linear combination of
atomic orbitals (LCAO) has been adopted. A linear
combination of two atomic orbitals ΨA and ΨB leads to the
formation of two molecular orbital Ψb and Ψa.
2. The energy of molecular
orbital Ψb known as
bonding molecular
orbital formed lower
than either of combining
atomic orbitals.
Ψb = ΨA + ΨB
Aryan Kumar 11B Student ID - 20230402193

3. The energy of the molecular orbital Ψa or Ψ* known as

antibonding molecular orbital formed higher than either of
combining atomic orbitals.
Ψ* = Ψa = ΨA – ΨB

4. The extent of lowering in energy of the bonding molecular

orbitals is lesser than to the extent of increase of energy of
the antibonding molecular orbitals when compared with
the atomic orbitals participating in bond formation.
Electrons in bonding molecular orbitals have greater
stability than the corresponding antibonding molecular
orbitals.
5. According to LCAO, only those atomic orbitals can combine
to form molecular orbitals which have comparable energies
and proper orientation. e.g., in homodiatomic molecule.
(a) A 1s atomic orbital will overlap with a 1s atomic orbital.
(b) A px will overlap with p, orbital only and not with py or p₂
orbital.
The filling of molecular orbitals take place according to the same
rules as those of the atomic orbitals.
(i) Aufbau's principle
(ii) Pauli's exclusion principle
(iii) Hund's rule of maximum multiplicity
Aryan Kumar 11B Student ID - 20230402193

Conditions for the combination of

Atomic Orbitals

1. The combining atomic orbitals must have the same or

nearby the same energy.
2. The combining atomic orbitals must have the same
symmetry about the molecular axis.
3. The combining atomic orbitals must overlap to the
maximum extent.

Types of Molecular Orbitals

Molecular orbitals of diatomic molecules are designated as σ

(sigma), π (pi), δ (delta), etc.
In this nomenclature, the sigma (σ) molecular orbitals are
symmetrical around the bond-axis while pi (π) molecular orbitals
are not symmetrical.
If internuclear axis is taken to be in the z-direction, it can be seen
that a linear combination of 2pz - orbitals of two atoms also
produces two sigma molecular orbitals designated as 2pz and
*2pz .
Aryan Kumar 11B Student ID - 20230402193

Energy Level Diagram for Molecular

Orbitals
Aryan Kumar 11B Student ID - 20230402193

Electronic Configuration and Molecular

Behavior
The distribution of electrons among various molecular orbitals is
called the electronic configuration of the molecule. From the
electronic configuration of the molecule, it is possible to get
important information about the molecule as discussed below.
Stability of Molecules: If Nb is the number of electrons
occupying bonding orbitals and Na the number occupying the
antibonding orbitals, then
(i) the molecule is stable if Nb is greater than Na, and
(ii) the molecule is unstable if Nb is less than Na.
In (i) more bonding orbitals are occupied and so the bonding
influence is stronger and a stable molecule results. In (ii) the
antibonding influence is stronger and therefore the molecule
is unstable.
Bond Order

Bond order is defined as one half the difference between the

number of electrons present in the bonding and the antibonding
orbitals.
Bond Order = (Nb – Na)
Nature of the bond

Integral bond order values of 1, 2 or 3 correspond to single,

double or triple bonds.
Aryan Kumar 11B Student ID - 20230402193

Bond length

The bond order between two atoms in a molecule may be taken

as an approximate measure of the bond length. The bond length
decreases as bond order increases.
Magnetic Nature

If all the molecular orbitals in a molecule are doubly occupied,

the substance is diamagnetic. However, if one or more
molecular orbitals are singly occupied it is paramagnetic.
Homonuclear Molecules Examples

1. Nitrogen Molecule (N2) :

Electronic configuration
of N2 molecule = σ1s2
Bond order = 6 – 0/2 = 3
It means three bonds are
present between two
nitrogen atoms.
Absence of unpaired
electrons in nitrogen atoms shows its diamagnetic nature.
2. Oxygen Molecule (O2) :
Electronic configuration of
O2 molecule = π*2p1y
Bond order = 10 – 6/2 = 2
It means two bonds are present
between two oxygen atoms.
Aryan Kumar 11B Student ID - 20230402193

unpaired electrons in oxygen atoms show its paramagnetic

nature.
3. Fluorine Molecule (F2) :
Electronic
configuration of O2
molecule = π*2p2y
Bond order = 10 – 8/2
=1
It means a single bond
is present between
two fluorine atoms.
Paired electrons in
fluorine atoms show
its diamagnetic nature.
Aryan Kumar 11B Student ID - 20230402193

Fajan’s Rule
In inorganic chemistry, Fajans' rules, formulated by Kazimierz
Fajans in 1923 are used to predict whether a chemical bond will be
covalent or
ionic, and
depend on
the charge
on the
cation and
the relative
sizes of the
cation and
anion.

Polarizing power
It is the size to which a cation can polarize an anion. It is proportional
to charge density. Charge density is the ratio of charge to volume.
Polarizing power α Charge density. The more the charge density, the
greater the polarizing power for that cation.

Polarizability
It is the range to which an ion can be polarized. It can also be
defined as the ease with which an ion can be polarized. Polarization
is the distortion of a spherically symmetric electron cloud to an
unsymmetric cloud.

Postulates of Fajans’ Rule

The rule can be stated on the basis of 3 factors, and they are:
Aryan Kumar 11B Student ID - 20230402193

1. Size of the ion: Smaller the size of the cation, the larger the size
of the anion and the greater the covalent character of the ionic
bond.
2. The charge of cation: Greater the charge of the cation, the
greater the covalent character of the ionic bond.
3. Electronic configuration: For cations with the same charge
and size, the one with (n-1)dn nso which is found in transition
elements, has greater covalent character than the cation with
ns2 np6 electronic configuration, which is commonly found in
alkali or alkaline earth metals.

Explanation of Fazans’ Rule

Rule 1:

The first rule speaks about the polarizing power of the cation. If the
cation is smaller, then we can say that the volume of the ion is less.
If the volume is less, we can conclude that the charge density of the
ion would be high.

Since the charge density is high, the polarizing power of the ion
would be high. This makes the compound to be more covalent.

Rule 2:

The second rule speaks about the polarizability of the anion. The
larger the anion, the less the effective nuclear charge that holds
the valence electron of the ion in place. Since the last electron is
loosely bound in large anions, it can easily be polarized by a
cation, thereby making the compound more covalent.

Rule 3:
Aryan Kumar 11B Student ID - 20230402193

The third rule is a special case. Let me use an example to explain

this point.

Example: If we want to find the more covalent compound among

HgCl2 and Calcium Chloride, we cannot use size as a factor to
conclude. This is because both Hg2+ and Ca2+ are of almost
equal size. To explain this, we employ the third rule.

The electronic configuration of Hg2+ is 6s0 5d10. This configuration

is called pseudo-octet because the d-orbital is fully filled, but the
element does not have 8 electrons or an octet.

We know that d orbitals are not good at shielding, so we can say

that the anion (Cl–) would be more polarized because the d
orbital is poor at shielding, making HgCl2 more covalent than
CaCl2 because Ca2+ ion has a noble gas configuration.

Now, to answer the question that we asked first, among the alkali
chlorides, which one is the most covalent:

Since the anion is the same, we have to compare the cations.

According to Fajans’ rules, the smaller the cation, the more the
covalency. Therefore, LiCl is the most covalent.

Fajans’ rule can be summarized as follows: