Paaras Thakur

Chemical Bonding

❏ MOT - 2
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JEELIVE
 Linear Combination of Atomic Orbitals (LCAO)

❖ When 2 AO combine, 2 MOs are formed

1. Bonding M.O. → Lower energy and greater stability.
2. Antibonding M.O. → Higher energy and lesser stability.
Linear Combination of Atomic Orbitals (LCAO)
 Conditions for LCAO

❖ Same or nearly same energy

❖ Maximum overlap of combining AOs.
❖ Same symmetry about the axis.
 Physical significance of M.O.

M.O.s have definite energy levels and their shapes depend upon the shape of
combining atomic orbitals.
Just as the electron distribution around the nucleus in an atom is given by an
atomic orbital, the probability distribution around a group of nuclei in a molecule is
given by M.O.
Physical significance of M.O.
Physical significance of M.O.
 M.O of H2 molecule

H2 molecule has 2 H-atoms represented by HA and HB. When these atoms

approach each other, two possibilities are:
M.O. Diagram of H2
 Differences between BMO and ABMO

BMO ABMO

ψBMO = ψA + ψB ψABMO = ψA - ψB

Gives max electron density in between Gives min electron density in between
the nuclei the nuclei

Orbitals of same sign(lobes) overlap Orbital lobes of opposite sign overlap.

Constructive interference Destructive interference

Lower in energy Higher in energy

 Types of Molecular Orbitals

Molecular orbitals of diatomic molecules are designed as σ, π, δ

σ MO: Symmetrical about the bond axis.
Π MO: Not symmetrical about the bond axis.
Sigma Overlap
 Molecular electronic configuration

The order of energy of MO has been determined mainly from spectroscopic data.
In simple homonuclear diatomic molecules, the order is:

But for lighter elements like B, C, N energy difference between 2s and 2p

orbitals is very close and due to mixing of 2s and 2p orbitals, energy reversal
takes place.
 s-p Mixing

After s-p mixing π2Py π*2Py

σ1s < σ*1s < σ2s < σ*2s < π2P < σ2Px < π*2P < σ*2Px
z z

s-p mixing takes place because orbitals of same symmetry repel each other.
Example Assuming 2s-2p mixing is NOT operative, the paramagnetic species among the
following is
(a) Be2
(b) B2
(c) C2
(d) N2
(JEE Advanced 2014)
Example Match the orbital overlap figures shown in List-I with the description given in
List-II and select the correct answer using the code given below the lists.
 Applications of MOT

❖ Stability of molecules
If bonding e- (Nb) > Antibonding e-(Na) = Stable molecule
If bonding e-(Nb) < Antibonding e-(Na) = Unstable molecule
❖ Bond Order: B.O = Nb-Na/2
If B.O is positive →
If B.O is negative →
If B.O is zero →
 Trick for calculating B.O.

(a) Molecules/ ions having total no. of electrons in the range 8-14.

B.O. = (N-8)/2

(b) Molecules/ ions having total no. of electrons in the range 15-20.

B.O.= (20-N)/2