Chapter 3

Introduction To Molecular
Orbital Theory
 CONTENTS

1) Types of Molecular Orbitals

2) Homonuclear Diatomic Molecules (Second Period

Elements)

3) Energy level diagram and electron configuration for the

diatomic molecule

4) Bond order
 LEARNING OUTCOMES

1) Explain the Molecular Orbital Theory.

2) Draw molecular orbital diagram.

3) Identify magnetism properties.

4) Calculate bond order

5) Identify the bond and existence of molecule.

 MOLECULAR ORBITAL THEORY
MO theory:

 Covalent bond formation involves atomic orbital overlap that results in

formation of new orbitals called molecular orbitals.

 The theory describes covalent bonds in term of molecular orbital, which

result from interaction of the atomic orbital of the bonding atom and are
associated with the entire molecule.
• While atomic orbital is associated with only one atom.
• atomic orbital + atomic orbital = molecular orbital
 MOLECULAR ORBITAL THEORY

 Molecular orbitals have shapes and energy levels that are

different from those of atomic orbitals.

 The electrons in molecular orbitals are delocalized

throughout the orbital.

 The overlap of 2 similar orbitals leads to formation of 2 MOs

– one bonding MO and one antibonding MO
 BONDING MO
 MO that has lower energy & greater stability than the atomic orbitals
from which it was formed.
 Electron density is greatest between the nuclei of the bonding atoms.
 Constructive interference.
-Increase in amplitude of two waves of the same wavelength &
amplitude.
 ANTIBONDING MO
 MO that has higher energy & lower stability than the atomic orbitals from
which it was formed.
 Electron density is decreases to zero between the nuclei.
 Destructive interference.
-Decrease in amplitude of two waves of the same wavelength &
amplitude.
 σ MO

 The electron density is concentrated symmetrically around a line

between two nuclei of the bonding atom.

 Can form sigma bonding molecular orbital (σ) & sigma antibonding
molecular orbital (σ ⃰ ).

Eg : Between two 1s orbital = (σ1s) & (σ ⃰1s).

Eg: Between two 2p orbital = (σ2p) & (σ ⃰2p).

 end-to-end overlap
 σ MO

 Between two 1s orbital = σ1s & σ ⃰1s

 σ MO

 Between two 2p orbital = σ2p & σ ⃰2p

 π MO

 The electron density is concentrated above and below a line joining the
two nuclei of the bonding atom.

 Can form pi bonding molecular pi bonding (π) & pi antibonding molecular

orbital (π ⃰ ).

Eg: Between two 2p orbital = (π2p) & (π ⃰2p).

 **overlaps sideways
 π MO

 Between two 2p orbital = σ2p & σ ⃰2p

 BONDING & ANTIBONDING MO

Bonding Molecular Orbital Antibonding Molecular Orbital

has lower energy

has higher energy

greater stability lower stability

electron density greatest between the

electron density decrease to zero
nuclei of the bonding atom
between the nuclei
 RULES FOR MO & STABILITY

 No of MO formed = No of atomic orbital combined.

 More stable bonding MO, less stable the corresponding antibonding

MO.

 Filling of MO proceeds from low to high energies.

 Each MO can accommodate up to two electrons

 No of electron in MO = sum of all electrons on the bonding atom.

 HOMONUCLEAR DIATOMIC MOLECULES

 Diatomic molecules containing atoms of the same element.

 Li2, Be2, B2, C2, N2, O2, F2, Ne2

 ENERGY DIAGRAM

Li2, Be2, B2, C2, N2 O2, F2, Ne2

 Li2 ENERGY DIAGRAM

*2s
ORBITAL DIAGRAM

Li:3 ↑↓ ↑
1s 2s ↑ ↑

2s 2s

Energy
↑↓
ELECTRONIC CONFIGURATION 2s
(σ1s)2 (σ⃰1s)2 (σ2s)2
*1s
↑↓

↑↓ ↑↓
1s 1s
↑↓

Li 1 1s Li 2
 Be2 ENERGY DIAGRAM

*2s
ORBITAL DIAGRAM ↑↓

Be:4 ↑↓ ↑↓
↑↓ ↑↓
1s 2s

Energy
2s 2s
↑↓
ELECTRONIC CONFIGURATION 2s
(σ1s)2 (σ⃰1s)2 (σ2s)2 (σ⃰2s)2
*1s
↑↓

↑↓ ↑↓
1s 1s
↑↓

Be 1 1s Be 2
 ⃰2px
B2 ENERGY DIAGRAM

π⃰2py π⃰2pz

↑ ↑
2px
2px 2py 2pz 2px 2py 2pz
Energy

π2py π2pz
↑ ↑

ELECTRONIC CONFIGURATION
*2s
(σ1s)2 (σ⃰1s)2 (σ2s)2 (σ⃰2s)2 (π 2p)2
↑↓

↑↓ ↑↓
2s
↑↓
2s

B1 2s B2
 ⃰2px
C2 ENERGY DIAGRAM

π⃰2py π⃰2pz

↑ ↑ ↑ ↑
2px
2px 2py 2pz 2px 2py 2pz
Energy

π2py π2pz
↑↓ ↑↓

ELECTRONIC CONFIGURATION
*2s
(σ1s)2 (σ⃰1s)2 (σ2S)2 (σ⃰2S)2 (π 2p)4
↑↓

↑↓ ↑↓
2s
↑↓
2s

C1 2s C2
 ⃰2px
N2 ENERGY DIAGRAM

π⃰2py π⃰2pz

↑ ↑ ↑ ↑ ↑ ↑
2px
2px 2py 2pz 2px 2py 2pz
Energy

↑↓
π2py π2pz
↑↓ ↑↓

ELECTRONIC CONFIGURATION
*2s
(σ1s)2 (σ⃰1s)2 (σ2s)2 (σ⃰2s)2 (π2p)4 (σ 2p)2
↑↓

↑↓ ↑↓
2s
↑↓
2s

N1 2s N2
 ⃰2px
O2 ENERGY DIAGRAM

π⃰2py π⃰2pz
↑ ↑

↑↓ ↑ ↑ ↑↓ ↑ ↑
π2py π2pz
2px 2py 2pz 2px 2py 2pz
Energy

↑↓ ↑↓

2px
↑↓

ELECTRONIC CONFIGURATION
*2s
(σ1s)2 (σ⃰1s)2 (σ2s)2 (σ⃰2s)2 (σ2p)2 (π2p)4 (π⃰2p)2
↑↓

↑↓ ↑↓
2s
↑↓
2s

O1 2s O2
 ⃰2px
F2 ENERGY DIAGRAM

π⃰2py π⃰2pz
↑↓ ↑↓

↑↓ ↑↓ ↑ ↑↓ ↑↓ ↑
π2py π2pz
2px 2py 2pz 2px 2py 2pz
Energy

↑↓ ↑↓

2px
↑↓

ELECTRONIC CONFIGURATION
*2s
(σ1s)2 (σ⃰1s)2 (σ2s)2 (σ⃰2s)2 (σ2p)2 (π2p)4 (π⃰2p)4
↑↓

↑↓ ↑↓
2s
↑↓
2s

F1 2s F2
 ⃰2px
Ne2 ENERGY DIAGRAM
↑↓
π⃰2py π2p⃰ z
↑↓ ↑↓

↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓
π2py π2pz
2px 2py 2pz 2px 2py 2pz
Energy

↑↓ ↑↓

2px
↑↓
ELECTRONIC CONFIGURATION
(σ1s)2 (σ⃰1s)2 (σ2s)2 (σ⃰2s)2 (σ2p)2 (π2p)4 (π⃰2p)4 (σ2p)2
*2s
↑↓

↑↓ ↑↓
2s
↑↓
2s

Ne 1 2s Ne 2
 ENERGY LEVEL
B, C and N
 Atoms are larger, when 2p AO are half-filled, repulsion are relatively small
 2p energy are much closer with 2s energy – some mixing occurs
 This orbital mixing lowers the energy of the σ2s and σ*2s MO and raises the
energy of σ2p and σ*2p

O, F and Ne
 Atoms are small, so relatively strong repulsion occur as the 2p electron
pair up
 These repulsion raise energy of the 2p orbitals high enough above the
energy of 2s orbitals to minimize orbital mixing
 MAGNETISM

 Diamagnetic:
 Substances that do not contain unpaired electrons. (All
electrons are paired)
 Magnetic effect cancel out, thus repel a magnet.

 Paramagnetic:
 Substances that contain at least one unpaired electrons.
 Attracted by a magnet
 BOND ORDER
 Bond order is an indication of bond strength because it reflects the
difference between the number of bonding electrons and the number of
antibonding electrons.

BO = number of bonding electrons – number of antibonding electrons

2

 can be a fraction.

 A larger bond order indicates a greater bond strength and a shorter bond
length.
 BOND ORDER
 Uses:
1) To evaluate the stabilities of a compound.
2) As an indication of the strength of a bond.
3) As an indication of the existence of a molecule.

 bond order of 1 = a single bond

 bond order of 2 = double bond

 bond order of 3 = triple bond

 ½, 3/2 or 5/2 also possible

 bond order of 0 or (-) = no bond

 BOND ORDER
Calculate Bond Order for each of the molecule & indicate the type of
bond present.

a) Li2
b) Be2
c) B2
d) C2
e) N2
f) O2
g) F2
h) Ne2
 Figure 11.21

MO occupancy
and molecular
properties for B2
through Ne2
 Sample Problem 11.4 Using MO Theory to Explain Bond Properties

N2 N2+ O2 O2 +

2p 2p

2p 2p

2p 2p

2p 2p

2s 2s

2s 2s
1/2(8 − 2) = 3 1/2(7 − 2) = 2.5 1/2(8 − 4) = 2 1/2(8 − 3) = 2.5
O2 forms O2+, bond order increase,
N2 forms N2+, bond order decrease, bond O2+ has a stronger, shorter bond than
N2+ has a weaker, longer bond than N2 orders
O2
 HOMO & LUMO
 Highest Occupied Molecular Orbital = HOMO
• electrons from the HOMO are donated
• most available for bonding
• most weakly held electrons
• characteristic for nucleophilic component

 Lowest Unoccupied Molecular Orbital = LUMO

• LUMO receives electrons
• lowest energy orbital available
• characteristic for electrophilic component
 HOMO & LUMO

LUMO

HOMO
 Example: The MO diagram for H2.

H2 bond order
= 1/2(2-0) = 1

*1s
Energy

Structure
= H-H
1s
1s

Magnetism
1s =Diamagnetic
AO MO AO
of H of H2 of H HOMO
=1s

LUMO
=*1s
 SUMMARY

 Overlapping of atomic orbitals formed bonding & antibonding MO.

 Molecules are stable if the number of electrons in bonding MO is

greater than that in antibonding MO.

 Filling the electrons in the MO is in the order of increasing energy

levels.

 A larger bond order indicates a greater bond strength and a shorter

bond length.