Theory of Chemical Bonding

Introduction
The theories of molecular bonding are:
 Valence Bond Theory (Includes the hybrid orbital

theory)
 Molecular Orbital Theory

 Valence Shell Electron Pair Repulsion (VSEPR)

Theory
One theory does not describe all the properties of
molecular bonds and each theory may describe a set of
properties better than another
Valence Bond Theory
When two atoms get close together to form a covalent
bond, the valence orbital of one atom overlap with the
valence orbital of the other atom
 A pair of electrons in the covalent bond is shared

between the atoms in the area where the orbitals

overlap
 The larger the area of overlap, the stronger the

covalent bond
The theory may be used to describe (or predict) the
kind of covalent bonds present in a molecule:
 the sigma (σ) bond

 the pi (π) bond

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• The sigma (σ) bond may be produced in 3 ways:
(i) Overlapping of one s orbital with another s orbital
(eg H-H bond in the H2 molecule)
H : 1s1

H : 1s1 H H
(ii) Overlapping of one s orbital with a p orbital
(eg H-F bond in the HF molecule)

H : 1s1
F : 2p1 H F
(iii) Head-on overlapping of one p with another p
orbital (eg Cl-Cl bond in the Cl2 molecule)

Cl : 3p1 Cl : 3p1 Cl Cl

• The pi (π) bond is produced by the sideways

overlapping of one p orbital with another p orbital
The double (X=X) and triple (X≡X) bonds contain pi
bonds, thus there exist sideways overlap of the p
orbitals

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 The following figure shows the sideways orbital
overlap in the O2 molecule

Pi bond
Ikatan pi

Ikatan bond
Sigma sigma
O : 2p1 2p1 O : 2p1 2p1 O O

Sample problem 1
Using the valence bond theory, show the overlapping
orbitals in (a) AsH3 (b) O2 (c) N2
Solution
(a) The valence electron configurations for As and H:
Three H atoms: 1s1 ↑ ↑ ↑
1s1 1s1 1s1
One As atom: ..4s2 4p3 ↑ ↓ ↑ ↑ ↑
4s 4px 4py 4pz
Each p orbital of the As atom overlaps one s
orbital of the H atom (sharing 2 electrons) so that
three sigma bonds are formed

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(b) The valence electron configuration for O:
1st O atom : … 2s2 2p4 ↑ ↓ ↑↓ ↑ ↑
2s 2px 2py 2pz
2nd O atom : … 2s2 2p4 ↑ ↓ ↑↓ ↑ ↑
2s 2px 2py 2pz
The pz orbitals overlap head-on to form one σ
bond and the py orbitals overlap sideways to form
one π bond
π bond

σ bond

(c) The valence electron configuration for N:

1st N atom : …2s2 2p3 ↑↓ ↑ ↑ ↑
2s 2px 2py 2pz
2nd N atom : …2s2 2p3 ↑↓ ↑ ↑ ↑
2s 2px 2py 2pz
The pX orbitals overlap head-on to form one σ
bond, the py orbitals overlap sideways to form a π
bond and the pz orbitals overlap sideways to form
a second π bond

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 π bond

σ bond

π bond

 The pi bonds (dotted lines) envelope the sigma bond

like a cylinder in three-dimension
 Lewis structures may be used as a guide to
determine (or check) the number of bonds between
atoms (bear in mind that each bond is formed by the
overlap of 2 orbitals which contain 1 electron each):
H
H-As-H O=O N≡N
(Three σ) (one σ + one π) (one σ + 2 π)

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Molecular Orbital Theory
The covalent bond is formed by the sharing of
electrons in the molecular orbitals (MO) which are
produced from the interaction (overlap) of the atomic
orbitals (AO) of the atoms involved
Two types of molecular orbitals (MO) are formed from
the combination of two atomic orbitals (AO) :
 The bonding molecular orbital has lower energy and

greater stability than the atomic orbitals from which

they were formed
(This MO stabilizes the molecule, exists between the
nucleus of the bonded atoms and is a result of the
attraction between the nucleus and valence electrons)
 The antibonding molecular orbital has higher
energy and lower stability than the atomic orbitals
from which they were formed
(This MO destabilizes the molecule, is designated by
the symbol (*), exists outside the bonded atoms and is a
result of the repulsion of electrons)
The formation of the bonding MO and anti bonding
MO is shown in the following figures

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(1) σ1s and σ1s*

[The antibonding MO are designated by * ]

(2) σ2px and σ2px*

(3) π2pz and πpz* or π2py and πpy*

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 The Molecular Orbital Theory can be used to predict
(i) magnetic property of a molecule - paramagnet
molecules have unpaired electrons
(ii) bond stability - molecules that have bond
order equal to zero do not exist
 Disadvantage: The MO Theory is limited to diatomic
molecules (molecules that have only two atoms
bonded together)
 The MO Theory has five basic rules:
- The number of molecular orbitals (MO) = the
number of atomic orbitals (AO) combined
- One MO is a bonding orbital (lower energy) and one
MO is an anti-bonding orbital (higher energy)
- Electrons enter the lowest MO before the higher
one’s available (obeying the Aufbau Principle)
- The maximum number of electrons in an orbital is 2
(obeying the Pauli Exclusion Principle)
- Electrons spread out before pairing up (Obeying the
Hund's Rule)

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Molecular orbital energy level diagram
• A molecular orbital energy level diagram is
analogous to the orbital diagram for an atom (but
the number of electrons arranged in the MO energy
level diagram is equal to the number of electrons of the
molecule)
• The order of MO energy levels of a diatomic
molecule is shown in the following figure:
(Energy levels for molecules of atoms in group VIA-
VIIIA differ from group IA-VA due to decreasing
repulsion of the σ1s and σ2s across a period)

Energy

Atomic orbitals
Molecular orbitals Molecular orbitals
Group IA-VA Group VIA-VIIIA

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Procedure for drawing MO energy level diagram:
 Determine the total number of electrons in the

molecule (Total electrons for both atoms)

 Draw the MO energy levels (Obey Aufbau principle)

 Fill the MO energy levels with electrons (Use arrows

/ Obey the Hund’s rule and Pauli’s principle)

The following figure shows how electrons are
arranged in the MO energy level diagram :

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Electronic configuration of a diatomic molecule
• Aufbau rule for diatomic molecules of atoms from
group IA-VA :
σ1s < σ1s* < σ2s < σ2s* < π2py = π2pz < σ2px < π2py* =
π2pz* < σ2px*
• Aufbau rule for diatomic molecules of atoms from
group VIA-VIIIA :
σ1s < σ1s* < σ2s < σ2s* < σ2px < π2py = π2pz < π2py* =
π2pz* < σ2px*
• The number of electrons is written as superscripts
eg The electronic configuration of B2 (containing a
total of 10 electrons) is:
(σ1s)2 (σ1s*)2 (σ2s)2 (σ2s*)2 (π2py)1 (π2pz)1
• The (σ1s and σ1s*) are generally not shown or just
written as KK, thus the configuration for B2 may be
written as :
(σ2s)2 (σ2s*)2 (π2py)1 (π2pz)1 or
KK (σ2s)2 (σ2s*)2 (π2py)1 (π2pz)1
A sigma bond exists when a pair of electrons fill up
either σ1s, σ2s or σ2px orbitals
Pi bonds exists when a pair of electrons fill up either
π2py or π2px orbitals
Electrons in antibonding orbitals will cancel out
electrons in bonding orbitals

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Bond stability and magnetic property of a molecule
The stability of the molecule is determined by the
bond order
Bond order = 1/2 (number of e in bonding MOs -
number of e in anti bonding MOs)
 A bond order equal to zero suggests that the
molecule does not exist because the bonds are
unstable
 A bond order of greater than zero suggests a stable
molecule
 A fractional bond order suggests that the bond is
relatively unstable compared to a whole number
A MO energy level diagram can be used to predict
whether a molecule is diamagnetic (all electrons are
paired) or paramagnetic (one or more electrons are
unpaired)
The following figure show a summary of the MO
energy level diagram, bond order and magnetic
property of some diatomic molecules of the 2nd period

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Energy

Bond order

Sample problem
Consider the Li2 molecule
(a) Draw the molecular orbital energy level diagram
(b) Write down the electron configuration for Li2
(c) Explain the molecule’s stability and bond property
(d) Determine the molecule’s magnetic property

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Solution
The total number of electrons in Li2 is 3x2=6
(a) The molecular orbital energy level diagram of Li2:

(b) Electron configuration of Li2 : (σ1s)2 (σ1s*)2 (σ2s)2

(c) Bond order = 1/2 (number of e in bonding MOs -
number of e in anti bonding MOs)
= ½ {(2+2) – (2)} = 1
The molecule is stable with a sigma bond
The pair of electrons in σ1s are cancelled out by a
pair of electrons in σ1s*, thus only the pair of
electrons in σ2s contribute to one sigma bond
(σ1s)2 (σ1s*)2 (σ2s)2
(cancel out) (contribute to sigma bond)
(d) The Li2 molecule is diamagnetic (there are no
unpaired electrons present)

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Explaining Lewis Structure using MOT
The Lewis structure of N2 shows the
existence of a triple bond :
N N
Using MOT we know that the electron configuration of
N2 (having 14 electrons) is as follows:
(σ1s)2 (σ1s*)2 (σ2s)2 (σ2s*)2 (π2py)2 (π2pz)2 (σ2px)2
 The electrons in the following MO cancel each

other:
σ1s and σ1s* σ2s and σ2s*
 The electrons in these MOs contribute to bonding:

σ2px produces one sigma bond

π2py produces one pi bond
π2pz produces one pi bond
 Electrons in σ2s dan σ2s* are the lone pair (non

bonding) valence electrons

Sample problem
(a) Write the electron configuration of O2
(b) Determine the bond order and stability of the
molecule
(c) Which electrons are involved in bonding ?
(d) How many lone pair electrons are there ?
(e) Write the Lewis structure of O2 according to the
MO Theory

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Solution
(a) The O2 molecule has 2x8=16 electrons, thus the
electron configuration is :
(σ1s)2 (σ1s*)2 (σ2s)2 (σ2s*)2 (σ2px)2
(π2py)2 (π2pz)2 (π2py*)1 (π2pz*)1
(b) Bond order = 1/2 (number of e in bonding MOs -
number of e in anti bonding MOs)
= ½ {(10) – (6)} = 2
The molecule is stable because the bond order is
not equal to zero
(c) A pair of electrons in the σ2px is involved in one
sigma bond
A pair of electrons in the π2py is involved in one pi
bond (assuming that the two electrons in π2pz are
cancelled out by the electrons in π2py* and π2pz*)
(d) There are 8 lone pair electrons
4 electrons from (σ2s)2 (σ2s*)2 and
4 electrons from (π2pz)2 (π2py*)1 (π2pz*)1
(e) The Lewis structure of O2 is O O
Notice the arrangement of the lone pair electrons

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