MODULE ONE

BOND THEORY

UNIT ONE - IINTRODUCTION

A chemical bond is the force to attraction between atoms, ions or molecules that keeps
them together to form molecules, crystals, solid or liquid states. Chemical bonds are
formed by the transfer or sharing of electrons or being surrounded by an electron cloud.
 Molecules are formed from covalent bond between atoms (H2O, BF3).
 Crystals are formed from ionic bond between ions (salts like NaCl, KNO3).
 Solid or liquid states are formed by bonds between ions (salts), atoms (metal
atoms), or molecules (water).

Types of Bonds
PRIMARY BONDS
• Ionic
• Covalent
• Coordinate covalent bond (dative bond)
• Metallic bond
SECONDARY BONDS
• Hydrogen bond
• Dipole –dipole interactions
• Van der Waals forces
There are 3 theories used to explain bonding
• Valence Shell Electron Pair Repulsion (VSEPR) Theory
• Valence Bond Theory (VBT)
• Molecular Orbital Theory (MOT)
UNIT TWO - VALENCE SHELL ELECTRON PAIR REPULSION (VSEPR) MODEL (INTRO)
This model is based on the fact the valence shell holds the electrons that are usually
involved in bonding. A stable compound is formed when the valence shell of the atoms
involved in bonding have 8 electrons each. It is said to have a complete octet. This
excludes H and He, as these would only require 2 electrons in their valence shell to attain
stability These electron pairs experience electrostatic repulsion thus would stay far away
from each other as possible, resulting a definite geometric arrangement of these electrons
around the central atom, which in turn causes the molecule to adapt a specific shape.

1
The valence electrons in a molecule would experience 3 types of repulsion: - lone pair-
lone pair repulsion, lone pair-bond pair repulsion, bond pair-bond pair repulsion. Lone
pair (lp) are 2 electrons that are not involved in bonding and bond pair (bp) are those
involved in bonding. In the order of increasing strength of repulsion bp-bp < lp-bp <lp-
lp. This means that lp-lp is the strongest and bp-bp is the weakest.

LEWIS STRUCTURE
This is a diagram that shows the bonding between atoms of a molecule as well as any lone
pairs of electrons that may exist in the molecule. Single covalent bond has 2 electrons,
double bond has 4 electrons, triple bond has 6 electrons.

By drawing Lewis structure, you can predict the number of bond pairs and lone pairs
present in a molecule.

Writing Lewis Structure

1. Write the skeletal structure of the compound, using chemical symbols and placing
bonding atoms next to one another.
2. Count the total number of valence electrons present
a) For polyatomic anions e.g. 𝐶𝑂32− add the additional number electrons responsible
for the charges
b) For polyatomic cations e.g. 𝑁𝐻4+ remove the number of electrons responsible
positively charge.
3. Draw a single covalent bond between the central atom and each of the
surrounding atoms, show complete octet of the surrounding atoms, and add extra
electrons to central atom as lone pair.
4. If after steps 1-3 the central atom has less than 8é, then add double bonds or triple
bonds between the central atom and the surrounding atoms using lone pairs from
the surrounding atoms to complete the octet of the central atom.

2
 Step 1 Step 2 Step 3 Step 4
xx
NF3 N = 5e F N F
F N F
F 3F = 3 X 7e= 21e F
Total = 26e

CS2

S C S C = 4e
S C S S C S S C S
2S = 2 X 6e = 12e
Total = 16e

HNO3
H = 1e
O N O H O N O H O N O H O N O H
N = 5e
O O O O
3O = 3 X 6e = 18e
Total = 24e

CO32- 2- 2-
C = 4e
3O = 3 X 6 e= 18e
O C O O C O O C O 2-
O C O
O O O
O charge = 2e
Total = 24e

Formal Charge (FC):

This is the charge assigned to an atom in a molecule, assuming that electrons in the bond
are shared equally irrespective of the relative electronegativity differences or type of
bonding. By determining FC on each atom we can determine the distribution of electrons
in the molecules or ions and then draw the most plausible Lewis structure.
Formal charge of an atom is the electrical charge difference between the valence
electrons in an isolated atom and the number of electrons assigned to that atom in the
Lewis Structure. To determine FC:
(i) draw the Lewis structure
(ii) assign all nonbonding electrons of an atom to that atom
(iii) bonding electrons should be shared equally between sharing atoms.
For electrically neutral molecules has total formal charge of zero 0. For cations the sum
of the formal charge must be equal to the positive charge and for anions it must be equal
to the negative charge.

3
 FC of a given atom is expressed as
𝐵
𝐹𝐶 = 𝑉 − 𝑁 −
2
V = is the number of valence electrons of the particular isolated atom.
N = is the number of nonbonding electrons of that same atom when in a molecule.
B = is the number of bonding electrons of the same atom when in a molecule.
Therefore for 𝐶𝑂32− its Lewis structure is

c
a 2- C Oa Ob Oc
O C O V 4 6 6 6
N 0 4 6 6
O B/2 4 2 1 1
b ∴FC 0 0 -1 -1
Resonance
The Lewis structure of O3 can be represented in 2 ways which are equivalent

O O O O O O

If any of these are the true structure of O3 then the bond length of the double bond would
be shorter than the bond length of the single bond. However experimental results have
shown that these oxygen-to-oxygen bond lengths are equal. The structures above are not
absolutely true and are called Resonance structures.
Resonance structures are two or more Lewis structures for a single molecule that cannot
be represented accurately by only one single Lewis structure. Similarly 𝐶𝑂32− has 3
resonance structures.

O C O O C O O C O

O O O

Exception to the Octet Rule

1. Incomplete octet: This occurs when the central atom of a stable compound has less than
8 electrons. Examples are Beryllium, Boron and Aluminium.

BeH2
x x
H Be H H Be H

4
 Because of the incomplete octet these class of compound can react with other compound
that have lone pair via coordinate bonding.

F H
F H
F B + N H
F B N H
F H
F H

2. Odd Electron molecules: These molecules contain an odd number of electrons and
therefore do not obey the octet rule e.g. NO (nitrogen(II) oxide) and NO2 (nitrogen(IV)
oxide).
Odd electron molecules are often called radicals, they are very reactive and have the
tendency to form covalent bond with other unpaired electron on another molecule e.g.
N2O4 dinitrogen tetraoxide.

O O O O
N + N N N
O O O O

3. The Expanded Octet: This occurs when the central atom of the molecule can take more
than 8 electrons in its valence shell. Atoms in the second period cannot do this, only
those in the 3rd and above periods of the periodic table. This is because they can make
use of the d, f, … orbitals as the case may be to form an expanded octet.

Cl S Cl F F

SCl2 F S F
F F
SF6

In selecting the most preferred Lewis structure, the follow serves as guide lines
 A Lewis structure where there is no formal charge on each atom is the preferred more
than those with formal charges.
 Lewis structures with smaller formal charges on each atom are more preferable
 For Lewis structures that have the same total formal charge, the more preferable one
is the one which the –ve formal charge is place on the more electronegative atoms.
 For central elements that can undergo expanded octet, the resonance structure where
it obeys the octet rule is preferred even if the expanded octet has fewer formal charges.

5
Home work
1. Draw the Lewis structure of XeF4
2. Write the Lewis structure of the following molecules and ions
(a) OF2
(b) Si2H6
(c) 𝐶𝐻2 𝐶𝑙𝑂𝑂−
(d) CH3NH3+
3. Write the Lewis structure and show formal charges of the following
(a) 𝑂22− (b) 𝐶22− (c) 𝑁𝑂+
4. Draw 3 resonance structures of the chlorate ions 𝐶𝑙𝑂3−
5. Draw the Lewis structure(s) of 𝐻2 𝑆𝑂4, which would be the preferred structure?

UNIT THREE – MOLECULAR GEOMETRY BASED ON VSPER THEORY

The molecular geometry of a molecule has an important influence on its physical and
chemical properties such as melting point, boiling point as well as its reactivity. Molecular
geometry is a 3-d arrangement of atoms in a molecule.
We shall consider 2 cases:
Case I: Molecules in which the central atom has no lone pair
Case II: Molecules in which he central atom has lone pair(s)
CASE I
Taking into consideration a molecule made up of 2 types of atoms A and B, where A is the
central atoms and B is the surrounding atoms so that the formula would be ABx (x = 1,
2,3….6). The electrons only experience bond pair-bond pair repulsion. The balloons
represent the shape the molecule would have when x = 2,3,4,5 and 6.

2 Balloons give a linear geometry

3 Balloons give a trigonal planar geometry
4 Balloons give a tetrahedral geometry

6
5 Balloons give a trigonal bipyramid geometry
6 Balloons give an octahedral geometry

X No of Electron Formula Bond Angles Molecular Examples

Pair Geometry
2 2 AB2 180° Linear BeCl2, HgCl2

3 3 AB3 120° Trigonal Planar BF3

4 4 AB4 109.5° Tetrahedral CH4, NH4+
5 5 AB5 a = 120° Trigonal PCl5
b = 90° bipyramid
6 6 AB6 a = 90° Octahedral SF6
b = 90°

CASE II
The valence electrons in this molecule would experience 3 types of repulsion: - lone pair-
lone pair repulsion > lone pair-bond pair repulsion > bond pair-bond pair repulsion. The
formula in this case is AXpEq. A= central atom, X = surrounding atoms and E = lone pair.
p = no of bond pair, q = no of lone pair.

7
 Molecular
p q TEP AE Formula Examples
Geometry
Bent or
2 1 3 Trigonal planar AB2 SO2
Angular

Trigonal
3 1 4 Tetrahedral AB3 NH3
pyramidal

Bent or
2 2 4 Tetrahedral AB2 H2O
Angular
Trigonal Sawhorse or
4 1 5 AB4 SF4
bipyramid Seesaw
Trigonal
3 2 5 AB3 T-shape ClF3
bipyramid
Trigonal
2 3 5 AB2 Linear 𝐼3−
bipyramid
Square
5 1 6 AB5 BrF5
Octahedral pyramidal

4 2 6 AB4 Square planar XeF4

Octahedral

3 3 6 AB3 T-shape
Octahedral

2 4 6 A B2 Linear
Octahedral

TEP = Total no of electron pairs

AE = Arrangement of electrons (Electronic geometry)

PREDICTING SHAPE

Guide lines for applying VSEPR model

1. Write the Lewis structure of the molecules considering the electron pair around
the central atom of the molecule.
2. Count the number of electron pairs around the central atom (bonding pairs and
lone pairs). Treat double bonds and triple bonds as though they are single bonds

Below is a summary of all of possible molecular geometries and their corresponding

names, use it to predict the geometry noting where there might be lone pairs or not

8
 No lone pairs (lp)

2 ė pairs
1 lp

3 ė pairs

2 lp

4 ė pairs
3 lp

5 ė pairs
4 lp

6 ė pairs

7 ė pairs 3. Draw the molecule. Below are sketches of what each

shape looks like. Dots represent lp or bp and circles
represent atoms

9
AlCl4- Al = 3e
Cl Cl
4Cl 4 x 7 = 28e
Cl Al Cl Cl Al Cl
charge = 1e
Cl Cl
Total = 32e

-
Cl Cl -
no of lone pair around Al = 0
Cl Al Cl -
no of bond pair around Al = 4 Al
Cl Cl
:. AB4 tetrahedral Cl
Cl
Lewis Structure

SO2 S = 6e
2O = 2 x 6 = 12e
O S O O S O
Total = 18

+
S
no of lone pair around S = 1
O S O O S O O O
no of bond pair around S = 2
Lewis Structure
:. AB2 Bent

Home Work
Sketch the shape of the following compounds
a. BF3 e. XeF4
b. CH4 f. XeF5
c. SF6 g. XeF2
d. SF4 h. H2O

UNIT FOUR - VALENCE BOND (VB) THEORY (INTRO)

This theory is based on quantum mechanics; it describes the electronic structure of
molecules as well as covalent bond formation. The theory assumes that electrons occupy
atomic orbitals of individual atoms within a molecule, and that the electrons of one atom
are attracted to the nucleus of another atom. This attraction increases as the atoms
approach one another until the atoms reach a minimum distance where the electron
density begins to cause repulsion between the two atoms. This electron density at the
minimum distance between the two atoms is where the lowest potential energy is
acquired, and it can be considered to be what holds the two atoms together in a chemical
bond (see picture below).

10
 Potential energy diagram of the bonding of 2 H-atoms.

BONDING
Before bonds are formed the atomic orbitals would undergo hybridization. Hybridization
is an imaginary mixing of process that converts a set of atomic orbital to a new set of
hybrid orbitals.
The atomic orbital involved are in phase and so amplitude increase hence the probability
of finding an electron also increases. It is the overlapping of the orbitals that result in
bonding. Strong bonds are due to greater overlapping. As set of overlapping orbitals can
only contain a maximum of 2 electrons of opposite spin.
VSEPR theory VB theory
Based on Lewis structures Based on quantum mechanics
Covalent bond are formed by sharing Covalent bonds are formed by overlapping of
electrons atomic orbitals
The atomic orbitals are the same in the The valence atomic orbitals in a molecule are
molecules. Pure orbitals different from those in isolated atoms. Hybrid
orbitals
Cannot explain differences in bond length Can explain differences in bond length and
(BL) and bond energy (BE) between in bond energy can be explained. H-H BE
different molecules. 436.4kJ/mol, BL 74 pm; F-F BE 150 kJ/mol, BL
142 pm.
Assumes that bonds in all molecules are Can distinguish between sigma bonds and pi
the same as it does not distinguish bonds.
between sigma bonds and pi bonds

11
Limitations of VSEPR Theory
Using methane (CH4) as an example

Ground State (GS) 2s2 2p2

electron configuration
of the valence orbital
of carbon

Excited State (ES)

electron configuration
of the valence orbital 2s1 2p3
of carbon

If one of the 2s electron is promoted to the empty 2p orbital (energetically excited as

illustrated above) there would four unpaired electrons for bonding however this does
not solve the problem as the 3-2p orbitals would be 90° to each other (p-orbitals are 90°
to each other) but the bond angles in 𝐶𝐻4 are 109.5° VB theory is able to explain this
phenomena using hybrid orbitals.

UNIT FIVE - HYBRIDIZATION

We can define hybrid orbitals as atomic orbitals obtained when two or more non-
equivalent orbitals of the same atom combine in preparation for covalent bond formation.
Hybridization is the mixing of atomic orbitals in an atom (usually the central atom) to
generate a set of hybrid atomic orbitals. Hybridization is favourable because the energy
lost during bond formation (exothermic) compensates for the energy required
(absorbed) for hybridization (endothermic). The number of hybrid orbitals is equal to
the number of pure atomic orbitals involved in the hybridization.
sp3 Hybridization
In the case of CH4 in order to for carbon to bond with 4-H atoms to form the stable
compound, the 2s and 3-2p orbitals of carbon would mix to form a hybrid called
sp3orbitals. They are four in number (1-s + 3-p = 4 sp3), are form regular tetrahedral
shape (no lone pair) as described in VSEPR model.

2s2 2p2 sp3

pure orbitals hybrid orbitals
unbonded carbon bonding carbon in CH4
Use a blue pen to add the electrons from the surrounding
atoms into the hybridized orbital for all the examples.

12
For NH3, the valence orbital of N is sp3 hybridized but it’s bond angle is 107.3° because of
the lone pair-bond pair repulsion effect therefore trigonal pyramidal in shape.

lone pair

2s2 2p2 sp3

pure orbitals hybrid orbitals
unbonded nitrogen bonding nitrogen in NH3

sp3(C) -Is(H)

4 1s(H) 4 sp3(C)
CH4

lone pair

sp3(N) -Is(H)
+

3 1s(H) 4 sp3(N) NH3

sp2 Hybridization
This is the mixing of a 1-s orbital with 2-p orbitals to form the hybrid sp2 which are three
orbitals in number (1-s + 2-p = 3-sp2). In the absence of lone pair, the molecular
geometry of such a molecule would be trigonal planar as in the case of BF3 as each of sp2
orbitals of Boron overlap with one 2p orbital of F.
pure p orbital (empty)

2s2 2p1 sp2 2p

pure orbitals hybrid orbitals
unbonded boron bonding boron in BF 3
.

sp2(B)-2p(F)

2p(B)

+ 2p(F)

BF3
3 2p(F) + 3 sp2(B) +2p (B)

13
The unhybridized empty 2p orbital of B is therefore available to accept lone pair
(coordinate bonding).
sp hybridization
From the previous examples we can say that it involves the mixing of 1-s orbital with 1-p
orbital, such that the total number of hybrid orbital is 2 with 2 empty pure p orbital (1-s
+ 1-p = 2-sp). The shape of such hybridization in the absence of lone pair of electrons is
linear as in the case of BeCl2.

sp 2p
2s2 2p2
bonding Be in BeCl 2 unhybridized 2p (pure) of Be
unbonded Berylium
2p(Be)

2p(Cl) sp(Be)-2p(Cl)

2 2p(Cl) + 2 sp(Be)+ 2 2p(Be) BeCl2

Hybridization involving s, p, and d orbitals

This type of hybrid orbitals account for the expand octet as in the case PCl5 and SF6 and
in formation of complexes between a transition metal and ligands.
Below are some examples (in the absence of lone pairs) Note that if there are lone pairs
then the shape would change.
Hybrid No of electron Shape Not involved in Examples
orbital pairs hybridization
dsp2 4 Square planar 4-d, 1-p Pt(NH3)42+
d2sp3 6 Octahedral 3-d [PtCl6]2-
sp2d 4 Square planar 4-d, 1-p -
sp3d 5 Trigonal bipyramid 4-d PCl5
sp3d2 6 octahedral 3-d SF6
spd3 5 Trigonal bipyramid 2-d, 2-p -
sp3d3 7 Pentagonal 2-d IF7
bipyramid

Transition metals make use of inner d orbital because they have low energy and are not
completely filled (for this reason they form complexes) while main group element make
use of outer d orbitals.

14
 SF6

3s2 3p4 3d0

unbonded sulphur

sp3d2 unhyrbidized 3d
bonding S in SF6

Pt(NH3)42+

5d9 6s1 6p0

unbonded platinium

unhybridized 5d dsp2 unhybridized 6p

bonding Pt inPt(NH3)42+

UNIT SIX –SIGMA AND PI BONDS

Under this theory there are two types of covalent bonds- sigma bond (σ bond) and pi
bond (π bond).
• When atomic orbitals (hybridized or not) overlap horizontally they form sigma
covalent bond (simply sigma bond, 𝜎 bond). This is described as end-to-end
overlapping. All the bond described above are sigma bonds.
• When the atomic orbitals overlap vertically i.e. side-to-side they form pi covalent
bonds (simply pi bonds 𝜋 bond)
H3C CH3
CH4 sp3(C)-sp3(C)
sp3(C)-1s(H)

sp3(C)-1s(H)

Six 𝜎𝑠𝑝3 (𝐶)−1𝑠(𝐻) bonds

Four 𝜎𝑠𝑝3 (𝐶)−1𝑠(𝐻) bonds One 𝜎𝑠𝑝3 (𝐶)−𝑠𝑝3 (𝐶) bond

15
 sp(C)-sp(C)
H2 C CH2 p(C)-2p(C)
HC CH
sp(C)-1s(H)

sp2(C)-1s(H)

pz(C)-2pz(C) py(C)-2py(C)
sp2(C)-sp2(C)
Four 𝜎𝑠𝑝3 (𝐶)−1𝑠(𝐻) bonds Two 𝜎𝑠𝑝3 (𝐶)−1𝑠(𝐻) bonds
One 𝜎𝑠𝑝3 (𝐶)−𝑠𝑝3 (𝐶) bonds One 𝜎𝑠𝑝3 (𝐶)−𝑠𝑝3 (𝐶) bonds
One 𝜋2𝑝(𝐶)−2𝑝(𝐶) bond Two 𝜋2𝑝(𝐶)−2𝑝(𝐶) bonds
Two-Electron, Three-Center Bonds
In this type of bonding, three atoms are bound by a single molecular orbital containing
two electrons. This phenomenon occurs with molecules that have incomplete octet or are
electron deficient. An example is diborane (B2H6), boron has 3 valence electrons and each
hydrogen atom has one. Each boron atom therefore can form bonds with 3 hydrogen
atoms. But after these bonds are formed there is no additional electrons to bond the two
BH3 together.

Experimental studies have shown that the formula of diborane is B2H6 and this structure
has a total of 12 electrons. 2(BH3) would need 14 electrons. In order to form this
molecule, B is sp3 hybridized and each B atom forms 2 regular sigma covalent bonds (B-
H) with 1s orbitals of 2 H-atoms, resulting in 4𝜎𝑠𝑝3 (𝐵)−1𝑠(𝐻) bonds. The remaining 2 sp3
orbital of each B share the remaining 2 H-atom, in such a way that 1 sp3 orbital of one
boron atom overlap with 1 hydrogen atom while another sp3 orbital of the other boron
overlaps the same hydrogen atom resulting a sigma bond B-H-B 𝜎𝑠𝑝3 (𝐵)−1𝑠(𝐻)−𝑠𝑝3 (𝐵) . Two
sets of these are formed and each set accommodates a pair of electrons and forms a two-
electron, three-center B-H-B Bridge between the two boron atoms.

16
 H H H H H
H B B H B B
H
H H
H H

sp3(B) - 1s(H) - sp 3(B)

1s (H)

sp3(B) - 1s(H) sp3(B) - 1s(H)

sp3(B) sp3(B)

Home Work.
1. What is the geometry of the following ions or molecules SnCl5, SeF4, CdCl42-, SnI2?
2. Draw and label the types of bonds formed in the molecule CH3CCCH2OH.
3. Describe the change in hybridization if any of Al atom and B atom in the following
reactions.
𝐴𝑙𝐶𝑙3 + 𝐶𝑙 − → 𝐴𝑙𝐶𝑙4−
𝐵𝐹3 + 𝑁𝐻3 → 𝐹3 𝑁 − 𝑁𝐻3
4. Determine the type of shape and hybridization that exist in the following
(a) XeF2 (b)XeF4 (c) XeF6

UNIT SEVEN – MOLECULAR ORBITAL THEORY (INTRO)

ATOMIC ORBITALS
This is the region of space where there is the probability of finding an electron. Depending
on the shape of the orbital, the lobes are where the electrons reside. The region with an
orbital where an electron cannot be found is the node. It could be radial or a plane. The s
orbitals are spherical. The 1s orbital has no nodes but 2s and above have radial nodes. 2s
has 1, and 3s has 2, … 5s will have 4. The p-orbitals have dumbbell shapes and so have
nodal planes.

17
 Radial nodes

Radial nodes

Use the 3d orbitals

• The 𝑑𝑥𝑦 has its lobes in between the 𝑥 and 𝑦 axes and 2 nodal planes (𝑥𝑧 and 𝑦𝑧 planes in
line with the z-axis).
• 𝑑𝑥𝑧 has its lobes between the 𝑥 and 𝑧 axes and has 2 nodal planes (𝑦𝑧 (in line with the z-
axis)and 𝑥𝑦 planes).
• The 𝑑𝑦𝑧 has its lobes between 𝑦 and 𝑧 axes with 2 nodal planes (𝑥𝑧(in line with the z-axis)
and 𝑥𝑦 planes).
• The 𝑑𝑥 2 −𝑦 2 orbital has its lobes on 𝑥 and 𝑦 axes and has 2 nodal planes (at 45 to the these
axis and in line with the 𝑧 axis).
• 𝑑𝑧 2 has no nodal plane because it is symmetrical around the z-axis. It nodal region is cone
shaped.

18
MOLECULAR ORBITAL THEORY
This theory is based on quantum mechanics and the images you see above are computer
simulated, based on certain mathematical models. Instead of hybridization as in VBT, the
interactions of atomic orbitals (AO) result in the formation of molecular orbitals (MO). In
VBT, the overlapping of AOs are associated only with valence orbitals of the individual
atoms, where as in MOT the interactions involves all the atomic orbitals. For there to be
overlapping the atomic orbitals must have the same symmetry, align on same axis and be
close in energy.
According to MO theory, when 1 AO overlaps with another 1 AO it creates two MO, one
which is a bonding MO (BMO) and the other is an anti-bonding (AMO). Similarly, 3 AO +
3 AO = 6 MO (3 BMO and 3 AMO). BMOs have lower energy and therefore greater stability
than its initial AOs from which it was formed while AMOs have higher energy and lower
stability that its initial AOs from which it was formed. Non-bonding molecular orbitals
(NMO) have the same energy as the AOs. These are orbitals that are present but did not
overlap because one or more of the conditions listed above are not present. Therefore, an
electron occupying an NMO does not affect the stability of the molecule.
MO

AMO

AO NMO AO
from from
atom A BMO atom B
WAVE FUNCTION
In terms of wave function, the formation of BMO corresponds to constructive
interferences of the wave function of each AO. This results in a new wave function of
lower energy than those of the parent AOs and an increased probability of finding an
electron in the MO.
𝝋𝑨𝑶 + 𝝋𝑨𝑶 = 𝝋𝑴𝑶 𝝋𝑨𝑶 + 𝝋𝑨𝑶 = 𝝋∗𝑴𝑶
𝝋𝑨𝑶 > 𝝋𝑴𝑶 𝝋𝑨𝑶 < 𝝋∗𝑴𝑶

19
 In-phase resulting in decrease amplitude Out-of-phase resulting in decrease amplitude

While AMO is produced from destructive interaction of the wave function of each AO. This
results in new wave function of higher energy than those of the AOs. with a decreased
probability of finding an electron in the molecular orbital.

UNIT EIGHT – TYPES OF OVERLAPPINGS

OVERLAPPING OF TWO s-ORBITALS
These orbitals have spherical around the inter-nuclear axis and approach each other end-
to-end. This interaction between any two s-orbitals produces σ MOs – sigma bonding (𝜎)
and sigma antibonding molecular orbitals (𝜎 ∗ ). The BMO is symmetrical around the inter-
nuclear axis. The inter-nuclear axis is an imaginary line joining the nucleus of the bonding
atoms and it is take as the z-axis.

* AMO
+
s s  BMO

OVERLAPPING OF TWO p-ORBITALS

The p-orbitals, because of their dumbbell shape can overlap in two ways: horizontally or
vertically. There 3-p orbitals, the 𝑝𝑥 orbital lies on the x-axis, the 𝑝𝑦 on the y-axis and the
𝑝𝑧 on the z-axis. The 𝑝𝑥 and the 𝑝𝑦 overlap vertically (side-to-side) resulting in π-
molecular orbital. While the overlapping of the 𝑝𝑧 is end-to-end resulting in σ-molecular
orbitals.
Note:
𝑝𝑧 will overlap with only 𝑝𝑧
𝑝𝑥 will overlap with 𝑝𝑥 and 𝑝𝑦
They lie on the same
𝑝𝑦 will overlap with 𝑝𝑥 and 𝑝𝑦
plane

20
 * AMO
z-axis
+
pz pz  BMO
z-axis

z-axis * AMO

two px or py
z-axis  BMO

s-orbitals or pz-orbitals overlapping have only 1 node (nodal plane) in the AMO. A node
is a region where no electrons would be found.

px and py-orbitals have only 1 node (nodal plane) in their BMO which is in-line with the
inter-nuclear axis (z-axis). In their AMO there are 2 nodal planes, one is in-line with the
inter-nuclear axis and the other is perpendicular to it.
nodal plane

nodal plane

nodal plane

21
OVERLAPPING OF s- AND p- orbitals
This is possible provided:
• The p-orbital is lying on the z-axis just as the s-orbital is. This way they would overlap
end-to-end resulting in a sigma MO (bonding and antibonding). Therefore, only the pz-
orbital will overlap with an s-orbital.
• They must be close in energy. 1s cannot overlap with 3s but may overlap with 2s.

AMO

AOs

BMO
UNIT NINE - OVERLAPPING OF d-ORBITALS
The d orbitals are 𝑑𝑥𝑦 , 𝑑𝑦𝑧 , 𝑑𝑥𝑧 , 𝑑𝑧 2 and 𝑑𝑥 2 −𝑦 2
SIGMA BONDS IN d-ORBITALS
• The 𝑑𝑧 2 orbitals can form d-d sigma bonds since it has cylindrical symmetry w.r.t. the
inter-nuclear axis (z-axis). It can also overlap with s and pz-orbitals.
• Two 𝑑𝑥 2 −𝑦 2 can also form sigma bond. This is because their lobes lie on the x and y axes
therefore, these sigma bonds will be formed along these axes.

PI BONDS IN d-ORBITALS
• 𝜋 bonds are those bonds with one nodal plane is in line with the inter-nuclear axis.
• The d-orbitals that would exhibit this are the overlapping of the 𝑑𝑥𝑧 and 𝑑𝑦𝑧 .
• They can also form pi bonds with 𝑝𝑥 and 𝑝𝑦 orbitals because they lie in the same plane.
(Have the same symmetry).

22
 DELTA BONDS IN d-ORBITALS (𝜹-BONDS)
• 𝛿 bonds are those bonds with two nodal planes is in line with the inter-nuclear axis.
• The d-orbitals that would exhibit this are the overlapping of the 𝑑𝑥𝑦 and 𝑑𝑥 2 −𝑦2 .

UNIT TEN – MOLEUCLAR ORBITAL ELECTRONIC CONFIGURATION

Just as we have atomic orbital electronic configuration and we have rules guiding this,
we have molecular orbital electronic configurations and there are also rules guiding
this.
Rules
1. The number of MO formed is equal to the sum of number of all the atomic orbitals
involved.
2. The filling of MO proceeds from the low energy orbitals to the high energy orbitals
(from bonding to anti bonding).
3. It obeys Pauli's Exclusion Principle – electrons fill in pair i.e. a maximum of 2
electrons per MO.
4. It obeys Hund's rule - electron will fill in MO of the same energy singly before
pairing.
5. The number of electrons in the MO is equal to the sum of all the electrons in the
bonding atoms.

HOMONUCLEAR DIATOMIC MOLECULES OF THE FIRST PERIOD (H2 AND He2)

Homonuclear means exactly the same type of atoms and diatomic means 2 atoms. H and
He below to the first period in the periodic table having only 1s orbital. Since it two atomic
orbital overlapping (1s) and overlapping of s-orbitals produces sigma molecular orbitals,
∗
we then have 2 molecular orbitals 𝜎1𝑠 , 𝜎1𝑠 to be filled by the electrons of this group.

23
 Dihydrogen molecule (H2)
∗
H – 1s1 𝜎1𝑠
H – 1s1
Total number of electrons = 2e
1s
Overlapping of the two 1s orbital 1s
∗ H H
atomic orbitals = 𝜎1𝑠 , 𝜎1𝑠 2 molecular
𝜎1𝑠
orbitals
2 ∗
Filling of these orbital = 𝜎1𝑠 , 𝜎1𝑠

Dihelium molecule (He2)

He – 1s2
He – 1s2 ∗
𝜎1𝑠
Total number of electrons = 4e
Overlapping of the two 1s orbital
∗
atomic orbitals = 𝜎1𝑠 , 𝜎1𝑠 2 molecular 1s
orbitals 1s
H H
2 2∗
Filling of these orbital = 𝜎1𝑠 , 𝜎1𝑠 𝜎1𝑠

BOND ORDER, STABILITY, MAGNETIC PROPERTY

We can determine the stability of the molecule can be from the bond order using
𝟏
𝒃𝒐𝒏𝒅 𝒐𝒓𝒅𝒆𝒓 = (𝒏𝒐 𝒐𝒇 𝒆𝒍𝒆𝒄𝒕𝒓𝒐𝒏𝒔 𝒊𝒏 𝑩𝑴𝑶 − 𝒏𝒐 𝒐𝒇 𝒆𝒍𝒆𝒄𝒕𝒓𝒐𝒏𝒔 𝒊𝒏 𝑨𝑴𝑶)
𝟐
For H2 the bond order is 1 and therefore this molecule is stable and is a single bond.
There are no unpaired electrons so it is diamagnetic.
1
(2 − 0) = 1
2
For He2, the bond order is 0 and therefore this molecule does not exist.
1
(2 − 2) = 1
2

UNIT ELEVEN - HOMONUCLEAR DIATOMIC MOLECULES OF THE SECOND PERIOD (Li2,

Be2, B2, C2, N2, O2, F2, Ne2)
In this group the general atomic are is 1s, 2s, 2px, 2py, 2pz (at most 5 atomic orbitals from
each atom) such that when two of atoms form a diatomic molecule, the interaction of the
atomic orbital would produce at most 10 molecular orbitals.
Below is the molecular orbital electronic configuration for Li2, Be2, B2, C2, N2
∗ ∗ ∗
𝜎1𝑠 , 𝜎1𝑠 , 𝜎2𝑠 , 𝜎2𝑠 , (𝜋2𝑝𝑥 𝜋2𝑝𝑦 ) , 𝝈𝟐𝒑𝒛 , (𝜋2𝑝 𝜋 ∗ ) , 𝜎2𝑝
𝑥 2𝑝𝑦
∗
𝑧

24
For O2, F2, Ne2
∗ ∗ ∗
𝜎1𝑠 , 𝜎1𝑠 , 𝜎2𝑠 , 𝜎2𝑠 , 𝝈𝟐𝒑𝒛 , (𝜋2𝑝𝑥 𝜋2𝑝𝑦 ) , (𝜋2𝑝 𝜋 ∗ ) , 𝜎2𝑝
𝑥 2𝑝𝑦
∗
𝑧

The pi orbital in the bracket are degenerate i.e. they are equal in energy (𝜋2𝑝𝑥 = 𝜋2𝑝𝑦 )

∗ ∗
and (𝜋2𝑝𝑥
= 𝜋2𝑝𝑦
) therefore electrons would fill in singly before pairing.

Notice that the position of the 𝜎2𝑝𝑧 orbital is different. This is due to sharp decrease in the
energy of the 2s orbital as you move across the period which is most prominent from O
to Ne (see diagram below).

Energy level of the 2nd row of homonuclear diatomic molecules

Molecules Li2, Be2, B2, C2 and N2 Molecules O2, F2 and Ne2 have π(2p)
have π(2p) lower in energy than σ(2p) higher in energy than σ(2p)

25
Diboron molecule B
2
B – 1𝑠 2 , 2𝑠 2 , 2𝑝𝑥1 , 2𝑝𝑦0 , 2𝑝𝑧0
B – 1𝑠 2 , 2𝑠 2 , 2𝑝𝑥1 , 2𝑝𝑦0 , 2𝑝𝑧0
Total number of electrons = 10e
Overlapping of the two of 1s, 2s and 2p atomic orbital
x
(total of 6 atomic orbital) = 6
∗ ∗
molecular orbitals = 𝜎1𝑠 , 𝜎1𝑠 , 𝜎2𝑠 , 𝜎2𝑠 , (𝜋2𝑝𝑥 , 𝜋2𝑝𝑦 )
2 ∗2 2 ∗2 1 1
Filling of these orbital = 𝜎1𝑠 , 𝜎1𝑠 , 𝜎2𝑠 , 𝜎2𝑠 , (𝜋2𝑝𝑥
, 𝜋2𝑝𝑦
)
We can determine the stability of the molecule can be from
the bond order using
1
𝑏𝑜𝑛𝑑 𝑜𝑟𝑑𝑒𝑟 = (𝑛𝑜 𝑜𝑓 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠 𝑖𝑛 𝐵𝑀𝑂 − 𝑛𝑜 𝑜𝑓 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛𝑠 𝑖𝑛 𝐴𝑀𝑂)
2
1
(6 − 4) = 1
2
The bond order is 1 and therefore this molecule is stable, it
a single bond and does exist. It has 2 unpaired electrons and
therefore paramagnetic.

Diflourine molecule F2
2 2 2 2 1
F – 1s , 2s , 2px , 2py , 2pz
2 2 2 2 1
F – 1s , 2s , 2px , 2py , 2pz
Total number of electrons = 18e
2 2 2 2 1
Overlapping of the two of 1s , 2s , 2px , 2py , 2pz
(total of 10 atomic orbitals) = 10 molecular orbitals
∗ ∗
𝜎1𝑠 , 𝜎1𝑠 , 𝜎2𝑠 , 𝜎2𝑠 , 𝜎2𝑝𝑧 , (𝜋2𝑝𝑥 𝜋2𝑝𝑧 ), (𝜋2𝑝 𝜋 ∗ ) , 𝜎2𝑝
𝑥 2𝑝𝑦
∗
𝑧

Filling of these orbital =

2 ∗2 2 ∗2 2 2
𝜎1𝑠 , 𝜎1𝑠 , 𝜎2𝑠 , 𝜎2𝑠 , 𝜎2𝑝𝑧 (𝜋2𝑝 𝜋 2 ) (𝜋2𝑝
𝑥 2𝑝𝑦
∗2
𝜋 ∗2 )
𝑥 2𝑝𝑦
FRONTIER MOLECULAR ORBITALS
We determine the stability of the molecule
1
(10 − 8) = 1
2
The bond order is 1 and therefore this molecule is
stable and exists. It is diamagnetic.

26
Highest Occupied Molecular Orbital (HOMO)
Lowest Unoccupied Molecular Orbital (LUMO)
The HOMO and the LUMO are known as FRONTIER ORBITALS and these orbital are used
to explain a lot of reaction mechanism, kinetic, structural and spectroscopic studies.
The HOMO for B2 is 𝜋2𝑝𝑥 𝜋2𝑝𝑦 and its LUMO is 𝜎2𝑝𝑧
∗
The HOMO for F2 is 𝜋2𝑝 𝜋 ∗ , and its LUMO is 𝜎2𝑝
𝑥 2𝑝𝑦
∗
𝑧

UNIT TWELVE – GERADE AND UNGERADE ORBITALS

An orbital with a center of symmetry (inversion) is called to gerade (g) and one that does
have one is called ungerade (u). A center of inversion is a symmetry operation that
involves starting at an arbitrary point in the molecule, travelling in a straight line to the
center of the molecule and then continuing an equal distance out on the other side of the
center.

According to the Laporte selection rules, electron will moving from g  u and u  g are
allowed, but g g and u  u are forbidden.

The following little table will help you to label molecular orbitals as g or u. For σ-overlap,
the bonding orbitals are g, while the antibonding orbitals are u, while for π–overlap the
opposite is true:

27
 bonding MO anti-bonding MO
σ-bonding g u
π-bonding u g

Below is the molecular electronic configuration of F2,

2 ∗2 2 ∗2 2 2
𝜎1𝑠 , 𝜎1𝑠 , 𝜎2𝑠 , 𝜎2𝑠 , 𝜎2𝑝𝑧 (𝜋2𝑝 𝜋 2 ) (𝜋2𝑝
𝑥 2𝑝𝑦
∗2
𝜋 ∗2 )
𝑥 2𝑝𝑦

To rewrite this based on symmetry would become

𝜎𝑔2 , 𝜎𝑢∗2 , 𝜎𝑔2 , 𝜎𝑢∗2 , 𝜎𝑔2 (𝜋𝑢2 , 𝜋𝑢2 )(𝜋𝑔∗2 , 𝜋𝑔∗2 )
Home Work
1. 𝑁2+ was formed by bombarding 𝑁2 with a fast moving electron. Confirm the existence
of 𝑁2+ and its magnetic properties. Draw the molecular orbital energy diagram of 𝑁2
and determine how many bonds it has.
2. Write the electron configuration of 𝑂2 , 𝑂2− , 𝑂22− in terms of symmetry and determine
their stability and magnetic properties.

UNIT THIRTEEN - HETERONUCLEAR DIATOMIC MOLECULE (HF, LiF, CO, NO etc)

These molecules are made of 2 atoms of different elements and because of these
differences their contribution to the formation of the molecular orbital would not be the
same. This is unlike the case of homonuclear diatomic molecule whose contribution to
the molecular orbital is the same. The differences arise as a result of the difference in
electronegativity
In drawing the molecular orbital diagram of heteronuclear diatomic molecules we follow
the procedure below
 Place the more electronegative atom on a lower level, while the less
electronegative atom is place on a higher level. The larger the electronegativity
difference the wide this gap between the combining species
atom F Li H C N O
χ 3.98 0.98 2.20 2.55 3.04 3.44
 In drawing the MO diagram, the more electronegative atom has the BMO closer to
it while the less electronegative atom has the AMO closer to it.
 Only orbital of the similar energy and symmetry would overlap to produce MO.
 Because this time when an s atomic orbital would overlap with a p z orbital to
produce a sigma MO the labelling of the MO of heteronuclear diatomic molecules
is 1σ, 2σ, 3σ, 4σ, 1π, 2π, 3π, 4π etc. Another style of labelling would be
1𝜎, 1𝜎 ∗ , 2𝜎, 2𝜎 ∗ , 1𝜋, 1𝜋 ∗ , 2𝜋, 2𝜋 ∗ . These two are the same.

28
 HF
H 1𝑠1
F 1𝑠 2 2𝑠 2 2𝑝𝑥2 2𝑝𝑦2 2𝑝𝑧1
Total number of electron 1+7 = 10
Total number of atomic orbitals involved = 6
Therefore, total number of molecular orbitals = 6
MO electronic configuration of HF = 1𝜎 2 , 2𝜎 2 , 3𝜎 2 , 1𝜋 4

Because of wide energy difference between the 1s(F) and 2s(F) they cannot
overlap with 1s(H) and are therefore NMOs. 1s(H) overlaps with 2p z(F) to

yield the 3σ (BMO) and 3σ* (AMO). The 2px and 2py did not overlap with any

orbital and because of their symmetry are labelled as 1π, these are also NMO.
NOTE: The number 1, 2, 3 is just serial labelling of the MO as they occurred.

H-F the bond pair of electron are not shared equally rather due to high electronegativity
of F the bond pair have more F character and due to this polarization the bond has partial
ionic character (polar bond) hence is illustrated in the MO energy diagram to be more
towards F than central.
Bond order = ½ (2-0) =1, the compound has a single polar covalent bond. It is stable and
is diamagnetic.

LiF
Because the difference in energy between the 1s of
Li and 1s of F is very large, they do not overlap and
therefore ignored.
Total number of valence electron 1+7 = 8
Total number of atomic orbitals involved = 5
Therefore, total number of molecular orbitals = 5

It is for the same reason the 2s orbitals do not overlap. For 2s(Li) = -5.5 eV and for
2s(F) = - 48.5 eV. However, the 2s(Li) overlaps with the 2p(F) because it relatively
closer in energy (2p(F)) = -21.6 eV). The wide difference in energy account for the
ionic nature of LiF bond.
(Energy of 1s(H) =13.6 eV is much closer to that of the 2p(F) = 21.6 eV).

29
Molecular orbital electronic configuration of LiF = 1𝜎 2 , 2𝜎 2 , 1𝜋 4
We can also ignore the 1s(F) orbital in HF therefore its electronic configuration =
1𝜎 2 , 2𝜎 2 , 1𝜋 4

NO, CO, 𝐂𝐍−

C 1𝑠 2 , 2𝑠 2 , 2𝑝𝑧1 , 2𝑝𝑦1 , 2𝑝𝑥
N 1𝑠 2 , 2𝑠 2 , 2𝑝𝑥1 , 2𝑝𝑦1 , 2𝑝𝑧1
O 1𝑠 2 , 2𝑠 2 , 2𝑝𝑥2 , 2𝑝𝑦1 , 2𝑝𝑧1
Just as with LiF we are going to ignore the 1s orbitals cos their energies are very low and
not really involved directly in bonding. There are two possible order of arrangement of
the molecular orbitals of the species, A or B.
The pattern observed is due to the 2s (O) and 2p(O) are wide apart in energy compared
to those of N and C, causing energy of the π-MOs to be lowered and the 2σ-MO raised.

30
 MO electronic configurations
HF 1𝜎 2 , 2𝜎 2 , 3𝜎 2 , 1𝜋 4 , 3𝜎 ∗0
LiF 1𝜎 2 , 2𝜎 2 , 1𝜋 4 , 2𝜎 ∗0
NO 1𝜎 2 , 2𝜎 2 , 1𝜋 4 , 3𝜎 2 , 1𝜋 ∗1 , 3𝜎 ∗0

CO 1𝜎 2 , 2𝜎 2 , 1𝜋 4 , 3𝜎 2 , 1𝜋 ∗0 , 3𝜎 ∗0
CN − 1𝜎 2 , 2𝜎 2 , 3𝜎 2 , 1𝜋 4 , 1𝜋 ∗0 , 3𝜎 ∗0

Bond order Stability No of bonds Magnetic

property
HF 1 stable Single bond diamagnetic
(2 − 1) = 1
2
NO 1 stable It has a double bond and a paramagnetic
(8 − 3) = 2.5
2 radical
CO 1 stable It has a triple bond diamagnetic
(8 − 2) = 3
2
CN− 1 stable It has a triple bond diamagnetic
(8 − 2) = 3
2

Home work
a. Sketch the MO energy diagram of the following compounds
i. ICl
ii. NO−
iii. NO+
b. Write their molecular electronic configuration not showing the specific AO and
showing the specific AO.
c. Discuss the properties of this compound.

31