CH-803

Lecture-03
Basic Concepts of Inorganic
Chemistry

Dr. Muhammad Adil Mansoo

Associate Professor
Department of Chemistry
SNS-NUST
H-12, Islamabad
 Objectives
Recap of Previous Lecture (Class participation
required)

Different Examples of VSEPR using Inorganic

Molecules
Why do we need MOT
Wave nature of e-
S-p mixing
Examples
Valance and Conduction band
 Geometrical Shape of ABnE0 type Molecules

AB2

AB3

AB4
 Geometrical Shape of ABnE0 type Molecules

AB5

AB6
Geometrical Shape of ABnEx type Molecules
Geometrical Shape of ABnEx type Molecules
Geometrical Shape of ABnEx type Molecules
Geometrical Shape of ABnEx type Molecules
Geometrical Shape of ABnEx type Molecules
 Class Assignment
• H3BO3

• SF4 Vs IF4-
Molecular Orbital Theory
 Molecular Orbital Theory
However, Lewis structure of
O2 indicates that all es- are
paired.
VBT and Lewis-structure model does not
predict the presence of these two unpaired
electrons.
MOT was proposed by Hurid and Mullikan
(1927) to account for this discrepancy and
further developed by Lennard & Jones (1929).
Molecular orbital theory (MO theory)
provides an explanation of chemical bonding
that accounts for the paramagnetism of the
oxygen molecule.
It also explains the bonding in a number of
other molecules, such as violations of the octet
 Molecular Orbital Theory (Postulates)
MOT deals whole molecule as a single unit.
Just like electrons around isolated atoms,
electrons around molecules are limited to
discrete (quantized) energies. The region of
space in which electrons in a molecule is likely to
be found is called a molecular orbital.
MOT assumed that all atomic orbitals (i.e.
both inner & valence) of the bonding atoms
merged together to form equal no. of new
Molecular orbitals which are characteristics of
whole molecule.
Molecular orbitals surround all nuclei (i.e.
two or more) of the bonded atoms.
Like an atomic orbital, a molecular orbital is
full when it contains two electrons with opposite
 Molecular Orbital Theory (Postulates)
The mathematical process of combining atomic
orbitals wave functions to generate molecular orbitals
is called the linear combination of atomic orbitals
(LCAO).
Combining waves can lead to constructive
interference i.e. in-phase waves combinations, in
which peaks line up with other wave peaks and
produces a wave with greater amplitude, or
destructive interference i.e. out-of-phase waves
combination, in which peaks line up with other wave
troughs and produces a wave with less (or no)
amplitude.
Atomic orbitals comprises 3D standing waves,
when they combine with in-phase waves of other
atomic orbitals then producing regions with a higher
probability of e- density and if with out-of-phase
waves then producing nodes, or regions of no e-
 Molecular Orbital Theory (Postulates)
Types of molecular orbitals
i. Bonding Molecular Orbital (BMO)
In-phase combination of atomic orbitals produces a
lower energy molecular orbital in which most of the
electron density lays between the nuclei. Therefore,
electrons in these orbital are attracted by both nuclei
at the same time and are more stable (of lower
energy) than they would be in the isolated atoms.
Adding electrons to these orbitals creates a force that
holds two nuclei together.
 Molecular Orbital Theory (Postulates)
Types of molecular orbitals
ii. Anti Bonding Molecular Orbital (ABMO)
Out-of-phase addition (which can also be thought of
as subtracting the wave functions) produces a higher
energy molecular orbital in which there is a node or
minimum electron density lays between the nuclei.
Electrons in these orbitals are located well away from
the region between the two nuclei. The attractive
force between the nuclei and these electrons pulls
the two nuclei apart.
Electrons fill lower-energy bonding orbital before
higher energy antibonding orbital, just as lower-
energy atomic orbitals fill before higher-energy
atomic orbitals.
 Molecular Orbital Theory (Postulates)
Types of Orbital Combination
i. Head On Approach or Linear Combination
Linear combination of atomic orbitals would results in
two types of sigma molecular orbitals i.e. very low
energy containing (more stable) Bonding sigma
molecular orbital (σ) and very high energy containing
(less stable) Antibonding sigma molecular orbital
(σ*).
E.g. s-s and p-p linear combinations.
 Molecular Orbital Theory (Postulates)
i. Head On Approach or Linear Combination

σ*1s

1s 1s

σ1s
 Molecular Orbital Theory (Postulates)
ii. Sideways Approach or Parallel
Combination
Side-by-side combination of each two p orbitals
result in the formation of two types of pi molecular
orbitals.
Combining the in-phase orbitals results in a
low energy containing bonding pi molecular orbital
(π) with one nodal plan directly along the
internuclear axis, whereas bonding pi molecular
orbital (π) is located b/w the nuclei and above &
below to this nodal plan.)
 Molecular Orbital Theory (Postulates)
ii. Sideways Approach or Parallel
Combination
Combining the out-of-phase orbitals results in a
high energy containing antibonding pi molecular
orbital (π*) with two nodal plans. One along
internuclear axis, and other perpendicular to it b/w
nuclei.
 Molecular Orbital Theory (Postulates)
When three degenerated
right angle p atomic
orbitals (px, py, pz) of two
bonding atoms combined
together then only one set
of atomic orbitals (px) is
allowed linear combination
resulted in σpx and σ*px
molecular orbitals while
remaining two atomic
orbitals (py & pz) are right
angle to internuclear axis
so only allowed sideways
combination to produce
πpy, πpz, π*py & π*pz
molecular orbitals.
 Molecular Orbital Theory (Postulates)
πpy, and πpz are
degenerated b/c parent
atomic orbitals were
degenerated and mode of
combination is also same.
Similarly π*py & π*pz are
also degenerated.
Energies difference
b/w atomic & molecular
orbitals depends upon
interpenetration
extent of of atomic orbitals . A larger
interpenetration results in greater lowering of the energy
of bonding MO and corresponding large rise in energy of
anti bonding MO.
As in VBT, σ bonds are generally more stable than π
bonds formed from degenerated atomic orbitals. Similarly,
in MOT, σ orbitals are usually more stable (having lower
energy) than π orbitals. Therefore ascending sequence of p
 MOT (Postulates)
Molecular Orbital Energy Diagrams
Relative energy of atomic and
molecular orbitals are shown by a
molecular orbital energy diagram/
graph with energy coordinate at y-
axis.
Each atomic orbitals of
combining atoms are shown on
extreme sides by circle/box or
underline that can hold two
electrons at maximum.
Atomic orbitals of same energy
are shown at the same level.
Molecular orbitals formed by
the combination of AO are shown in
center. Dashed lines show which of
AO combine to form molecular
orbitals.
For each pair of AO that
 MOT (Postulates)
Molecular Orbital Energy Diagrams
es- are distributed in these
molecular orbitals by filling the
orbitals in same way as atomic
orbitals fill i.e. Lower-energy orbitals
fill first (Aufbau principle), electrons
spread out among degenerate
orbitals before pairing (Hunds rule),
and each orbital can hold a maximum
of two electrons with opposite spins
(Pauli exclusion principle).
It is common to omit core
electrons from molecular orbital
energy diagrams and include only the
valence electrons.
Molecular orbital energy diagram
for a homonuclear diatomic ion can
be obtained by adding or subtracting
 Molecular Orbital Theory (Postulates)
Bond Order (No. of Bonds)
A/c to MOT, an e- contributes to a bonding
interaction if it occupies a bonding orbital and it
contributes to an antibonding interaction if occupies
an antibonding orbital.
Therefore, bond order is calculated by
subtracting the destabilizing (antibonding) electrons
from the stabilizing (bonding) electrons. Since a bond
consists of two electrons, so it is divide by two to get
the bond order.
Bond Order = No. of Bonding es- - No. of Antibonding
es-
2
A bond b/w two atoms can be formed only when
no. of es- in bonding orbitals are greater than no. of
es- in antibonding molecular orbitals.

 Molecular Orbital Theory (Postulates)
ative energies of molecular orbitals in Diatomic molec
Orbital energies decrease across period as effective
nuclear charge increases and atomic radius decreases.
Generally molecular e- configuration can be written
down by filling energy wise ascending sequence of
molecular orbitals.
σ1s < σ*1s < σ2s < σ*2s < σ2px < π2py = π2pz < π*2py =
π*2pz < σ*2px
However, order of orbitals energy changes b/w N2 and
O2. For atoms with three or fewer electrons (i.e. unpair e-)
Li2 Be2 (LiBthrough O2
C2 N)Nσ2 orbital F2 Ne2
in 2p orbitals 2
p is higher in energy
than πp set. σ*2px
σ2px
σ1s < σ*1s < σ2s < σ*2s < π2py = π2pz < σ2px < π*2p π*2pπ*2p=
y, y z
π*2pz < σ*2px π2py,π2pz
E
σ2px
σ*2s
σ2s
 Molecular Orbital Theory (Postulates)
ative energies of molecular orbitals in Diatomic molec
This switch in orbital
ordering occurs because of a
phenomenon called s-p
mixing.
s-p mixing occurs when
the 2s and 2p orbitals have
close energies. Energy
difference b/w 2s and 2p is
554 KJ/mol for Boron, 846 s-p
kJ/mol for Carbon and 1195 mixing
KJ/mol for nitrogen as
calculated by spectroscopic
techniques.
s-p mixing does not
create new orbitals; it merely
influences the energies of the
 Molecular Orbital Theory (Postulates)
ative energies of molecular orbitals in Diatomic molec
The σs wavefunction mathematically combines
with the σp wavefunction, with the result that the σs
orbital becomes more stable (lower energy), and the
σp orbital becomes less stable (higher energy).
Similarly, the antibonding orbitals also undergo s-p
mixing, with the σs* becoming more stable and the σp*
becoming less stable.

On the other hand when a 2p orbital contains a

pair of electrons (like O, F, and Ne), the act of pairing
the electrons raises the energy of the 2p orbital. Thus
energy difference b/w 2s and 2p increases which do
not allow s-p mixing. Energy difference b/w 2s and 2p
is 1595 kJ/mol for O2 and 2078 kJ/mol for F2
respectively.
 MOT (Homonuclear Diatomic Molecules
Examples)
H2 molecule:

2H (1s1) H2 (σ1s2, σ*1so)

A dihydrogen molecule contains two bonding electrons
and no antibonding electrons so
Bond Order in H2 = 2 – 0 = 1
2
Hydrogen Molecule has single bond and
diamagnetic
 MOT (Homonuclear Diatomic Molecules
Examples)
He2 molecule:

Bond Order in He2

=
2–2 = 0
2
2He (1s2) He2 (σ1s2, σ*1s2)
Stabilizing effect of the two electrons in the lower-
energy bonding orbital would be offset by the
destabilizing effect of the two electrons in the
higher-energy antibonding molecular orbital. The net
energy change would be zero, so there is no driving
force for helium atoms to form the diatomic
molecule hence no bond is formed b/w two He
 MOT (Homonuclear Diatomic Molecules
Examples)
Li2 molecule:

2Li (1s2, 2s1)

Li2 (KK, σ2s2,

Bond0Order
σ*2s ) in Li2
=
2–0 = 1
2
Li2 Molecule has single
bond and diamagnetic
 MOT (Homonuclear Diatomic Molecules
Examples)
O2 molecule:
2O (1s2, 2s2, 2Px2, 2Py1,
2Pz1)

O2 (KK, σ2s2, σ*2s2, σ2px2,

π2py2, π2pz2, π*2py1, π*2pz1)
Bond Order in O2
=
8–4 = 2
O22 Molecule has double bond
and paramagnetic.
es- may be added or
subtracted according to charge
on ion e.g , O2+ (Oxonium ion),
− 2−
MOT (Homonuclear Diatomic Molecules
Examples)
 MOT Application (Band theory)

Likewise, antibonding orbitals will have higher

and slightly different energies to form a band, called
conduction band.
So valence band is lower in energy and the
conduction band is higher in energy.
 MOT Application (Band theory)

In order to conduct electricity, electrons must

move from the filled valence band to the empty
conduction band where they can move throughout
the solid.
Difference of the energies b/w highest
occupied (bonding) molecular orbital (HOMO) i.e.
top of the valence band and lowest unoccupied
(antibonding) molecular orbital (LUMO) i.e. bottom
of the conduction band, termed as band gap.
 MOT Application (Band theory)

Size of the band gap determines how easy it is

to move electrons between the bands.
In Conductor solids, band gap is very small (<
0.6 ev) so small amount of energy required by es-
to jump into conduction band.
In insulator solids, band gap is very large
(>3.5 ev) so high amount of energy required by es-
to jump into conduction band.
In Semiconductors solids, the band gap is of
medium size (0.6 to 3.5 ev) so moderate amount
of energy required by es- to jump into conduction
• Start of Coordination Chemistry (History and Basics)

BOOK: Coordination Chemistry by Fred Basalo