4 CHEMICALBONDING-||

"The most incomprehensible thing about the world is that,

it is comprehensible"
-Albert Einstein

CHAPTER QUTLINE
4.1 Molecular Orbital Theory 4.7 Werner's Theory of Coordination Compounds
4.2 Linear Combination of Atomic Obitals: 4.8 Effective Atomic Number
4.3 Energy Level Diagram for Molecular Orbitals 4.9 Isomerism in Coordination Compounds
4.4 Filling of Electrons in Molecular Orbitals Structural Isomerism
4.5 Homonuclear Diatomic Molecules Stereo Isomerism
4.6 Heteronuctear diatomic molecules

4.1 MOLECULAR ORBITAL THEORY

According to Valence Bond Theory discussed earlier, a covalent bond is formed by the overlapping
of atomic orbitals and the bonded atoms in the molecule are held together by one or more pair of
electrons. According to this theory, the atoms retain their identity even after bond formation.
On the other hand in the molecular orbital method, the valency electrons are considered to be
associated with all the nuclei in the molecule i.e. electrons move in the field of more than one
nucleus.
The molecular orbital theory given by R.S. Mulliken and F. Hund
incorporates the following
points.
1. When nuclei of two atoms come close to each other, their atomic orbitals interact, to form
molecular orbitals in which the identity of both the atomic orbitals is lost.
2. The number of molecular orbitals is equal to the number of atomic orbitals involved in
their formation.
3. Just as atomic orbitals in an atom are quantized, similarly molecular orbitals are also
believed to be quantized.
4. The electrons in the atomic orbital are influenced by one nucleus, the eldctrons in the
molecular orbitals are influenced by all the nuclei.
5. Electrons are filled in the molecular orbitals in the same way as they are filled in atome
orbitals, following Aufbau principle, Hund's rule of maximum multiplicity.
Chemical Bonding-l 239

6Themolecular orbitals
are represented
by o o* nr etc.
orbital;is construeted by combinatiou o two atomic orbitals and this method is
Amolecular
as
bination of Atomic orbitals (LCAO).
Linear Combi
known.

Table 4.1 Differenee between Valence Bond Method and Molecular Orbital Method

Valence Bond Method Molecular Orbital Method

In valence bond method, a molecule is

In molecular orbital method, the combining atoms
composed of atoms which retain their lose their individual identity.
individual identity even after bond formation.
in the field of one nucleus An electron moves in the field of more than one
9. An electron moves
atomic orbitals are monocentric. nucleus i.e. molecular orbitals are polycentric.
only, i.e.
s Valence bond method does not explain the Molecular orbital theory explains the paramagne
paramagnetism of O, successfully. tism of oxygen successfully.
4. t does not involve the formation of bonding It involves the formation of bonding and
and antibonding orbitals. antibonding orbitals
5. Atomic orbitals in valence bond method are Molecular orbitals in molecular orbital method
represented by s, p, d and f. are represented by o o* Tt* etc.

4.2 LINEAR COMBINATION OF ATOMIC ORBITALS

Electrons may be considered either as particle or waves. An electron in an atom may therefore be
described by a wave function y, which is a solution to Schrodinger wave equation. According to
Molecular Orbital Theory the electrons in a molecule are said to occupy molecular orbitals. The
wave function describingamolecular orbital may be obtained by the method of linear combination
of atomic orbitals.
Consider two atoms A and B which have atomic orbitals described by the wave functions "
and g. The electron clouds ofthese two atoms overlap when the atoms approach each other. The
wave function for the molecular orbitalMO can be obtained by a linear combination of the atomic
orbitals A and ¥B
Mo C'A+ C¥B
Where C and C, are the coefficients chosen to give the lowest-energy for the molecular
orbital. For homoatomic systems atoms A andB are same, and hence
C, and C, are equal.
Now the probability of
finding an electron in a volume of space du is du, so the probability
density for the combination of two atoms is given by:
VMO (G¥A +C,¥p)*
vMO= (Cy +2C,C,¥AYs +C$vi)
The term
C¥ gives the probability of finding an electron on atom A, if A is an isolated
aOm. The term
Cfvß gives the probability of finding an electron on atom B, ifB is an isolated
aom. The middle term 2C,C,YYR is called the overlap integral as this term represents the
difference between the electron clouds in individual atoms and in the molecule. The larger
this term the
stronger the bond.
a has a positive sign when the superimposed regions of the two orbitals have the same
. . both (+) or both (-) (same phase). Overlap has a negative sign when the superimposed
regi
T h e two orbitals have opposite signs (different phase). Zero overlap results when there
 240 Engineering Chemistry
are equal regions of overlap with opposite signs. Let us discuss this in more detail by
nore detail by coOneia.
the overlap of different orbitals.
considering
Combination of s-s orbitals
Consider a simple case of combination of 1s atomic orbital of one hydrogen atom (A) with 1,
atomic orbital of another hydrogen atom (B). Let wave function ¥A and ¥ represent the 1
atomic orbitals ofthe atoms A and Brespectively. There are two possible ways of linearly combini
the atomic orbitals. ing
) Additive combination-where the signs of the two wave functions are the same.*
) Subtractivecombination-where the signs of the two wave functions are different.*(Fi
4.1)
Wave functions which have the same
sign may be regarded as waves that are in
phase, which when combined add up to YAA YA+YB
give a larger resultant wave. Similarly
wave functions of different
signs (a)
correspond to waves that are completely

AA
out of phase and which cancel each other
by destructive interfer-ence. Thus two
combinations are-

A
The molecnlar crbital wave functions
are designated by Yand Yigstands
for gerade (even) andu for
ungerade (odd).
)
F7| YA YB

AA
Actually the terms g and u refer to the
symmetry of the orbital about its centre.
If the sign of the lobe remains unchanged
when the orbital is rotated about the line
Fig. 4.1 (a) Additive effect of the electron waves in
joining the two nuclei and then about a phase.
line perpendicular to this, then, the orbital
(b) Subtractive effect of the electron waves out
is termed gerade and if the sign
as of phase.
changes, the orbital is termed as ungerade.

Bonding Molecular Orbital

The molecular wave function Y leads to increased electron density in between the nuclei and is
therefore aBonding Molecular Örbital. The probability density of electron cloud can be obtaln
by squaring the wave function Y
= (¥A +¥p)

*One of the wave function ¥' is arbitrarily assigneda positive sign, the other
may be eer ue or-ive. The
signs +and-refer to signs ofthewave functions, which determine their symmeuy u

electrical charges.
A
Chemical Bonding-l 241
From the above equation, overlap criteria becomes clear. In a region where two orbitals PA
aind have positive overlap, the electron density is higher than the mere sum of the electron
densities of the two separate orbitals i.e. (¥ + V i s greater than v'A+*B by 2 VA VB-The
attraction of both nuelei for these electrons is greater than the mutual repulsion of the nuclei. A
net attractive lorce or bonding interaction results in the formation of stable chemical bond.

Antibonding Molecular Orbial

Conversely Vay results in two lobes of opposite signs giving zero electron density in between the
nuclei and hence iscalled the antibonding molecular orbital. The probability density of electron
cloud in this case also is obtained by squaring the wave function y,

=
Vå + V -2"AYB
From the above equation it is clear that if vj and vg have negative overlap, the electron
density is lower than the sum of electron densities of the two separate orbitals.
Fig 4.2 represents the pictorial representation of bonding and antibonding orbitals of H2
molecule.

Atomic Orbitals Molecular Orbitals

Bonding Orbitals

S S

NODE

(:0) O O :Antib nding Orbitals

(
S S

Fig 4.2 s-s combination of atomic orbitals

The energy of the bonding molecular orbital is lower than that of the atomic orbital by an
amount A. This is known as stabilization energy. Similarly the energy of the antibonding
molecular orbital is increased by A. The relative energies of the two molecular orbitals and the
atomic orbitals are shown in Fig. 4.3.

ANTIBONDING

A
Y1S ATOMIC
1s ATOMICC
ORBITAL
ORBITAL
A
Yio) BONDING

Fig. 4.3 Molecular Orbitals (Bonding and Antibonding)

 242
Engineering Chemistryy
Purther. since the overlapofss orbital is along the axis joining the nuclei, the resulting mole
orbitals are designated as O orbital. As a convention the antibonding molecular orbitalisdela
with an asterisk o*. Thus the two orbitals formed in the case of two combining
designated as o, and ojs
hydrogen atome 8, are

Table 4.2 Difference between Bonding and Antibonding Molecular Orbitals

Bonding Molecular Orbital Antibonding Molecular Orbital

1. They are formed by the additive effect of the They are formed by the subtractive effect of the
atomic orbitals atomic orbitals

2. It increases the electron density between the

MOV-¥
It decreases the electron density between the
nuclei nuclei
These orbitals have lower energy than the These orbitals have higher energy than the atomic
atomic orbitals from which they
are formed. orbitals from which they are formed.
4. Bonding molecular orbitals stabilize the Antibonding molecular orbitals destabilize the
molecule. molecule.
5. These are represented by o, T etc. These are represented by o*, T* etc.

Combination of s-p orbitals

An orbital may combine with ap orbital
s

internuclear axis. When the lobes, which are

provided the lobes of p orbital are directed along the
orbitals are formed with an increased electron overlapping have the same sign, bonding molecular
molecular orbital is lower than the density between the nuclei. The energy of this
energy of the atomic orbitals which have gone into its formation.
The corresponding
antibonding orbital is formed when the lobes of opposite signs overlap, with a
reduced electron density in between the nuclei
Fig. 4.4.

Osp Overlap
Bonding Orbital

-OKD:-OO
*

sp Overlap
(Node) Antibonding Orbital
Fig. 4.4 Combination of s-p orbitals

Combination of p-p orbitals

The overlap of the two p orbitals, which have lobes
results in O2 bonding o2 antibonding orbitals.
pointing along the axis
joining the nuclei
Chemical Bonding-II
243

2Pz 2P
2p,(Bonding)

2P 2P2
2p, (Antibonding)
Fig. 4.5 Combination of p-p orbitals

Electron charge density between the two nuclei in o is enhanced whereas the electron
reduced.
density in o2p gets
The overlap between the two p orbitals, which both have lobes perpendicular to the axis
ioining the nuclei, is lateral. This results in the formation oft bonding and antibonding
molecular orbitals.

-Z

p2Px (BONDING)
2Px 2Px

8-98
2Px
Fig.
2Px
4.6
P2px (ANTIBONDING)

Formation of n and r* molecular orbitals.

lt 1s to be noted that for t molecular orbitals, y is zero along the internuclear line and
consequently the electron density v is also zero. This is in contrast to a orbitals.

Combination of p-d Orbitals

and
rbital on one atom may overlap with a d orbital on another atom forming bonding as T
antibonding orbitals. Since the overlap is lateral and hence molecular orbitals are designated
orbitals.
244 Engineering Chemistry

-
(Atomic Orbitals) Ppd (BONDING)

Ppd (ANTIBONDING)
Fig. 4.7 p-d combination of atomic orbitals

Combination of d-d Orbitals

Two day or twod? orbitals may overlap to form molecular orbitals. The molecular orbitals
formed by the combination of d-d orbitals are designated as ð and 8 for bonding and
molecular orbitals respectively.
antibonding

Criteria for the Combination of Atomic Orbitals

Any two atomic orbitals will not essentially combine to form molecular orbitals. There are certain
rules which are followed for their combination. The rules are:
X
1. The atomic orbitals which are involved in the formation
of molecular orbitals should be
approximately of the ++
same energy. Overlap
2. The atomic orbitals must
overlap to a considerable
extent to form stable bonds. The overlap increases the
electron charge density in between the
3. The atomic orbitals must have the same
twonuclei.
respeet to the molecular axis, Out of the three
symmetrywith
which are designated as px, py and pz
p orbitals +

orbitals, pz Overlap
orbitals are considered as pointing along the
internuclear
axis by convention. Thus px or py orbital of one
atom
does not combine with s orbital of the other Non-bonding
atom. In
fact ++ overlap is cancelled by combination of atomic orbitals
+-overlap.
Fig. 4.8
4.3 ENERGY LEVEL DIAGRAM FOR
MOLECULAR ORBITALS
The order of energy of molecular orbitals has been
determined from spectroscopic data. The enerey
generally increases in the following order as we move from left to light-

O18 O18 O28 O28, O2pa Topx T

2p
2py T2py O2pz
increasng energ
Chemical Bonding-ll 245

Thebonding Tas andapy molecular orbitals have exactly the same energy and are said tobe
double degenerate. In a similar way the antibonding T2nr and T2ny molecular orbitals have same
energy and are also doubly degenerate.
The energy levels of different molecular orbitals are shown diagrammatically in Fig. 4.9.

2pz

-. .-. . .- .
******
OO
P2px P2py
OO0
2P
O00 2p
OO.
P2px(
202
- -----.---.
2s
- mmmm-- .
2S 2S

2s

.-********* 1s

O -u- - - .
1s 1s

- -. . -n-/ O O1s
---.

Ao's Mo's Ao's

Fig. 4.9 Energy levels of different molecular orbitals of O, Fg, Ne.

However, it has been revealed by spectroscopic studies that the above mentioned sequence of
energy levels is not correct for all molecules. In the case of homonuclear diatomic molecules of
ond row elements of the periodic table upto N, (viz. Lig, Beg, Bg Cg, N), the G2p: orbitalsa
0 higher energy than the t2x and T2py molecular orbitals. For these atoms the order is:

|18 O18
*

O2s O28
12p O2p2
T2py 7T2py
Lncreasng energy
The energy level diagram for these molecules is given in Fig. 4.10.
 246 Engineering Chemistny
2pz

Pzpx P2py
OQO OOO2 2p
2p

A PanPay
O2s

*-***** 2s

- - - - - -O
2s

2s

O
**-*******
*p*=w-o=-*=-*wu*-~.*
C1s

1S
O 1s

O1s
Ao's Mo's Ao's

the c a s e of lighter elements.

Fig. 4.100 Energy levels of different molecular orbitals in
of molecular orbitals is different for
Now the question arises that why the order of energy
can be explained a s follows:
molecules lighter than F2, viz., N2, C2, Bz and Li, This
second row elements, if the energy difference
In case of homonuclear diatomic molecules of
between 2s and 2p atomic orbital is large,
then the 2s orbital of one atom interacts slightly
the symmetry is proper for overlap, but the
with the 2pz orbital of the other atom. Though
the two orbitals is so great that the overlap
is not effective.
energy difference between of
the two 2s atomic orbitals and the order
Thus o molecular orbitals are composed of
of O, and F2.
energy levels is as shown
in Fig. 4.11 This is true for diatomic molecules
and
the energy difference between 2s
In case of elements upto nitrogen, in the second row,
one atom is close to 2pz orbital
of second atom
2p atomic orbitals is small i.e. 2s orbital of cannot be ignored. As a resuit
o

As the two orbitals are of same symmetry their overlap

atom with the p orbital of the other and
vice versa, O2s
interaction between s orbital of one s character and O2p
and o
2p
and o2 molecular orbital do not retain their pure
molecular orbitals do not retain their pure p character.
Chemical Bonding-ll 247

Infact all the four molecular orbitals acquire a mixed sp character.

Due to this mixing, the energies of all the four orbitals change in such a way that the
resulting molecular orbitals 2, and and o . which also contaín some p character,
become more stable and are thus lowered in energy.
Similarly because ofthis mixing the molecular orbitals G and pwhich also
contain some s character now become less stable and molecular orbital are thus raísed
in energy. Thus there is an upward displacement of o2 80 that it lies above T2pannd
2p
Since T2 orbitals are not involved in mixing, the energies of T2n and o2p, molecular
orbitals remain unchanged, as shown in the Fig. 4.11.

2pz
2pz
-.

P2px P2py p2px P2p7

2 2pz

P2px P2py P2px P2py

2pz

S 2s

2s
' 2s

2s

MO DIAGRAM MO DIAGRAM
FOR O2 AND FOR
Fa Lig, Be, Ba Ca Na

Fig. 4.11 The change in energies of MOs due to mixing of orbitals of the same symmetry.

difference in 2s and
2p atomie
Considering the above points it can be concluded that the
these would overlap effectively resulting
orbitals of atoms up to nitrogen are small and hence
n the orbitals, the energies of which will be different than pure o2, and o2p: molecular
On the
orbitals. Same explanation is applicable for antibonding O2, and o2orbitals.
between 2s and 2p is quite large
Contrary, in the case of O, and F, the energy difference is of
and hence no overlapping between these atomic orbitals possible. Therefore energies
has lower energy
remain unaltered and hence O2nz molecular orbital
2, 2, O2pz, O2p2
Cnan the energies of T2 and t2py molecular orbitals.
248
Engineering Chemistry
4.4 FILLING OF ELECTRONS IN MOLECULAR ORBITALS

imilar fashion as in
For simple homoatomic molecules, the filling of electrons are carried out in a similar fashio
Atomie Orbitals. Following rules are followed:
1. Aufbau Principle: The orbital with lowest energy is to be filled first of all i.e. elect.
enter various molecular orbitals in the order of their increasing energies,
2. Pauli'sExclusion Principle: The maxmimum number
cannot exceed two and these should have opposite spins.
ofelectrons
in a moleoular orkisbital
3. Hund's of only when each molecular orbital
Rule: Pairing electrons takes place of the
of tha
same energy has at least one electron each.
4. between two atoms is said to be formed when the total number of electrone i
A bond
bonding orbitals is greater than the numbers in antibonding orbitals. in
5. Bond order: Bond order is defined as half of the difference between the number of electronss
present in the bonding and the antibonding orbitals i.e.

Bond order= (No.of bonding orbitals-No. of antibonding orbitals).

2
A negative or zero bond order corresponds to an unstable molecule whereas positive bond
order indicates a stable molecule.

4.5 HOMONUCLEAR DIATOMIC MOLECULES

1. Hydrogen molecule-ion H: This is the simplest molecular specie containing one electron
only. Its existence has been detected spectroscopically when electric discharge is passed through
hydrogen gas under reduced pressure. The only electron present in H ion enters the o
molecular orbital. Thus, electronic configuration of H is written as 1and bond order=

a-0) 2
2. Hydrogen molecule H Each hydrogen atom contains 1 electron and hence there are two
electrons in the molecule, occupying the lowest energy level. Thus, the electronic contiguration
ofH, will be o and bond order= (2-0) = 1.
3. Hydrogen molecular negative ion H: This is formed by the combination of one hydrogen
atom having one electron in 1s orbital with a hydrogen ion having 2 electrons. Thus H2 ion has

3 electrons. The electronic

configuration will thus be of, O1s and bond order = (2-1)
Table 4.3
Characteristics of H, , Hg, Ha

Specie Electronic config. Bond Order Magnetic character

H2 Paramagnetic
2
Diamagnetic
H2 Paramagnetic
Chemical Bonding ing-ll 249

H H+ H H

s
Ao's Mo's Ao's Ao's Mo's Ao's
H2

Ao's Mo's Ao's

H2

Fig. 4.12 Energy Level Diagrams for H H2 and H2

4.
Hetium Molecule ion He This:
may be considered to be formed
from He atom and Het ion.
In the molecular ion there are three electrons which are arranged in the molecular orbitals as
a

O s . Thus helium molecular ion can exist, but it is not very stable. Bond orderr=

--
He
-0-
G1 Het He He

He He2
Fig. 4.13
.Helium Molecule, He,: The electronic configuration of the atom is 1s. He molecule can be
COnsidered to form from two atomic orbitals. In the molecular He, there are four electrons
2
wnlch are
arranged as o, O1s. Thus, the stabilizing effect of bonding orbitals is cancelled
DY the destabilizing effect of antibonding orbitals and the molecule does not exist. Bond
order=
2-2) =0.
250
Engineering Chemistry
6. Lithium Molecule Li,: Each Li atom has two electrons in its inner shell and ona
valence shell. Thus in Lig, a total of six electrons are present. These are aranged as r2 in
o2 The inner complete shells do not contribute to the bonding and molecularelecth
cular electron ie.
configuration can be written as KKo where KK implies that K shell of the twoa
complete and do not contribute to bonding much. Bond order of lithium molecule atoms is
ule com comes out to
be 4-2)=1

Lithium molecules do exist in the vapour state but solid state oflithium is energetical
favourable.

0-

1
Ao's Mo's Ao's
Fig. 4.14 Energy level diagram for Lig.
7. Beryllium Molecule Be; Beryllium atom has 2 electrons in the valence shell. Hence in the
formation of the diatomic molecule, electrons from the valence shell of each atom i.e. a total ot

four electrons 2
are involved. These four electrons can be
arranged as KKo, 028. Thus, 1t15
apparent that the effects of the bonding o, and antibonding o levels cancel each other and

hence the molecule does not exist. Bond order= *(4-4) =0. This zero bond order furtner
suggests that existance of Be, molecule is not possible.
8. Boron Molecule B; The valence shell of each atom
of boron contains 3 electrons 10
When two atoms of boron combine to form
B, molecule the molecule contains a total

KKo O2s T2ply Tt may aga

electrons. These are arranged in the molecular orbitals as- *2

be pointed out here that boron is a Tt:2pl is

light atom and order of energies of molecularevel
different from the usual arrangement i.e T2px and aree at lower energy
than the Orbital for the
22py orbitals a
a2 reason explained in section 4.3. Since t2px and t2py are
egenera

as
Chemical Bonding-
251
olectrons are filled according to Hund's rule i.e each of these orbitals is singly occupied.
The order ofthe energies of moleeular orbitals as given above is supported by the experimental
facts also. Boron molecule is found to be paramagnetic in nature which can be very well
nlained on the basis of this order, as there are two unpaired electrons one each in tapr and
Tap molecular orbitals.

202

OON P 2px P20y

2P
2pz OOQ 2p

P2px
2s

2s 2S

2s

O1s

1s is

Ao's Mo's Ao's

Fig. 4.15 Energy level diagram for Boron Molecule.

9.
Carbon Molecule C Carbon atom has 6 electrons. In the formation of C, molecule, a total
4Electrons have to be accommodated in the molecular orbitals. These are arranged as:

KK o 0
02
(
O2 2 " . Bond order = 8 - 4) = 2. Thus the molecule should be stable.
2

agnetic because all the electrons are paired. Similar to the case of B, molecule, in C also
versa Cnergles of 2s and
o2pz and Tzpx, T2py orbitals take place, due to the mixing ofthe
252
Engineering ChemistrN
2p orbitals.Though it appears that C, molecule is stable, but carbon exists as macro
in graphite and diamond. These are even more stable than C2, hence in prefereneCule
diamond and graphite are formed. preference to C,,
2pz

.
P2py P2pz
ODO/
2p
2pz
2p

PaL
O2s

2S 2s

2s

1s
--- --- . 1s

O1s
AO'S Mo's Ao's

Fig. 4.16 Energy level diagram for Ca.

10. Nitrogen Molecule Ng: Nitrogen atom has
seven electrons. In the formation of
a total of 14 electrons Ng molecle
are arranged in molecular orbitals as:

KK 2 02s 9
Tw2 px p.Bond order =(10-4)=3.
Thus nitrogen molecule contains a triple bond and is highly stable therefore nitrogen ist as
N, molecule. Moreover all the electrons are paired therefore
it is diamagnetic.
ChemicalBonding-l eAS 253
2pz
O
OO P2py P2p

2p
O20 p

O2s

2S 2s

2s

is

)
1s 1s

O1s
Ao's Mo's Ao's

Fig. 4.17 Energy Level diagram for Ng.

N ion: N ion has one electron less than

N, molecule. This electron will be lost from O2p
orbital. Hence the molecular electronic
configuration will be-
N = KK o2 p py ap
ne 1on is
Bond order7-2)=2
paramagnetic due to the presence of unpaired electron.
adsa 0n has or one more electron than the nitrogen molecule. This extra electron is
dded in
+wapx T
T2py Orbital, thus molecular ion electronic configuration will be-
1
N =
KK o 2 px Tpy ipa T2px
Bondorder e-3)= 2 2
254
Engineering Chemistry
Moreover, as it contains one unpaired electron the ion is paramagnetic.

Nion: N ion has two more electrons than nitrogen molecule. These two extra elert..
are
added one each in 2pr and T2py orbitals. Electronic configuration of N ion can hbe wei.
written a
1
2 12px
N =KK o, o2 2p
2
|T2py T2py
Bondorder 8-4)=2
Purther it contains two unpaired electrons, it is paramagnetic.

Table 4.4 Comparision of Ng, Ng, N and N

Molecular Electronic Bond
Specie Configuration Order Magnetic
Character
3
Diamagnetic
N KK Tpr Tpy aps Paramagnetic
Ng KK o pppe Paramagnetic
2
Paramagnetic
Stability of these species is in the order:
N,> N =N,N
Oxygen Molecule O,; Each oxygen atom has 6 valence electrons.
do not participate in Assuming that inner orbitals
bonding, altogether 12 electrons have to be accomodated
The molecular electronic in molecular orbitals
configuration will be:
py 2py
O KK 2 ga2 p
2 1

0
T2px 72px
In the case of oxygen, the difference
between the
large (1430 kJ/mol) and hence interaction betweenenergiesthese
of 2s and 2p, atomic orbitals is
que
order of energies of molecular orbitals do not take orbitals and subsequent changes n
given in section 4.3 is followed. As is evident from theplace. Thus, the usual order of energes
electrons are present, thus the molecule is energy level diagram that two unpa
paramagnetic.
molecular orbital theory, as it could predict the This is one of the great
sucessd
not be explained on the basis of valence bond paramagnetism oxygen molecule whien co
of
theory.
Bond order = (10-6)/2=2. Thus a
double bond is present the molecule.
in
Chemical Bonding-ll
255

202
O
Papx P2Px P2py ***

2pz
2s

O2s

01s

1s
Ao's Mo's Ao's
Fig. 4.18 Energy level diagram for O, molecule
ion: These superoxide ions O has 17 electrons,i.e., one electron more than Og and hence
this extra electron enters t h e * or T2py orbital. The molecular orbital electron configuration

becomes:
1T2py
= KK o2, a p 2
2px |T2px
Bond order =(10-7)/2=1
The superoxide ion is paramagnetic.
256 Engineering ChemistryN
05 ion:The peroxide ion 03 has 18 electrons and has molecular orbital configuration as:

T2p
2 2
12px 12px
Bond order = 10-8/2 = 1.

o ion: This ion has 15 electrons. The molecular orbital configuration can be written as:

KK o 02 Ope
1p 2p
12px 1
2
T2px
BondOrder =8-3)
2 2
Higher bond orders are associated with shorter bond lengths and higher bond strengths.
Threfore we can conclude that bond strength of the above specie in decreasing order oanbe
arranged as:

Table 4.5 Comparision of O, 0, 0, 0

Molecular Electronic Bond Magnetie
Species Configuration Order Character
0 Paramagnatic.
O KK 3 p apy p Tpy 2 Paramagnatic.
O KK 2 O2 p p 2
Tp 2p T2PY Paramagnatic.
0 KK
2 p2py tp tpy 1 Diamagnetic
Flourine Molecule Fz Flourine atom has 7
electrons in the outermost shell and hence
electrons are arranged in the molecular orbital as: 1
2
= KK o2 0 ap |T02py
2
1T2px 02px
Bond Order 8-6) =1
=

The F-F bond is rather weak. Since there le is

are no
diamagnatic. unpaired electrons, the moleu
Chemical Bonding-l 257

O 2pz

P2px P2py
0,
rsg- - - - . P2px(AP2py
202
2s
.

2s

1s*

1s
Ao's Mo's Ao's
Fig. 4.19 Energy level diagram of flourine molecule.

veon Molecule, Ne,: Neon atom has 8 electrons in its valence shell. In the formation of Neon
ecule, if possible, 16 electrons have to be accommodated in molecular orbitals. The molecular
eectronic econfiguration of Neon
molecule would be
2
Ne: KK o O28 O2pz TT2P2G2p
2 2
T2p Tt2p*
apparant that the effects of the bonding orbitals and autibonding orbitals cancel, so the
molecule does not exist.
4.6
HETERONUCLEAR DIATOMIC MOLECULES
The nolecular orbitals of
iatomic molecu heteron diatomic molecules differ from those of homonuclear
cules. Sincelthe two atoms are of their atomic orbitals
are
different,
the energies
 258
Engineering Chemistry
the electrona
difference in the electronegativities ofthe atoms,
slightly different. Due to the electronegativity. The elect
to the atom having high
bonding nmolecular orbital will lie closer electronegative atom.
ons
molecular orbitals are closer to the less
in an antibonding
Moreover, there is the energy difference
between the two sets atomic orbitals on thettwo
of
different atoms. It means that two levels will
interact less strongly and the energy lowering ae
result of the orbitals on different atoms in a heteronuclear molecule la
overlap of atomic
is
than in homonuclear molecule, the
when the orbitals have energies. Let 11
same
pronounced
discuss the electronic structures and molecular orbitals diagrams for some heteronuclear diatomic

molecules.
1. Hydrogen Fluoride molecule, HF: The electronic configuration of hydrogen and fluorine
atoms are
H 1s
F 1s22s 2p
The formation of HF molecule takes place by linear combination of the H (1s) atomic orbital
with one of the F atomic orbitals. Spectroscopic evidence shows that energies of 1s and 2s2
electrons of fluorine are very low and these do not take part in the bonding. Out of the three 2p
orbitals,only 2pz orbital is able to combine with an s-orbital because of symmetry considerations.
Therefore, in the formation of HF molecule, the (1s) electrons and
bonding results from the H
2P, electrons of F and the other electrons of fluorine remains in atomicorbitals

o*(sPz)

1s

F 2Px F 2Px 2Py 2Pz

2Py

GSPz

H F(2s)

Fig. 4.200
The structure of HF molecule, therefore, may be written as
H (1s) + F (1s 28
2p5) HF [K(2s)* (gD(2p (2p,)
The bonding G2 is the only molecular orbital formed in
HF molecule.
The rest of the electrons remain in their atomic cule,
orbitals. The configuration ofHF mo
closely resembles that of the neon atom (1s*2s* 2p°). However, in neon, all the omic.

It may be noted that orbitalsa oins

oap) 1s the only MO formed in HF molecule and bonding M0 co
tains

two electrons.
In case of heteronuclear HF molecule, the electrons are no n
the
longer shared equally betwe
two nuclei. The F(2p,) atomic orbital is cular

contributing more than the H (1s) orbital to the mole

Chemical Bonding-l 259

rhitals. As seen in Fig. 4.20, the molecular orbital has an energy which lies closer to that of 2p,
or
orbital of fluorin tham to that of 1s-orbital of hydrogen.
Similarly, the other HHX molecules have single bond with an unequal sharing of the electrons
hetween the nuclei. The chlorine, bromine and iodine atoms contribute respectively 3p, 4p, and
5p, atomic orbitals in tormation of HX molecules.
The molecular orbital diagram for HCl will be similar to HF.
9.Nitric Oxide Molecule (NO): The electronicconfigurations of N and O atoms are:
N= 1s2 2s 2p2p,
2P
O 1 s 2s*
2p,2 2p,1 2p
There are five electrons in the outer most shell of N atom and six electrons in outer shell of O
atom.Thus, a total of 11 electrons are to be accommodated in the molecular orbitals of NO
molecule.The MOdiagram for NO molecule is shown in Fig. 4.21. It is clear from the
that the bonding MO's are closer to oxygen and antibonding MO's are closer to N atomdiagram
because
oxygen is more electronegative than nitrogen.
The molecular orbital electronic configuration of NO molecule is:

NO = o 2 G2pz ap 2p
12p
Bond order = = 2

NO is paramagnetic. As is evident from the fig. 4.21 that it is similar to as that of diatomic
molecules such as O, or F, but energy level of N and O are not the same.

O2pz
T2px T2py
2P 2p
O00% -0000
2py.
2pz

2s

-0-
2s

-0-
O2s
N NO

Fig. 4.211 Molecular orbital diagram for NO molecule.

260
Engineering Chemistry
carbon and oxygen:
3. Carbon monoxide molecule, CO: The electronic configuration off carbon oxygen atomg
are:
C: 18 2s 2p2 and 0:1 2822p
There are four electrons in the outermost shell of carbon atom and six electron in the outer
shell of oxygen. Thus, a total of 10 electrons are to be accommodated in the molecular orbitals
CO molecule. The MO diagram for CO molecule may be drawn similar to NO molecule as sho
in Fig. 4.21.Then the molecular orbital configuration may be written as: shown

CO: KK o o

Bondorder = =3

Thus CO molecule has a triple bond. Its bond dissociation energy has been found ta
1067 kJ mol and bond length equal to 1.128 A. However, it maybe noted that the molecular
orbital diagram or CO is somewhat complieated than NO molecule.The above configuration
is not correct.
Oxygen is more electronegative than carbon and therefore, the atomic orbitals of oxygen are
lower than those of carbon. Due to this difference, the o2 MO is slightly higher in energy than
2pz Tapx and T2py MOs. The diagram for CO molecule is shown in 4.22.
The better understanding ofthe structure is possible by comparison of C0 and CO*. Cois
formed by the loss of one electron from cO molecule. f the electronic coinfiguration for CO molecule
similar to NO, is correct, then electronic configuration for CO* is

cO KK 0, o

Bondorder =

Thus, when CO is ionized to CO", then its bond order should be reduced to 2 and the bond
2
length should be increased. However, the bond length in COt is 1.115 Å and is less than in CO
(1.128 A). This means that the simple picture of CO molecule similar to other molecules is not
correct. In fact, there is slight increase in bond order when CO is changed toCo*. The most likely
explanation for the increase in bond order or decrease in bond length is that the electron must
have been removed from antibonding molecular orbital. This has been on the basis
energy levels of C and O atoms in Fig. 4.22.
explained 0
The above figure shows that o2s
MO is higher in energy than ony, Tyor and T2yMO'
P) S. NO
when an electron is lost, it is removed from O2s MO and
therefore, bond order increases. A
result, CO" has slightly strong bond than does CO and bond length in Co is less than that m
molecule.
The molecular orbital configuration may be written
as

co:KK o 2P
Chemical Bonding-ll
261

2px 2py
0-
000
2
00
2px 2py
0-
O2pz

O2s
Ao's
Mo's
C Ao's
CO O
Fig. 4.22 Molecular orbital diagram for CO
molecule.

QUESTIONS
SHORT ANSWERS QUESTIONS
(Refer to the Respective Sections for Answers)
Section 4.1
1. What do you understand by
2. molecular orbital?
What is the difference between VBT and
MOT?
3. What are the main point of MOT?
Section 4.2
4. What do you understand by LCAO method
5. Sketch the shapes of molecular orbitals formed the
by overlap of
) Two s-orbitals.
i) End on overlap of two p-orbitals.
(11) Side on overlap of two
p-orbitals. Name the orbitals formed in each case.
.What is the maximum number of electrons that can occupy a molecular orbital? How many MO.s
of
H originate from the hydrogen 1s atomic orbitals?
What is meant by bonding and antibonding molecular orbitals?
What are the conditions of combination of atomic orbitals?
Section 4.3
v e molecular orbital description of hydrogen molecule and deduce the bond order.
.Discuss the energy level diagram of F2, Og and Neg row
**What is the order of the energy of the molecular orbitals in case of diatomic molecular of second
elements of the periobic table up to Ng.