B.sc.

III
Chemistry
Paper C
Submited by :-
Dr. Sangeeta Mehtani
Associate Professor
Deptt. Of Chemistry
PGGCG, sec11
Chd
Quantum Mechanics
PART 2 B
 Linear combination of atomic orbitals

Rules for linear combination

1. Atomic orbitals must be roughly of the same energy.

2. The orbital must overlap one another as much as

possible- atoms must be close enough for effective
overlap.
3. In order to produce bonding and antibonding MOs,
either the symmetry of two atomic orbital must remain
unchanged when rotated about the internuclear line or
both atomic orbitals must change symmetry in identical
manner.
 Rules for the use of MOs
* When two AOs mix, two MOs will be produced

* Each orbital can have a total of two electrons

(Pauli principle)

* Lowest energy orbitals are filled first (Aufbau

principle)

* Unpaired electrons have parallel spin (Hund’s rule)

Bond order = ½ (bonding electrons – antibonding

electrons)
 Linear Combination of Atomic Orbitals (LCAO)

The wave function for the molecular orbitals can be

approximated by taking linear combinations of atomic
orbitals.

A B
A B

AB = N(cA A + cBB) c – extent to which each AO

contributes to the MO
2AB = (cA2 A2 + 2cAcB A B + cB2 B 2)

Probability density Overlap integral

 Constructive interference

. + .
+. +.
g bonding
cA = c B = 1

g = N [A + B]
Amplitudes of wave
functions added
2AB = (cA2 A2 + 2cAcB A B + cB2 B 2)
density between atoms

electron density on original atoms,

The accumulation of electron density between the nuclei put the
electron in a position where it interacts strongly with both nuclei.

Nuclei are shielded from each other

The energy of the molecule is lower

 node

+. -. +. .-
cA = +1, cB = -1 u
antibonding
u = N [A - B]

Destructive interference
Nodal plane perpendicular to the
H-H bond axis (en density = 0)
Energy of the en in this orbital is
higher.
A-B

Amplitudes of wave
functions
subtracted.
The electron is excluded from internuclear region  destabilizing

Antibonding
 When 2 atomic orbitals combine there are 2
resultant orbitals
orbitals..
Eg.. s orbitals
Eg

s*1s
E high energy antibonding orbital
1sb 1sa

s1s

Molecular
orbitals
low energy bonding orbital
Molecular potential energy curve shows the variation
of the molecular energy with internuclear separation.
 Looking at the Energy Profile
 Bonding orbital
 called 1s orbital
 s electron
 The energy of 1s orbital
decreases as R decreases
 However at small separation,
repulsion becomes large
 There is a minimum in potential
energy curve
 H2

11.4 eV
LCAO of n A.O  n M.O.
109 nm

Location of
Bonding orbital
4.5 eV
 The overlap integral

The extent to which two atomic orbitals on different atom

overlaps : the overlap integral

S    B d
*
A
 S > 0 Bonding S < 0 anti

Bond strength depends on the

S = 0 nonbonding
degree of overlap
 Homonuclear Diatomics
• MOs may be classified according to:
(i) Their symmetry around the molecular axis.
(ii) Their bonding and antibonding character.
• s1s s1s* s2s s2s* s2p y(2p) = z(2p)
y*(2p) z*(2p)s2p*.
 dx2-dy2 and dxy

2-
Cl4Re ReCl4
 g- identical B
under inversion
A
u- not identical
Place labels g or u in this diagram

s*u

*g

u

sg
 First period diatomic molecules
H H2 H s1s2

su*
Bond order: 1
Energy

1s 1s

sg

Bond order =
½ (bonding electrons – antibonding electrons)
 Diatomic molecules: The bonding in He2

He He2 He
s1s2, s*1s2

su*
Bond order: 0
Energy

1s 1s

sg

Molecular Orbital theory is powerful because it allows us to predict whether

molecules should exist or not and it gives us a clear picture of the of the
electronic structure of any hypothetical molecule that we can imagine.
Three Conditions for Overlap/Combining of
Atomic Orbitals
 Symmetry of the orbitals must be such
that regions with the same sign of 
overlap.
 Overlap of s atomic orbital with p atomic
orbitals
 Energies of the overlapping orbitals must
be similar.
 The distance between overlapping orbitals
must be short to be effective.
Hybridization
 An orthonormal set of hybrid orbitals is
created by applying a transformation on
the orthonormal hydrogenic orbitals. The
sp3, sp2 or sp hybrid orbitals are linear
combinations of the AO’s, they appear as
the resulting interference between s and p
orbitals
QUANTUM MECHANICAL
PRINCIPLES OF HYBRIDIZATION
 The hybrid orbitals are formed by linear
combination of atomic orbitals belonging to
the same atom.
 As the s-orbital is spherically symmetrical its
charge density will be equally distributed
among n possible hybrid orbitals.
 Each wave function is normalized.
 The wave functions of the hybrid orbitalls as
well as atomic orbitals are orthogonal to each
other.
QUANTUM MECHANICAL
PRINCIPLES OF HYBRIDIZATION
 In the formation of sp2 hybrid orbitals as
well as atomic orbitals the first hybrid
orbital may be considered to have
maximum charge density along X-axis.
Then py and pz will not contribute towards
this hybrid orbital
 In the formation of sp3 hybrid orbitals the
second orbital may be considered to be in
a plane say xz then py will not contribute
towards this hybrid orbital
CALCULATION OF THE COEFFICIENTS OF
ATOMIC ORBITAL IN SP3 HYBRID ORBITALS

 The four sp3 hybrid orbitals are as follows:

Ψ 1 = a 1 ф s + b 1 ф py +d 1 ф pz
Ψ 2 = a 2 фs + b 2 ф py +d 2 ф pz
 Ψ 3 = a 3 ф s + b 3 ф py +d 3 ф pz
 Ψ 4 = a 4 ф s + b 4 ф py +d 4 ф pz
CALCULATION OF THE COEFFICIENTS OF
ATOMIC ORBITAL IN SP3 HYBRID ORBITALS

 Since the s-orbital is equally distributed

among the four hybrid orbital, we will get
the following:
a 2 1 = a 2 2 = a 2 3 = a 2 4 = 1/4
Hence,
a 1 = a 2 = a 3 = a 4 = 1/4 1/2 = 1/2
CALCULATION OF THE COEFFICIENTS OF
ATOMIC ORBITAL IN SP3 HYBRID ORBITALS

 Let us suppose that ф 1 is developed along

the x-axis, that is this hybrid orbital will get
contribution from s and px orbitals only.
Because of this the contribution from ф py and
ф pz will get vanished.
Hence we can write:
c1=d1=0
As Ψ1 is in normal form, we will get:
a21+b21+c21+d21=1
Or we can rewrite it as:
a21+b21=1
CALCULATION OF THE COEFFICIENTS OF
ATOMIC ORBITAL IN SP3 HYBRID ORBITALS

 (Because c 1 = d 1 = 0)
Therefore b 1 = (1 – a 2 1) 1/2
= (1 – 1/4) 1/2
= (3) 1/2 / 2
The requirement of orthogonality condition
for Ψ1 and Ψ2 , Ψ1 and Ψ3, ф1 and Ψ4, it
will give:
a1a2+b1b2=0
a1a3+b1b3=0
a1a4+b1b4=0
CALCULATION OF THE COEFFICIENTS OF
ATOMIC ORBITAL IN SP3 HYBRID ORBITALS

 Hence, b 2 = b 3 = b 4
=–a1a2/b1
= – a1 a 3 / b1
=–a1a4/b1
 = – [ (1/2) (1/2) ]/[ (3)1/2 / 2]
 = – 1/ (2 (3) 1/2)
 Suppose that Ψ2 lies in the XZ plane, the
hybrid orbital will have contributions form s ,
px and pz orbitals only. The contribution of py
to ф2 would be equal to zero. Hence,
CALCULATION OF THE COEFFICIENTS OF
ATOMIC ORBITAL IN SP3 HYBRID ORBITALS

 c2 = 0
The normalization requirements for Ψ2 will
be:
a22+b22+c22+
d22=1
Or we can rewrite it as:
a2 2 + b 2 2 + d 2 2 = 1
(Because c 2 = 0)
CALCULATION OF THE COEFFICIENTS OF
ATOMIC ORBITAL IN SP3 HYBRID ORBITALS

 Because d 2 2 = 1 – (a 2 2 + b 2 2)
= 1 – (1/4 + 1/12) = 2/3
Therefore d2 = (2/3)1/2
The requirement of orthogonality condition
for and Ψ2 , Ψ3 and
Ψ 2 , Ψ 4 will give:
a 2 a 3 + b 2 b3 + d2 d3 = 0
a 2 a 4 + b 2 b4 + d2 d4 = 0
Hence, d3 = d4
CALCULATION OF THE COEFFICIENTS OF
ATOMIC ORBITAL IN SP3 HYBRID ORBITALS

 = [ - a2 a3 - b2 b3 ]/ d2
 Or
[- a2 a4 + b2 b4] / d2
 = – [(1/4 + 1/12)]/[ (2/3) 1/2]

 = – 1/ (6) 1/2
CALCULATION OF THE COEFFICIENTS OF
ATOMIC ORBITAL IN SP3 HYBRID ORBITALS

 The normalization requirement for Ψ3 will

be given as:
a23+b23+c23+
d23=1
c 2 3 = 1- (a 2 3 + b 2 3 +
d 2 3)
= 1 – (1/4 + 1/12 + 1/6) = 1/2
Therefore c3 = + 1/2
CALCULATION OF THE COEFFICIENTS OF
ATOMIC ORBITAL IN SP3 HYBRID ORBITALS

 The normalization requirement for Ψ4 and

orthogonality condition between Ψ3 and
Ψ4 gives:
 c4 = – 1/ (2) 1/2
CALCULATION OF THE COEFFICIENTS OF
ATOMIC ORBITAL IN SP3 HYBRID ORBITALS

 Hence, the four sp3 hybrid orbital’s wave

functions are:
 Ψ 1 = 1/2 ф s + {(3) 1/2} / 2 ф px
Ψ 2 = 1/2 ф s – {1/2(3) 1/2} ψ px +
(2/3) 1/2 ф pz
 Ψ 3 = 1/2 ф s – {1/2(3) 1/2} ф px +
1/(2)sup>1/2 ф py – 1/(6) sup>1/2 ф pz
 Ψ 4 = 1/2 ф s – {1/2(3) 1/2} ф px +
1/(2)sup>1/2 ф py – 1/(6) sup>1/2 ф pz