INFRA-RED

SPECTROSCOPY

Dr. Nasrin Akhter

Senior Lecturer,
Dept. of Pharmacy, NSU
Types of stretching vibration

Two types:
Symmetric stretching vibration
Asymmetric stretching vibration
 Symmetric stretching vibration
Properties

The movement of atoms with respect to

a particular atom is in the same
direction
Inter atomic distance is altered
No change in valence angle
 Asymmetric stretching vibration
Properties

One atom approaches the central atom

and interatomic distance decreases
While the other departs from it and
interatomic distance increases
No change in valance angle
Different types of stretching
vibrations
 Types of bending vibration
(Deformation)
1) In plane bending vibration, which is further
subdivided into two types:

a) Scissoring: In this type-

-Two atoms approach each other i.e. move either
toward or away from each other
b) Rocking: In this type-
- the movement of atoms take place in the same
direction i.e. structural unit swings back and forth in the
plane of the molecule
 Types of bending vibration
(Deformation)
2) Out of plane bending vibration, further
subdivided into two types:

a) Wagging: In this type-

- Two atoms move up and down the plane with
respect to the central atoms
b) Twisting: In this type-
- One of the atoms moves up the plane
while other moves down the plane with respect to
central atoms
Different types of bending
vibrations
Calculation of stretching vibrational
frequency of a bond
Hookes Law:
The stretching vibrational frequency of a bond may be
calculated with fairly accuracy by the help of Hookes
Law
The expression is-
v = 1/2 [k/{m1m2/( m1+m2)}]
where, v= frequency
k= force constant of the bond
and relates to the strength of the bond
m1 and m2=masses of the atoms concerned in grams in
a particular bond
 Calculation of stretching vibrational
frequency of a bond

For a single bond, the bond strength is

approximately 5x105gm sec-2
It becomes double and triple for the double and
triple bond respectively
The quantity m1m2/( m1+m2) is often expressed
as , the reduced mass of the system
 Calculation of stretching vibrational
frequency of a bond

So, v = 1/2 k/

The value of frequency can be converted into

wave number as follows,
v = v/c = 1/2c k/
Where,
c is velocity of radiation= 2.998x 1010 cm sec-1
 Calculation of stretching vibrational
frequency of a bond
Thus the value of vibrational frequency or wave
number depends upon
- the bond strength and
- reduced mass

Clearly it can be said that if the bond strength

increases or the reduced mass decreases,the
value of the vibrational frequency increases
 Selection rules for molecular
vibration

IR light is absorbed only when the dipole

character of the molecule takes place
Complete symmetry about a bond eliminates
some absorption bands
Some of the fundamental vibrations are IR active
and some are not
All these are governed by selection rules
 The selection rules are-

1. If a molecule has a centre of symmetry, then the

vibrations are centrosymmetric and are inactive in the
IR, but are active in the Raman
2. The vibrations which are not centro symmetric are
active in the IR, but inactive in Raman

Since in most of the organic compound, the functional

groups are not centrosymmetric,IR spectroscopy is
more informative for them
 Intensity and position of IR
absorption band

The intensity of a fundamental absorption

depends on the difference between the dipole
moments of the molecule in the ground state
and the vibrational excited state
Greater the difference, more is the intensity of
absorption
Intensity and position of IR absorption band

Since the intensity of absorption band in IR

spectroscopy cannot be measured with greater
accuracy, it is sufficient to know whether the
absorption is strong, minimum or weak

The more intense peak is taken as an intensity

of 100%,then the relative intensities of other
peaks can be estimated