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