IR Spectroscopy

Types of vibrations
• Bending vibrations require less energy and therefore take place at
lower wave number, i.e., vibrational frequency than stretching

• Usually bending vibrations occur at frequencies below 1500 cm–1. These

are not useful for structural elucidation as the numbers of bands are
large and often bands are obscured due to overtones and combination
bands
Selection rule

• The most fundamental requirement for infrared activity is that a

vibration must cause a change in the dipole moment of the molecule

HCl, CO: Polar (IR active)

H2, N2: Nonpolar (IR inactive)

• Exception: CO2 is nonpolar still IR active. This is due to the fact that in
asymmetric stretching of CO2, there occurs a change on dipole moment
and is active. Both possible bending modes are active and occur at the
same frequency
Fundamental vibrations
• The IR spectrum of a molecule results due to transition
between two vibrational energy levels.
• The vibrational motion resembles that of a harmonic
oscillator.
• The vibrational energy of a chemical bond is quantized
and can have values

Where, V is the number of vibrational level and can

have values 0, 1, 2, 3, and so on,
h is Planck’s constant, and
v is the vibrational frequency of the band
• Transition from the ground state (V = 0) to the first
excited state (V = 1) absorbs radiation strongly and
gives rise to intense band called fundamental band

• The other transitions such as from the ground state to

the second excited state (V = 2) and so on gives rise to
weak bands called overtones

• Polyatomic molecules may exhibit more than one

fundamental vibrational absorption bands

• The number of these fundamental bands is related to

the degrees of freedom in a molecule
• The number of degrees of freedom is equal to the sum
of coordinates necessary to locate all the atoms of a
molecule in space. In a molecule the total number of
degrees of freedom is equal to 3n

Linear molecule

• Here translational degrees of freedom = 3,

• Rotational degrees of freedom = 2, as the rotation of
such a molecule about its parent axis do not bring
any change in the position of atoms
• Vibrational degrees of freedom = 3n-5
Nonlinear molecule
• Here, translational degrees of freedom = 3
• Rotational degrees of freedom = 3, as the rotation of such a
molecule about all the three axes bring change in the
position of atoms
• Vibrational degrees of freedom = 3n-6
Note:
• It has been observed that the theoretically calculated numbers of
fundamental vibrations are usually more than found in an IR
spectrum. The reason for the smaller number of fundamental
vibrations than expected number are as follows:
• Several of the vibrations are redundant or degenerate, i.e., energies
of two or more vibrations are identical or nearly identical.
• Symmetry of the molecule
• Undetectable low absorption intensity.
• Out of the instrumental detection range
Vibrational Frequency

Example
Calculate the wave number of stretching vibration of a carbon–
carbon double bond. The force constant is given 106 dynes cm–1.
1. Conjugation lowers the stretching frequency. With
increase in conjugation multiple bond character is
reduced which reduces bond strength. The following
example is illustrating the drop in stretching frequency
value for C = C bond due to conjugation arising out of
resonance.
2. As the “s” character increases in a bond, the bond
becomes stiffer. We already have seen that sp hybridized
C-C bonds are stiffer than sp3 hybridized C-C bonds. The
same is also true for carbon–hydrogen bonds
3. The competition between I-effect and R-effect sometimes
becomes important in deciding the magnitude of stretching
frequency
O-H and N-H stretching:

• Both of these occur around 3300 cm–1, but they look

different

• Alcohol O-H: broad with rounded tip

• Secondary amine (R2NH): broad NH band around

3500 cm-1

• Primary amine (RNH2): broad with two sharp spikes

for symmetrical and unsymmetrical stretching

• No signal for a tertiary amine (R3N)

CH3 CH2 CH2 NH2
(CH3 CH2 CH2)2 NH2