IR Spectros

IR Spectroscopy
Principle: Infrared Spectroscopy is also called as vibrational spectroscopy as it involves the

transition between vibrational energy levels of the molecules having change in dipole
moment.
Dipole moment is the product of charge and distance. Only those molecules which undergo a
net change in dipole moment because of its vibrational or rotational motion absorb in the IR
region.
• When a heteronuclear diatomic molecule undergoes stretching vibration, the dipole

moment changes with the internuclear distance and absorb in the infrared region and
so they called as IR active.
• When a homonuclear diatomic molecules do not show any net change in dipole
moment during vibration and hence they do not absorb in the infrared region and
called IR inactive.
The effective transitions for infrared region range from 500 – 4000cm-1.
This technique is a powerful tool for:
• Determination of the structure of the compound.

• To establish the intensity of the compound.
• Predict the presence of the functional groups which absorbs at definite frequencies.
Types of vibration
There are two types of vibration
1. stretching 2. Bending
Stretching:
In this type of vibration, the distance between the atoms increases or decreases but the atoms
remain in the same bond axis. There are two types of stretching vibrations. They are:
1. Symmetric stretching: Movement of atoms with respect to a particular atoms in

the molecules.
2. Asymmetric Stretching: one atom approaches the central atom and the other
departs from it.
Bending vibrations
The position of the atom changes with respect to the original bond axis but the distance
between the atoms remains constant.
1. In plane bending vibrations: here the atoms remain in the same plane.
a. Scissoring b. rocking
2. Out of plane bending

a. Wagging b. twisting
More energy requires to stretch than bending, hence stretching vibrations appear at higher
frequency as compared to bending.
Number of fundamental vibrational modes in a molecule

• The number of vibrations depend upon the degrees of freedom in a molecule.
• The number of degrees of freedom depend is equal to the sum of the coordinates
necessary to locate all the positions of atom in the space.
• For a molecule,
Types of degree of freedom = translational + rotational + vibrational
Total degrees of freedom= 3n; where n is the number of atoms in a molecule
a. For linear molecule
total degrees of freedom = 3n
translational degrees of freedom = 3
rotational degrees of freedom = 2
 number of vibrational of freedom = 3n-3-2 = 3n-5
Eg:
i. HCl
No:of atoms=2
No:of vibrational modes=3n-5 = 3x2-5 =1
Stretching vibrations only.
ii. CO2
No:of atoms = 3
No:of vibrational modes = 3n-5 = 3x3-5 = 4
b. For Non-linear molecules

Total degrees of freedom = 3n
Translational degree of freedom = 3
Rotational degree of freedom = 3
 vibrational degree of freedom = 3n – 3 – 3 = 3n-6
Eg: H2O
Total no. of atom = 3
No. of vibrational mode = 3 x 3 – 6 = 3
Vibrational energy states of a simple Diatomic Molecule
Consider a diatomic molecule associated with diploe moment. The vibrational motion of
atoms of a diatomic molecule is perpendicular to the vibration of simple harmonic oscillator.
When a photon of frequency come in resonance with the frequency of vibration of a
molecule, the absorption of photon takes place and molecules starts oscillating with the
frequency of radiation.
According to Hooke’s Law, the force required to restore an atom to its original state is
proportional to the displacement of the vibratory atom from its original position,
i.e., F  x
F = -Kx
Where, K = force constant in Nm-1 x = displacement (-ve sign implies the restoring force)
According to Hooke’s Law, the potential energy of simple harmonic oscillator is
V = - ½ Kx2
This is the equation of parabola.
Consider two masses m1 and m2 connected by means of chemical bond of force constant K.
1 𝑘
Fundamental frequency 0 = 2𝜋 √𝜇
𝑚 𝑚
Where,  = reduced mass = 𝑚 1+𝑚2
1 2
The solution of Schrodinger equation for a simple harmonic oscillator gives quantized
vibrational energy levels.
E = (V + ½) h 0
Where, V = vibrational quantum number as 0,1,2,3,…
In the ground state; v=0, E = ½ h0 , termed as zero point energy. At zero-point energy, even
at absolute zero, there will be vibration.
Energy Levels of Harmonic Oscillator
If a diatomic molecule undergoes transitions from lower ‘V’ level to upper ‘V’ level
E = (V’ + ½ ) h0 – ( V+ ½ ) h0
But, E = h
 (V’ + ½) h0 – (V + ½) h0 = h
(V’ – V) h0 = h = hC Also, h = h c/ = hC
Thus for a diatomic molecule, two consecutive levels are equally spaced and they are equal to
h and hC .
Selection Rule
The selection rule for vibration transitions in a simple harmonic oscillator is V = ±1
+ve sign indicates absorption and -ve sign indicates emission spectra.
At room temperatures the molecules are in ground vibrational state (V=0), hence the
transitions will occur from V= 0 to V= 1, corresponding frequency is called fundamental
vibrational frequency.
Anharmonic Vibrations
In harmonic oscillator model, the diatomic molecule reaches equilibrium state and never
dissociate, but for a real molecule, as the displacement increases, the restoring fore becomes
weaker and then the molecule gets dissociate into atoms. Such an oscillator is called
anharmonic oscillator.
Applications
• It is an important tool used to determine the structure of organic compounds.

• It can be studying any sample state from liquids to solutions, pastes, powders, films,
fibers.
• Determination of force constant of a diatomic molecule.
1 𝑘
We know, fundamental frequency, 𝜈0 = 2𝜋 √𝜇
1 𝑘
Also, 𝜈̅ = 2𝜋𝑐 √𝜇
By squaring we get the equation for finding the force constant as:
𝒌 = 𝟒𝝅𝟐 𝒄𝟐 𝝂̅𝟐 𝝁
• Identification of functional groups in organic compounds.
Eg. CO in ketones – 1700-1725 cm-1
OH in alcohol – 3300-3500 cm-1
NH2 – 3200-3300 cm-1
C=C – 1620 – 1650 cm-1
C-H – 2900 -3000 cm-1
• Identification of unknown compounds by comparison of IR spectrum of unknown
compound with that of a known compound.
• Determination of purity.
• Distinguish between inter molecular and intramolecular hydrogen bonding.
• On dilution, intermolecular hydrogen bonding in p-hydroxy phenol weakens and
show a shift in absorption spectrum. In o-hydroxy phenol, the hydrogen bonding type
is intramolecular which is not affected by dilution.

IR Spectros

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IR Spectroscopy

Principle: Infrared Spectroscopy is also called as vibrational spectroscopy as it involves the

• When a heteronuclear diatomic molecule undergoes stretching vibration, the dipole

This technique is a powerful tool for:

• Determination of the structure of the compound.

1. Symmetric stretching: Movement of atoms with respect to a particular atoms in

2. Out of plane bending

Number of fundamental vibrational modes in a molecule

No:of vibrational modes=3n-5 = 3x2-5 =1

Stretching vibrations only.

No:of vibrational modes = 3n-5 = 3x3-5 = 4

b. For Non-linear molecules

According to Hooke’s Law, the potential energy of simple harmonic oscillator is

This is the equation of parabola.

Where, V = vibrational quantum number as 0,1,2,3,…

E = (V’ + ½ ) h0 – ( V+ ½ ) h0

 (V’ + ½) h0 – (V + ½) h0 = h

(V’ – V) h0 = h = hC Also, h = h c/ = hC

The selection rule for vibration transitions in a simple harmonic oscillator is V = ±1

• It is an important tool used to determine the structure of organic compounds.

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