IR Spectroscopy

Engineering Chemistry

Dr. Kalyan S Ghosh

Department of Chemistry

Infra-Red (IR) Spectroscopy

This is Vibrational Spectroscopy
Transition between vibrational energy levels due to absorption of
radiations in the range of 500-4000 cm-1
Vibrational energy change is also accompanied by a large number of
rotational energy changes therefore Vibrational Spectra appear as
vibrational-rotational bands

IR active molecules:

During vibration of a molecule, if there is a change in dipole moment,

it will lead to the generation of an oscillating electric field. Now if
the frequency of the oscillating electric field is equal to the
frequency of the fluctuating electric field of radiation, resonance
will occur.
Therefore energy can be transferred from the radiation to the
molecule or vice-versa. Hence all types of molecules cannot interact
with IR radiation.
Homonuclear diatomic molecules (H2, O2, N2 etc) will not show
change in dipole moment during vibration so do not exhibit IR.

IR spectra of polyatomic molecules

In a polyatomic molecule, the bonds can vibrate in several ways and

these are known as vibrational modes and each vibration has an
associated fundamental frequency.

Symmetric Stretching

Both the bonds (a and b) are

shortened or elongated to the
same extent simultaneously
No dipole change IR Inactive

Asymmetric Stretching

One of the bonds (a and b) is

shortened; while the other (b or
a) elongated
Dipole moment change IR
Active

Bending

Periodic change of bond angles

within a plane
Dipole moment change IR
active

Vibrational spectra of diatomic molecule

The vibrational motion of a diatomic molecule can be considered as
the vibration of simple harmonic oscillator , whose restoring force
(F) is proportional to the displacement x (Hookes Law)

The vibrational frequency () of such a molecule behaving as a

simple harmonic oscillator is given by
Where k = force constant
and = reduced mass
Expressing in wave number

Where c = velocity of light

Prob: Compare the Stretching frequencies of (i) CC and C=C

and (ii) C-C and O-H

Like all other molecular energies, vibrational energy is also quantized

and the permitted vibrational energy can be calculated by Schrodinger
eqn. The energy associated with any vibration state is:
v is vibrational quantum number (0, 1,
Joules
2 etc), 0 is Fundamental Frequency
The vibrational energy levels are much more widely spaced than the
rotational energy levels. Even in ground vibrational state (v = 0), the
molecule has the vibrational energy (1/2h0). This is called as Zero
point energy, which signifies that a molecule must always vibrate can
never be at rest.

Selection Rule for a harmonic vibrational transition

The increase or decrease in the vibrational quantum number is by one

unit only, i.e. = 1
The energy difference between two vibrational levels involved in a
transition is h0

Vibrational Energy Levels

When a molecule absorbs energy in the IR region, transitions take

place between in vibrational as well as in rotational energy levels.
Rotational transitions exhibit fine structures (in gaseous state), but
in liquid or solids, the rotational fine structure becomes buried and
consequently a broad peak

Application of IR-spectroscopy
Determination of force constant from IR spectrum
Identification of functional groups in organic compounds

Regions for characteristic class of Organic Compounds

Alkane

Alkene

Comparison of Alkane and Alkene

Alkyne

Alcohol

Hydrogen bonding leads to higher wavenumber

Ethers
Alkyl Ethers: Strong broad band 1200-1275 cm-1
Aryl and vinyl Ethers: Strong broad band 1060-1150 cm -1

Ketone

Aromatic Compounds

Benzene

Carboxylic acid

Ester

Nitro Compounds