Fourier Transform IR

Spectroscopy

Saptarshi Basu
 Introduction
Absorption peaks in an infrared absorption spectrum arise
from molecular vibrations
Absorbed energy causes molecular motions which create a
net change in the dipole moment.
 What is FTIR
Fourier-transform infrared spectroscopy is a vibrational
spectroscopic technique, meaning it takes advantage of
asymmetric molecular stretching, vibration, and rotation of
chemical bonds as they are exposed to designated
wavelengths of light.
Fourier transform is to transform the signal from the time
domain to its representation in the frequency domain
 Theory and Instrumentation

Light enters the spectrometer and is split by the beam

splitter. The figure above shows what is referred to as the
Michelson interferometer
 Theory and
Instrumentation(contd.)
The light originates from the He-Ne laser
Half of the light is reflected 90 degrees and hits a fixed
mirror, while the other half passes through the beam
splitter and hits the moving mirror
The split beams are recombined, but having traveled
different distances, they exhibit an interference pattern
with each other
As they pass through the sample, the detector collects the
interfering signals and returns a plot of response v.
mirror displacement known as an interferogram
 Mathematics

I ( )

Optical path difference is

Intensity of the detector I ( ) has maxima at
n , n 0,1,2
and minima at ( n 1 / 2)
 Mathematics (contd.)
The resulting interferogram is described as an infinitely long
cosine wave

B( ) cos( 2 ) where B ( ) =intensity as F(v)

For non-monochromatic source treat each frequency as if it
resulted in a separate cosine train.
 Mathematics (contd.)
An infrared source is typically approximated as a black body
radiator and the summation can be replaced by an integral.

I ( ) B( ) cos( 2)d
0
At = 0, signal always has a strong maxima called Centreburst
Outwards from the centreburst the cosine waves cancel and
reinforce and the amplitude of the interferogram dies off.
 Mathematics (contd.)

Spectroscopists are interested in the spectrum in the

frequency domain i.e intensity versus wavenumber
If the mathematical form of the interferogram is
known,spectrum in the frequency domain can be
calculated by Fourier Transformation

B( ) I ( ) cos(2 )d

For mathematical validity this integration must be

carried out over all possible values of delta i.e + to

 Measurement Techniques
Though some emission spectroscopy is done most of the
work is in the absorption spectra area using FTIR.
1. If there is no sample present the spectrum is that
of a black body radiator modified by any transmission
characteristics of the interferometer components.
2. If the interferometer chamber is not evacuated or
purged with dry gas some absorption from the
atmospheric Co2 and H20 is observed. This is called the
background spectrum.
3. When the sample is introduced the spectrum now
is a superposition of the absorption bands of the sample
on an uneven background.
4. To obtain %T with wavenumber we ratio the
single beam sample spectrum with the background
spectrum.
Measurement Techniques(contd.)
Apodization
 Energy transitions

For the vibrational motion of a diatomic molecule, the

permanent electric dipole moment can be expanded in a
Taylor series about the equilibrium internuclear
separation

Hence
can be expressed as
 Energy transitions(contd.)

Therefore, diatomic molecules will only exhibit a

vibrational absorption spectrum if there is a
change in dipole moment with the vibrational
motion
Theory also dictates transition between 1
 Energy Transitions
A typical IR spectrum will have absorbance bands
which can be attributed to the presence of
individual chemical groups in the molecule under
study and a "fingerprint" region distinctive of the
individual compound.
 Applications
Applications are vast and diverse.Some of them are

Compositional analysis of organic,inorganic and

polymers
Biological and biomedical fields like detection of water
in biological membranes
Analysis of Aircraft exhausts
Measurement of toxic gas in fuels
Combustion
Gas analysis
and lots more
 Advantages and Disadvantages
FT IR can take wavelength readings across the whole IR region
simultaneously and smoothly, making this a very rapid technique.
The technique is non-invasive and non-destructive. Its resolution
of .125 cm-1 is not spectacular in comparison to other vibrational
techniques and it will not give the same detailed structural
information that NMR, MS, or X-ray crystallography.
IR spectroscopy is notoriously sensitive to the absorption of
water, and it has the tendency to overwhelm all of the other peaks.
If there is significant moisture in the sample the penetration
distance of the light decreases. It may be advantageous to go with
Raman in place of IR in the case of excess moisture.
Spectra in the frequency domain can never be eyeballed
conclusively. They are always subject to some sort of
manipulation, leading some to believe that the data can say
whatever the experimenter wants it to say depending on how it is
manipulated.
 Advantages and
Disadvantages(contd.)
Much higher signal to noise ratio.Felgetts
advantage=
Greater throughput of power.
Hard to do samples having low transmission and
weak spectra can be done with FTIR.
Greater wavenumber accuracy. Most FT
instruments have an accuracy of +/- 0.01 cm-1.