Fourier Transform IR

spectroscopy
Prof. Silvio Martinez
Absorption spectroscopy
The goal of any absorption spectroscopy is to
measure how well a sample absorbs light at
each wavelength.
The representation of such measurement is
the spectrum of the sample.
The most straightforward way to do this, the
"dispersive spectroscopy" technique, is to
shine a monochromatic light beam at a
sample, measure how much of the light is
absorbed, and repeat for each different
wavelength
The equation of a simple wave

X = A sin (ωt + φ)
or
X = A cos (ωt + φ)

• Remember that cos θ = sin (θ + π/2)

 A simple spectrum

2
1.5 cos 4π t
1.5 1.2 cos π t 1 cos 2π t 1.5
1.2
1 1

0.5

0
0 1.57 3.14 4.71 6.28 7.85 9.42 10.99 12.56 14.13 15.7
-0.5
 5

1.2 cos π t 1

-1 0 0.5 1 1.5 2 2.5 3

-3

-5

1 cos 2π t -1 0 1 2 3

-3

-5

1
1.5 cos 4π t -1 0 0.5 1 1.5 2 2.5 3
-3

-5
 5

-1 0 0.5 1 1.5 2 2.5 3

-3

-5

5
4
5
3 3

2 1

1 -1 0 1 2 3

0 -3

-5
-1 0 0.5 1 1.5 2 2.5 3
-2
-3 5

-1 0 0.5 1 1.5 2 2.5 3

-3

-5
 2

1.5 1.5
1.2
1 1

0.5

0
0 1.57 3.14 4.71 6.28 7.85 9.42 10.99 12.56 14.13 15.7
-0.5

5
4
3
2
1
0
-1 0 0.5 1 1.5 2 2.5 3
-2
-3
 Interference
The principle of superposition of waves states that when
two or more waves are incident on the same point, the
total displacement at that point is equal to the vector sum
of the displacements of the individual waves. If a crest of a
wave meets a crest of another wave of the same frequency
at the same point, then the magnitude of the displacement
is the sum of the individual magnitudes – this is
constructive interference. If a crest of one wave meets a
trough of another wave then the magnitude of the
displacements is equal to the difference in the individual
magnitudes – this is known as destructive interference.
 0.60
0.40
0.20

FROM 0.00
-0.20 0 0.5 1 1.5 2 2.5

-0.40
-0.60

3.5

2.5

TO 1.5

0.5

-0.5
0 0.5 1 1.5 2 2.5
-1.5

-2.5

-3.5
Fourier transform spectroscopy
• is a less intuitive way to obtain the same
information as using a dispersive system.
Rather than shining a monochromatic
beam of light at the sample, this technique
shines a beam containing many different
frequencies of light at once, and measures
how much of that beam is absorbed by the
sample.
 Fourier transform
The Fourier transform is a mathematical operation
that expresses a mathematical function of time as a
function of frequency, known as its frequency
spectrum; Fourier's theorem guarantees that this
can always be done.
For instance, the transform of a musical chord
made up of pure notes expressed as amplitude as a
function of time, is a mathematical representation of
the amplitudes and frequencies of the individual
notes that make it up.
 Mathematically
the Fourier transform of an integrable function ƒ can be defined as:
for every real number ξ .

for every real

number ξ

Where,
x represents time (in seconds), and
ξ represents frequency (in Hertz)

In many cases it is desirable to use Euler's formula, which states that

e2πiθ = cos 2πθ + i sin 2πθ, to write Fourier series in terms of the basic
waves e2πiθ
 SO!!

In principle, having an interference

pattern, It’s possible to know the
waves that originated that pattern
(Their amplitude and frequency – or
wavelength) and from them, to draw
the spectrum.
The instrument
Interferometer
Interferogram
• As mentioned, computer processing is
required to turn the raw data (light
absorption for each mirror position) into
the desired result (light absorption for each
wavelength, frequency or wave number).
The processing required is called the
Fourier transform (hence the name,
"Fourier transform spectroscopy"). The
raw data is sometimes called an
"interferogram".

Flash
 FROM

TO
 Advantages (Summary)
Speed: All the wavelengths are measured at the same
time. Scanning through the spectrum is not necessary
Sensitivity: Almost 50 % of the intensity coming from
source go to the detector.
Mechanical simplicity: The moving mirror in the
interferometer is the only continuously moving part in the
instrument.
Self-calibrating: Wavelength is internally calibrated by a
laser.
 Qualitative analysis
• FTIR can be used to identify chemicals from spills,
paints, polymers, coatings, drugs, and
contaminants. FTIR is perhaps the most powerful
tool for identifying types of chemical bonds
(functional groups). The wavelength of light
absorbed is characteristic of the chemical bond as
can be seen in this annotated spectrum.
• FTIR spectra of pure compounds are generally so
unique that they are like a molecular "fingerprint".
• For most common materials, the spectrum of an
unknown can be identified by comparison to a
library of known compounds
 Quantitative analysis
The sensitivity and accuracy of FT- IR
detectors, along with a wide variety of
software algorithms, have dramatically
increased the practical use of infrared for
quantitative analysis. Quantitative methods
can be more easily developed and calibration
can be incorporated into relatively simple
procedures for routine analysis.