Why IR

To understand the origin of electromagnetic

radiation.
To determine the frequency, wavelength, wave
number and energy change associated with an
infrared transition.
To appreciate the factors governing the intensity of
bands in an infrared spectrum.
To predict the number of fundamental modes of
vibration of a molecule.
To appreciate the different possible modes of
vibration.
Introduction
Infrared spectrometers have been commercially available
since the 1940s.
At the olden time, the instruments relied on prisms to act
as dispersive elements.
Mid 1950s, diffraction gratings had been introduced into
dispersive machines.
The most significant advances in infrared spectroscopy,
however, have come about as a result of the introduction
of Fourier-transform spectrometers.
This type of instrument employs an interferometer and
exploits the well established mathematical process of
Fourier-transformation.
The quality of infrared spectra and minimized the time
required to obtain data.
Infrared Absorptions
For a molecule to show infrared absorptions it must possess
a specific feature, i.e. an electric dipole moment of the
molecule must change during the vibration. This is the
selection rule for infrared spectroscopy.

Infra red active molecule = heteronuclear diatomic molecule

Infra red inactive molecule = homonuclear diatomic molecule
 Normal Modes of Vibration
The interactions of infrared radiation with matter may be
understood in terms of changes in molecular dipoles
associated with vibrations and rotations. In order to begin
with a basic model, a molecule can be looked upon as a
system of masses joined by bonds with spring-like
properties.

EXAMPLE

Taking first the simple case of diatomic molecules, such

molecules have three degrees of translational freedom and
two degrees of rotational freedom.
 The atoms in the molecules can also move relative to one
other, that is, bond lengths can vary or one atom can
move out of its present plane.

This is a description of stretching and bending

movements that are collectively referred to as vibrations.

For a diatomic molecule, only one vibration that

corresponds to the stretching and compression of the
bond is possible. This accounts for one degree of
vibrational freedom.
 Polyatomic molecules containing many (N) atoms will have
3N degrees of freedom.

Looking first at the case of molecules containing three

atoms, two groups of triatomic molecules may be
distinguished, i.e. linear and non-linear.

Two simple examples of linear and non-linear triatomics

are represented by CO2 and H2O
 Both CO2 and H2O have three degrees of translational
freedom.
Water has three degrees of rotational freedom, but the
linear molecule carbon dioxide has only two since no
detectable energy is involved in rotation around the O=C=O
axis.
Subtracting these from 3N, there are 3N5 degrees of
freedom for CO2 (or any linear molecule) and 3N6 for water
(or any non-linear molecule).
N in both examples is three, and so CO2 has four vibrational
modes and water has three.
The degrees of freedom for polyatomic molecules are
summarized in Table 1.1.
 A diatomic molecule has only one mode of vibration
which corresponds to a stretching motion.

A non-linear BAB type triatomic molecule has three

modes, two of which correspond to stretching motions,
with the remainder corresponding to a bending motion.

A linear type triatomic has four modes, two of which

have the same frequency, and are said to be degenerate.
 H2O: 3 fundamental vibrational modes 3N 3 3 = 3
 CO2: 4 fundamental vibrational modes 3N 3 2 = 4
 Vibrations can involve either a change in bond length
(stretching) or bond angle (bending) (Figure).

Some bonds can stretch in-phase (symmetrical stretching) or

out-of-phase (asymmetric stretching), as shown in Figure.

If a molecule has different terminal atoms such as HCN,

ClCN or ONCl, then the two stretching modes are no longer
symmetric and asymmetric vibrations of similar bonds, but
will have varying proportions of the stretching motion of
each group. In other words, the amount of coupling will vary.
 The IR Spectroscopic Process
1. The quantum mechanical energy levels observed in IR
spectroscopy are those of molecular vibration

2. We perceive this vibration as heat

3. When we say a covalent bond between two atoms is of a

certain length, we are citing an average because the bond
behaves as if it were a vibrating spring connecting the two
atoms

4. For a simple diatomic molecule, this model is easy to visualize:

5. There are two types of bond vibration:

Stretch Vibration or oscillation along the line of the bond

H H
C C
H H

symmetric asymmetric

Bend Vibration or oscillation not along the line of the bond

H H H H
C C C C
H H H
H

scissor rock twist wag

in plane out of plane
8. When a wave of infrared light encounters this oscillating EM
field generated by the oscillating dipole of the same frequency,
the two waves couple, and IR light is absorbed

9. The coupled wave now vibrates with twice the amplitude

IR beam from spectrometer

coupled wave

EM oscillating wave
from bond vibration
 Instrumentation
Dispersive Infrared Spectrometers
The first dispersive infrared
instruments employed prisms made of
materials such as sodium chloride.

The popularity of prism instruments

fell away in the 1960s when the
improved technology of grating
construction enabled cheap, good
quality gratings to be manufactured
Dispersion occurs when energy falling
on the entrance slit is collimated onto the
dispersive element and the dispersed
radiation is then reflected back to the exit
slit, beyond which lies the detector.

The dispersed spectrum is scanned across

the exit slit by rotating a suitable
component within the monochromator.

The widths of the entrance and exit slits

may be varied and programmed to
compensate for any variation of the source
energy with wavenumber.

In the absence of a sample, the detector

then receives radiation of approximately
constant energy as the spectrum is
scanned.
Atmospheric absorption by CO2 and H2O in
the instrument beam has to be considered in
the design of infrared instruments.

The spectrum of such atmospheric

absorptions occurs.

These contributions can be taken into account

by using a double-beam arrangement in which
radiation from a source is divided into two
beams.

These beams pass through a sample and a

reference path of the sample compartment,
respectively. The information from these
beams is rationed to obtain the required
sample spectrum.
A detector must have adequate sensitivity to
the radiation arriving from the sample and
monochromator over the entire spectral region
required.

In addition, the source must be sufficiently

intense over the wavenumber range and
transmittance range.

Sources of infrared emission have included the

Globar, which is constructed of silicon carbide.

There is also the Nernst filament, which is a

mixture of the oxides of zirconium, yttrium
and erbium.

A Nernst filament only conducts electricity at

elevated temperatures. Most detectors have
consisted of thermocouples of varying
characteristics.
 Limitations
The essential problem of the dispersive spectrometer lies with
its monochromator.

This contains narrow slits at the entrance and exit which limit
the wavenumber range of the radiation reaching the detector to
one resolution width.

Samples for which a very quick measurement is needed, for

example, in the eluant from a chromatography column, cannot
be studied with instruments of low sensitivity because they
cannot scan at speed.

However, these limitations may be overcome through the use of

a Fourier-transform infrared spectrometer.
Fourier-Transform Infrared Spectrometers

Fourier-transform infrared (FTIR) spectroscopy is based on the

idea of the interference of radiation between two beams to yield
an interferogram.

The latter is a signal produced as a function of the change of

pathlength between the two beams.

The two domains of distance and frequency are interconvertible

by the mathematical method of Fourier-transformation
 Source
The basic components of an FTIR
spectrometer are shown Interferometer
schematically in Figure.

The radiation emerging from the Sample

source is passed through an
interferometer to the sample before
reaching a detector. Detector

Upon amplification of the signal, in Amplifier

which high-frequency contributions
have been eliminated by a filter, the
data are converted to digital form by Analog to
an analog-to-digital converter and digital
transferred to the computer for converter
Fourier-transformation

Computer
Michelson Interferometers
The most common interferometer used in FTIR spectrometry is a
Michelson interferometer, which consists of two perpendicularly plane
mirrors, one of which can travel in a direction perpendicular to the plane.

A semi-reflecting film, the beamsplitter, bisects the planes of these two

mirrors.

The beamsplitter material has to be chosen according to the region to be

examined.

Materials such as germanium or iron oxide are coated onto an infrared-

transparent substrate such as potassium bromide or caesium iodide to
produce beamsplitters for the mid- or near-infrared regions.

Thin organic films, such as poly(ethylene terephthalate), are used in the

far-infrared region.
Sources
FTIR spectrometers use a Globar (Silicon Carbide) or Nernst source
(mixture of the oxides of zirconium, yttrium and erbium) for the mid-
infrared region.
If the far-infrared region is to be examined, then a high-pressure mercury
lamp can be used.
For the near-infrared, tungstenhalogen lamps are used as sources.

Detectors
There are two commonly used detectors employed for the mid-infrared
region. The normal detector for routine use is a deuterium tryglycine
sulfate (DTGS) in a temperature-resistant alkali halide window.
For more sensitive work, mercury cadmium telluride (MCT) can be used,
but this has to be cooled to liquid nitrogen temperatures.
In the far-infrared region, germanium or indiumantimony detectors are
employed, operating at liquid helium temperatures.
For the near-infrared region, the detectors used are generally lead sulfide
photoconductors.