VIBRATIONAL SPECTROSCOPY

Infrared spectroscopy (IR spectroscopy or Vibrational Spectroscopy) involves the

interaction of infrared radiation with matter. It covers a range of techniques, mostly
based on absorption spectroscopy. As with all spectroscopic techniques, it can be
used to identify and study chemicals. Sample may be solid, liquid, or gas. The
method or technique of infrared spectroscopy is conducted with an instrument
called an infrared spectrometer (or spectrophotometer) to produce an infrared
spectrum. An IR spectrum is essentially a graph of infrared light absorbance (or
transmittance) on the vertical axis vs. frequency or wavelength on the horizontal
axis. Typical units of frequency used in IR spectra are reciprocal
centimeters (sometimes called wave numbers), with the symbol cm −1. Units of IR
wavelength are commonly given in micrometers (formerly called "microns"), symbol
μm, which are related to wave numbers in a reciprocal way. A common laboratory
instrument that uses this technique is a Fourier transform infrared
(FTIR) spectrometer.
The infrared portion of the electromagnetic spectrum is usually divided into three
regions; the near-, mid- and far- infrared, named for their relation to the visible
spectrum. The higher-energy near-IR, approximately 14000–4000 cm −1 (0.8–2.5 μm
wavelength) can excite overtone or harmonic vibrations. The mid-infrared,
approximately 4000–400 cm−1(2.5–25 μm) may be used to study the fundamental
vibrations and associated rotational-vibrational structure. The far-infrared,
approximately 400–10 cm−1 (25–1000 μm), lying adjacent to the microwave region,
has low energy and may be used for rotational spectroscopy. The names and
classifications of these subregions are conventions, and are only loosely based on
the relative molecular or electromagnetic properties. The main region of interest for
analytical purposes is from 2.5 to 25µm (micrometres), i.e. 4000 to 400
wavenumbers(waves per centimetre, cm-1).
Normal optical materials such as glass or quartz absorb strongly in the infrared, So
instruments for carrying our measurements in this region differ from those used for
the electronic(visible/ultraviolet) region. Infrared
spectroscopy exploits the fact that molecules absorb frequencies that are
characteristic of their structure. These absorptions occur at resonant frequencies, i.e.
the frequency of the absorbed radiation matches the vibrational frequency. The
energies are affected by the shape of the molecular potential energy surfaces, the
masses of the atoms, and the associated vibronic coupling. Vibronic coupling (also
called nonadiabatic coupling or derivative coupling) in a molecule involves the
interaction between electronic and nuclear vibrational motion. The term "vibronic"
originates from the combination of the terms "vibrational" and "electronic". The word
coupling denotes the idea that in a molecule, vibrational and electronic interactions
are interrelated and influence each other, and the magnitude of vibronic coupling
reflects the degree of such interrelation.
In order for a vibrational mode in a sample to be "IR active", it must be associated
with changes in the dipole moment. A permanent dipole is not necessary, as the rule
requires only a change in dipole moment. A molecule can vibrate in many ways, and
each way is called a vibrational mode. For molecules with N number of atoms, linear
molecules have 3N – 5 degrees of vibrational modes, whereas nonlinear molecules
have 3N – 6 degrees of vibrational modes (also called vibrational degrees of
freedom). As an example H2O, a non-linear molecule, will have 3 × 3 – 6 = 3 degrees
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of vibrational freedom, or modes. Simple diatomic molecules have only one bond
and only one vibrational band. If the molecule is symmetrical, e.g. N 2, the band is not
observed in the IR spectrum, but only in the Raman spectrum. Asymmetrical
diatomic molecules, e.g. CO, absorb in the IR spectrum. More complex molecules
have many bonds, and their vibrational spectra are correspondingly more complex,
i.e. big molecules have many peaks in their IR spectra. The atoms in a CH 2X2 group,
commonly found in organic compounds and where X can represent any other atom,
can vibrate in nine different ways. Six of these vibrations involve only
the CH2 portion: symmetric and antisymmetric rocking, wagging and twisting, as
shown below. Structures that do not have the two additional X groups attached have
fewer modes because some modes are defined by specific relationships to those
other attached groups. For example, in water, the rocking, wagging, and twisting
modes do not exist because these types of motions of the H represent simple
rotation of the whole molecule rather than vibrations within it. The infrared spectrum
of a sample is recorded by passing a beam of infrared light through the sample.
When the frequency of the IR is the same as the vibrational frequency of a bond or
collection of bonds, absorption occurs. Examination of the transmitted light reveals
how much energy was absorbed at each frequency (or wavelength). This
measurement can be achieved by scanning the wavelength range using a
monochromator. Alternatively, the entire wavelength range is measured using a
Fourier transform instrument and then a transmittance or absorbance spectrum is
generated using a dedicated procedure.
Fourier transform infrared (FTIR) spectroscopy is a measurement technique that
allows one to record infrared spectra. Infrared light is guided through an
interferometer and then through the sample (or vice versa). A moving mirror
inside the apparatus alters the distribution of infrared light that passes through the
interferometer. The signal directly recorded, called an "interferogram", represents
light output as a function of mirror position. A data-processing technique called
Fourier transform turns this raw data into the desired result (the sample's
spectrum): Light output as a function of infrared wavelength (or equivalently,
wavenumber). As described above, the sample's spectrum is always compared to
a reference.

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Schematics of a two
-beam absorption spectrometer. A beam of infrared light is produced, passed
through aninterferometer
(not shown),and then split into two separate beams. One is passed through
the sample, the other passed through a reference. The beams are both reflected back towards a
detector, however first they pass through a splitter, which quickly alternates which ofs the two beam
enters the detector. The two signals are then compared and a printout is obtained. -beam"
This "two
setup gives accurate spectra even if the intensity of the light source drifts over time.
The normal instrumental process is as follows:
1. The Source: Infrared energy is emitted from a glowing black-body source. This
beam passes through an aperture which controls the amount of energy presented to
the sample (and, ultimately, to the detector). The main sources of infrared radiation
used in spectrophotometers are
(1) A nichrome wire wound on a ceramic support,
(2) the Nernst glower, which is a filament containing zirconium, thorium and cerium
oxides held together by a binder,
(3) the Globar,a bonded silicon carbide rod. These are heated electrically to
temperatures within the range1200-2000°C when they will glow and produce the
infrared radiation approximating to that of a black body.
2. Interferometer: The beam enters the interferometer where the “spectral
encoding” takes place. The resulting interferogram signal then exits the
interferometer.
3. Sample: The beam enters the sample compartment where it is transmitted
through or reflected off of the surface of the sample, depending on the type of
analysis being accomplished. This is where specific frequencies of energy, which are
uniquely characteristic of the sample, are absorbed.
4. Detector: The beam finally passes to the detector for final measurement. The
detectors used are specially designed to measure the special interferogram signal.
A range of detectors is available for this purpose, the type used in any particular
instrument depending upon the type and quality of the spectrophotometer.
i. The thermocouple is made by welding together two wires of metals 1 and 2 in
such a manner that a segment of metal 1 is connected to two terminal wires of metal
2. One junction between metals 1 and 2 is heated by the infrared beam, and the
other junction is kept at constant temperature: small changes in ambient temperature
are thus minimised. To avoid losses of energy by convection, the couples are
enclosed in an evacuated vessel with a window transparent to infrared radiation. The
metallic junctions are also covered with a black deposit to decrease reflection of the
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incident beam A bolometer is essentially a thin blackened platinum strip in an
evacuated glass vessel with a window transparent to the infrared rays: it is
connected as one arm of a Wheatstone bridge, and any radiation absorbed raises
the temperature of the strip and changes its resistance. Two identical elements are
usually placed in the opposite arms of a bridge;one of the elements is in the path of
the infrared beam and the other compensates for variations in ambient temperature.
Both the above receptors give a very small direct current,which may be amplified by
special methods to drive a recorder.
ii.The Golay pneumatic detector, which is sometimes used, consists of a gas-filled
chamber which undergoes a pressure rise when heated by radiant energy. Small
pressure changes cause deflections of one wall of the chamber;' this movable wall
also functions as a mirror and reflects a light beam directed upon it to a photocell, the
amount of light reflected bearing a direct relation to the gas-chamber expansion, and
hence to the radiant energy of the light from the monochromator. This detector
responds to the total light energy received as distinct from energy received per unit
area (thermocouples and bolometers).
Iii. The pyroelectric detectors fitted in many modern instruments use ferroelectric
Materials operating below their Curie-point temperatures. When infrared Radiation is
incident on the detector there is a change in polarisation which can be employed to
produce an electrical signal. The detector will only produce a signal when the
intensity of the incident radiation changes. These detectors are of a special value in
FT-IR where rapid response times are needed and for this purpose they use
deuterium triglycine sulphate as the detecting medium in an evacuated chamber.
5. Computer: The measured signal is digitized and sent to the computer where the
Fourier transformation takes place. The final infrared spectrum is then presented to
the user for interpretation and any further manipulation.
IR spectroscopy is often used to identify structures because functional groups give rise to
characteristic bands both in terms of intensity and position (frequency). The positions of
these bands are summarized in correlation tables as shown below.

Wavenumbers listed in cm−1.

Sample preparation
1. Gaseous samples require a sample cell with a long pathlength to compensate for
the diluteness. The pathlength of the sample cell depends on the concentration of
the compound of interest. A simple glass tube with length of 5 to 10 cm equipped
with infrared-transparent windows at the both ends of the tube can be used for
concentrations down to several hundred ppm. Sample gas concentrations well
below ppm can be measured with a White's cell in which the infrared light is
guided with mirrors to travel through the gas. White's cells are available with
optical pathlength starting from 0.5 m up to hundred meters.
2. Liquid samples can be sandwiched between two plates of a salt
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(commonly sodium chloride, or common salt, although a number of other salts such
as potassium bromide or calcium fluoride are also used). The plates are transparent
to the infrared light and do not introduce any lines onto the spectra.
3. Solid samples can be prepared in a variety of ways. One common method is to
crush the sample with an oily mulling agent (usually mineral oil Nujol). A thin film
of the mull is applied onto salt plates and measured. The second method is to
grind a quantity of the sample with a specially purified salt (usually potassium
bromide) finely
(to remove scattering effects from large crystals).
This powder mixture is then pressed in a mechanical press to form a translucent
pellet through which the beam of the spectrometer can pass. A third technique is the
"cast film" technique, which is used mainly for polymeric materials. The sample is
first dissolved in a suitable, non-hygroscopic solvent. A drop of this solution is
deposited on surface of KBr or NaCl cell. The solution is then evaporated to dryness
and the film formed on the cell is analysed directly. Care is important to ensure that
the film is not too thick otherwise light cannot pass through. This technique is
suitable for qualitative analysis. The final method is to use microtomy to cut a thin
(20–100 µm) film from a solid sample. This is one of the most important ways of
analysing failed plastic products for example because the integrity of the solid is
preserved.
Uses and applications
Infrared spectroscopy is a simple and reliable technique widely used in both organic
and inorganic chemistry, in research and industry. It is used in quality control,
dynamic measurement, and monitoring applications such as the long-term
unattended measurement of CO2 concentrations in greenhouses and growth
chambers by infrared gas analyzers.
It is also used in forensic analysis in both criminal and civil cases, for example in
identifying polymer degradation. It can be used in determining the blood alcohol
content of a suspected drunk driver.
IR-spectroscopy has been successfully used in analysis and identification of
pigments in paintings and other art objects such as illuminated manuscripts.
Infrared spectroscopy is also useful in measuring the degree of polymerization in
polymer manufacture. Changes in the character or quantity of a particular bond are
assessed by measuring at a specific frequency over time.
Infrared spectroscopy has also been successfully utilized in the field of
semiconductor microelectronics: for example, infrared spectroscopy can be applied
to semiconductors like silicon, gallium arsenide, gallium nitride, zinc selenide,
amorphous silicon, silicon nitride, etc.
Another important application of Infrared Spectroscopy is in the food industry to
measure the concentration of various compounds in different food products.
NB: vibrational spectroscopy is used for identification, characterisation, structure
elucidation, reaction monitoring, quality control, and quality assurance.
EXP 1: liquid capillary film
- In this technique, a drop of the liquid sample is pressed between sodium chloride
plates to produce a film of liquid with a thickness of 0.01mm or less, the plates being
held together by capillary forces.

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– the prepared plates are placed in the demountable cell holder, ensuring that the
gaskets are properly located and the quick release nuts are firmly screwed down
( but not too tightly , otherwise the liquid will exude from between the plates.
– The whole assembly is then in the sample beam path of the infrared
spectrophotometer.
- Obtain and identify the infrared spectra of the liquid samples provided.
EXP 2: Solid samples
- Weigh out 1mg of sample using analytical balance and grind thoroughly using
agate motar and pestle.
- 3mg powder potassium bromide and finally and finely powder the mixture, ensuring
uniform dispersion of the sample throughout the whole mass is attained.
- the mixture into a special dye and subject to pressure under vacuum. The disc so
produced is mounted directly in the sample beam path of the spectrophotometer and
the spectrum recorded.
- Obtain and identify the infrared spectra of the solid samples provided.

Compiled by E. Waithira,