1

INFRARED SPECTROSCOPY
SECTION A
IR REGION OF THE SPECTRUM AND UNITS
C

this IR region of the spectrum ranges from the end of the visible region (red @ ~ 780
nm) to about 1,000,000nm. In wave numbers, this is from ~ 12800 - 10 cm-1

three main process occur: emission, absorption reflection, due to the transition of
molecules from one vibrational or rotational energy state to another

the region is divided into three main sub-regions as follows:

Region

l range
(mm)

wave number (n or s)
(cm-1)

Near-IR
Mid-IR
Far-IR

0.78 - 2.5
2.5 - 50
50 - 1000

12800 - 4000
4000 - 200
200 - 10

Most used
region

2.5 - 15

4000 - 670

a linear wave number scale is used (usually) in IR spectroscopy because of the

direct relationship between wave number (s) and both energy (E) and frequency (n)
s = 1/l cm-1
and,

E = hc/l = hn

the energy of the transitions are low and are associated with vibrational and
rotational transitions

TYPES OF MOLECULAR TRANSITIONS

C

the relative positions of atoms in a molecule are not fixed but fluctuate continuously
due to different types of vibrations and rotations about the bonds in the molecule.

there are two types of vibrations

i) stretching (see overhead)
ii) bending (see overhead)

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41

energy
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the number of possible vibrations and rotations for a given molecule is related to the
number of atoms, and thus the number of bonds in the molecule

for a simple diatomic or tri-atomic molecule it is easy to define the number and
nature of these vibrations, but for larger molecules this is not easily done

thus, for most molecules, there is a multiple of quantized rotational and vibrational
levels associated with its bonds

all of the vibrations discussed can occur in a simple molecule (< 2 atoms)

in addition, interaction or coupling of vibrations can occur if the vibrations involve

bonds to a single central atom because of changes in the characteristics of the
vibrations involved

VIBRATIONAL MODES - Number of Possible Vibrations

C

to describe the motion of a molecule in space, the following have to be considered:

1. translational motion
- 3 degrees of freedom ( 3 coordinates in space)
2. rotation about its centre of gravity
- 3 degrees of freedom
3. vibrational motion
- (3N - 6) degrees of freedom for non-linear molecules, where N = no. of atoms
- (3N - 5) degrees of freedom for a linear molecule (rotation about its axis is not
counted)

for each normal mode of vibration there is a potential energy relationship

.iS{,r
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41

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3
DIPOLE CHANGES
Vibration
C in order to absorb energy, a molecule must undergo a net change in dipole moment
due to its vibrational and/or rotational motions
C under these condition, the alternating electrical field of the radiation interacts with
the molecule and a transfer of energy occurs causing a change in the amplitude of
one of the motions of the molecule
C through this process, molecules absorb IR radiation and are promoted to a higher
vibrational energy level
C the absorption of energy is quantized and corresponds to the mid-IR region of the
spectrum
Rotation
C rotation of molecules around their centre of mass also results in a periodic dipole
fluctuation that can interact with radiation < 100 cm-1 , i.e., > 100 mm
homonuclear and chiral molecules
C homonuclear molecules, e.g., O2, Cl2. N2 and chiral molecules in the crystalline state
have no net change in dipole moment during their vibration or rotation, thus these
molecules cannot absorb IR radiation
Note: chiral molecules - molecules that have non-superimposable mirror images
gases, liquids, solids
C absorption spectra by gases show discrete, well-defined rotational and vibrational
absorption lines
C in liquids and solids, intramolecular collisions and interactions cause broadening of
rotational and vibrational lines into a continuum, leaving only broadened vibrational
peaks or bands

4
SECTION B
IR instrumentation
-

three types: 1. Dispersive grating spectrophotometer

2. Multiplexed instruments, e.g., Fourier transform IR
3. Non-dispersive photometers

common to all three types: 1.

2.
3.

Source of e.m.r.
Optical materials
Detectors

1. Sources - several different sources

- some are specific for use in each IR region
I)

Nernst Glower - small cylinder (~ 1 -2 mm in diameter and ~ 20 mm in length)

made of rare earth oxides (e.g., ZrO2 and Y2O3) with platinum
leads attached to each end of the cylinder
- a current is passed through the device and temperatures of
1200 K to 2200 K occur
- the device emits black body radiation
- has a large negative temperature coefficient of resistance
(i.e., resistance decreases with increasing temperature), thus
it has to be externally heated to a dull red heat before the
current is large enough to maintain the desired temperature
- useful in the near- and mid-IR regions; not used in the far-IR
region

ii)

Globar

iii) Incandescent
wire

- is a silicon carbide rod (~ 5mm diameter and ~ 50 mm in

length) that is electrically heated (1300 - 1500 K)
- has a positive temperature coefficient of resistance (an
advantage)
- the electrical contacts have to be water-cooled to prevent
arcing
- the spectral outputs of the Nernst Glower and the Globar are
similar, except at wavelengths < 5 um the Globar provides a
significantly greater output
- useful in the near-, mid-IR, and far-IR regions

- a tightly wound nichrome wire that is electrically heated to ~

1100 K
- has a lower intensity than both the Nernst Glower and the
Globar
- has longer life than both the Nernst Glower and the Globar
- a rhodium wire heater sealed in a ceramic cylinder has
similar properties.

5
iv) Mercury Arc

v)

Tungsten
filament

vi) CO2 Laser

2. Optical Materials

- a high pressure mercury arc lamp provides sufficient radiant

energy in the far-IR region (none of the above sources do)
- consists of mercury vapour at a high pressure (> 1 Atm.) in a
quartz tube
- on passage of a current a plasma is formed. This excites the
Hg atoms and leads to emission in the far-Ir region of the
spectrum

- an ordinary tungsten filament bulb may be used as an IR

source in the near-IR region of the spectrum (0.78 - 2.5 um)
- a tuneable CO2 laser may be used as an IR source in the
region 900 - 1100 cm-1 (11 - 9 um)

- IR instruments require the use of several optical components.

All such components, e.g., mirrors including focusing and
gratings are made front surface reflecting
- sample holders and cell windows are made from materials
transparent to IR radiation
- near IR - fused silica or quartz, silicate glass, NaCl, KBr,
LiF, TlBr, TlI
- mid-IR - NaCl, KBr, TlBr, TlI, ZnSe
- far-IR - KBr, TlBr, TlI

3. Sampling Methods - capillary film (KBr or NaCl disks used)

- cast film (sample dissolved in a volatile solvent, placed on
KBr disk and solvent evaporated)
- Nujol mull (useful for samples that are insoluble; use ~0.02 g
of sample ground together with 1 -2 drops of the mineral oil;
the resulting mull is placed between NaCl or KBr disks)
- KBr pellet (~0.002 - 0.004 g of sample ground with ~ 0.2 g
KBr, ground and pressed into a disk)
- sealed liquid cells
- gas cells
Note: 1. samples must be dry to prevent etching of the
inorganic crystalline materials
2. Solvents must have few IR bands, e.g., carbon
tetrachloride (CCl4), chloroform (CHCl3), carbon
disulphide (CS2)

6
4. Detectors
- three types 1. thermal
2. pyroelectric
3. photo-conducting

1. Thermal detectors
- responses depend on the heating effects of radiation on different materials
- three main types: I) thermocouple
ii) bolometer
iii) Golay tube (pneumatic)
- mechanism - radiation is absorbed by a small black body, the
temperature of the body rises, and the rise in temperature
is measured
- temperature rises are small (a few thousandths of a Kelvin)
- requirements - absorbing element must be small
- heat capacity must be small
- all radiation must be focused on the absorbing element
- other - thermal noise from the surroundings is a problem
- the detector is housed in a vacuum and shielded from other
thermal noises
- the beam of radiation is chopped so that it can be detected apart
from extraneous noise

I) thermocouple (see figure 1)

- composed of two dissimilar metal wires (e.g., bismuth, antimony) welded
together at two junctions
- one junction is bonded to a heat sink that is shielded from the incident
radiation, and the junction thus remains at a constant temperature
- the other junction is placed in the radiation beam to be detected. A small
piece of blackened gold foil is usually attached to this junction in order to
collect as much of the radiant energy as possible
- a small voltage develops between the two thermocouple junctions. The
magnitude of this voltage depends on the temperature difference between
the junctions (can respond to temperature differences of 10-6 K)
- the incident radiation is chopped to reduce interference from other heat
sources
- to minimize conductive heat losses the entire assembly is sealed in an
evacuated housing that has an IR transmitting window
- several thermocouples may be linked together, in series, to form a
thermopile - provides better sensitivity

7
ii) bolometer (see figure 2)
-

iii)

is a device whose electrical resistance changes with temperature (i.e., it is a

resistance thermometer)
two types where the sensing elements are made from different materials:
a) - made from strips of Pt (0.4% change/oC) or Ni
b) - made from a semi-conductor material, e.g., the oxides of Ni, Co, or Mn
(that have high temperature coefficient of resistances ~ 4 - 7%
change/oC)
- called thermistors
- heat excites electrons from the valence band to the conducting
band
the responsive element is kept small and blackened to absorb the radiant heat
two matching sensing elements (filaments or thermistors) are placed in the
two opposing arms of a Wheatstone Bridge circuit to carry-out the
measurement

Golay or Pneumatic detector (see figure 3)

- based on the absorption of IR radiation by an inert gas and its subsequent
volume expansion
- IR radiation is absorbed by the blackened metal plate and this absorbed
energy causes the temperature of the metal plate to rise
- the increase in the plate temperature increases the temperature of the inert
gas within the detector.
- as the temperature of the gas increases, the gas expands causing
distortion/flexing of the flexible diaphragm
- this distortion of the thin metal diaphragm can be measured by:
a) an optical system in which a light beam is reflected to a phototube, or
b) making it one plate of a dynamic parallel-plate capacitor. The distortion
of the flexible diaphragm relative to the fixed plate, changes the
average plate separation and thus its capacitance
- sensitivity - equal to that of a thermistor in the near- and mid-IR regions (not
often used in this region; useful in the far-IR region, below 200 cm-1)

2. Pyro-electric detector (see figure 4)

-

Certain crystals, e.g., triglycine sulphate (TGS), deuterated tri glycine sulphate
(DTGS), lithium tantalate, etc., have an internal electric polarization along an
axis resulting from alignment of electric dipole moments
such crystals are known as ferroelectric materials (in a ferro-electric material,
the dipole moments remain aligned in the absence of an external electric field.
This gives the material a permanent electric polarization. One face of the
crystal is positive and the other negative. This polarization is temperature
dependent)
when these crystals absorb IR radiation, they heat up. This alters the lattice
spacings of the crystals which, in turn, causes a change in the electric
polarization
if placed between electrodes consisting of metal plates connected through an
external circuit, current will flow in the circuit to balance this charge
redistribution

8
-

the pyro-electric effect depends on the rate of change of temperature, not on

its absolute value
it therefore responds only to modulated radiation (not to slowly varying
background radiation)
this detector has a very fast response time and thus is used widely in Fourier
transform instruments (FTIR).

3. Photo-conducting detector
- consists of a thin film of semi-conductor material (e.g., lead sulphide,
mercury/cadmium telluride, indium antimonide. Lead telluride, or germanium
doped with copper or lead) deposited on a non-conducting glass and sealed in an
evacuated envelope to protect the semi-conductor from reaction with the
atmosphere.
- when IR radiation is absorbed by these materials some of the electrons in the
bound non-conducting valence levels are promoted to a higher energy conducting
state, resulting in a decrease in the resistance of the material.
- the photo-conductor is placed in series with a voltage source and a load resistor,
and the voltage drop across the load resister is measured - this is a measure of
the power of the IR beam of radiation.
- the lead sulphide photo-conductor detector is used widely in the near-IR (1 - 3
um, 10,000 -333 cm-1) region. It can be used at room temperature.
- the mercury/cadmium telluride photo-conductivity detector is used in the mid- and
far-IR regions.
- must be cooled in liquid nitrogen (77 K) to minimize thermal noise
- it has fast response times
- useful for Fourier Transform IR instruments

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SECTION C
1. Dispersive IR Spectrophotometer (see figure 5)
- double-beam, recording instruments, that use reflection gratings for dispersion
- double-beam

- less demanding with respect to source and detector

performance
- low intensity sources
- low sensitivity detectors
- need for large signal amplification
- atmospheric H2O and CO2 absorb in some important spectral
regions
- a double-beam instrument compensates for this absorption
signal chopping - at low frequency (5 - 13 cps)
- permits the detector to discriminate between the analyte
signal and extraneous signals
- low chopping rates required because of slow response
times of most IR detectors
- used in most IR dispersive instruments
optical design and
and configuration - similar to UV/VIS spectrophotometers
- sample compartment is located between the source and the
monochromator
- IR radiation (unlike UV radiation) is not energetic enough to
degrade (photo-chemical decomposition) the sample
- most scatter radiation generated within the cell is removed
by the monochromator
null type detector - the power of the reference beam is attenuated (reduced)
with a comb device
- the teeth of the comb are tapered so that there is a linear
relationship between the lateral movement of the comb and
the decrease in power of the beam of radiation
- when the detector senses a difference in the power of the
two beams (the analyte and the reference), the system
drives the comb to restore the null condition
- this movement is synchronized with the pen recorder so that
its position gives a measure of the transmittance of the
sample
limitations
- the reference beam attenuator system has three main
limitations:
1. the response of the attenuator always lags behind the
transmittance changes as they occur in real time,
particularly when scanning in regions where the signal is
changing rapidly
2. the momentum associated with the mechanical
attenuator and recorder system may result in the pen
drive overshooting the true transmittance
3. when the transmittance approaches zero, almost no
radiation reaches the detector, and the exact null position
cannot be established accurately - results in sluggish
detector response and rounded peaks

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10
2. Interferometric (multiplexed) Spectrometers
- two main types:
I) Fourier transform
ii) Hadamard transform (not widely used)
I) Fourier Transform Spectrometer (see figure 6)
- may be based on several types of optical systems
- will describe the Michelson interferometer (most widely used)
- consists of two plane mirrors (one fixed and the other moveable) set at right
angles to each other, with a beam splitter at 45o to the mirrors
- modulated light from the source is collimated and passed to the beam splitter
where one-half of the beam is reflected to the fixed mirror and the other onehalf passes through to the moving mirror
- when the mirrors are positioned such that the optical path lengths of the
reflected and transmitted beams are the same when they return to the beam
splitter, they will interact constructively
- if the moveable mirror is displaced 1/4 of a wavelength, when the beams return
to the beam splitter there will be a difference of -wavelength in their path
lengths, i.e., they will be 180o out of phase, and they will interact destructively
- if the moveable mirror is displaced another 1/4 of a wavelength, i.e., a total
displacement of of a wavelength, when the beams return to the beam
splitter there will be a difference of one wavelength in their path lengths, i.e.,
they will be in phase, and they will interact constructively
- as the mirror continues to move, there will be a series of constructive and
destructive interference patterns for each 1/4 wavelength displacement of the
mirror
- when the interferometer is illuminated by monochromatic radiation of
wavelength L, and the mirror moves at a velocity v , the signal from the
detector has a frequency, f=2v/L
- a plot of signal versus mirror distance is a cosine wave

- when several wavelengths of radiation, i.e., polychromatic radiation, are

incident on the interferometer, each wavelength puts out a unique cosine wave
- the total signal observed is thus the sum of all the cosine waves
- this is called the Fourier Transform of the spectrum
- the actual spectrum is them obtained by using an appropriate inverse
transformation of the spectrum
- data reduction requires digital computer techniques, and analogue conversion
devices
- the speed and position of the mirror has to be known accurately
- a line from a laser source is used to produce a discrete signal, which is then
time-locked to the motion of the mirror, and hence to the interferogram

11
Advantages -

signal/noise ratios are better than with dispersive IR instruments

low to moderate costs, comparable to dispersive devices
rapid scanning of the spectrum
high resolution
highly accurate and reproducible frequencies - important when
spectra are to be subtracted for background correction
- optics provide much larger energy throughput than dispersive
instruments

Disadvantage - requires a fast response detector - lower sensitivity

Application -

high resolution work

analysis of samples of high absorbance and weak absorbance
useful for kinetic studies
small samples
reflection and emission studies

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12
3. Non-Dispersive IR Photometers
- no monochromator (dispersive device) is used for wavelength discrimination
- several types:

- simple filter
- filter wedges - provides the entire spectrum
- no wavelength selection device
- the instruments are simple, rugged, easy to use and maintain, and costs are low
- used for quantitative analysis
- Non-Filter Photometer (see figure 7)
- no wavelength-restricting device is used
- widely used to monitor gas streams for a single component, e.g., CO2 in
automobile exhaust gases
- reference cell - filled with a non-absorbing gas
- sample cell - same length as the reference cell
- sample flows through the cell
- chopping
- beams from identical sources are chopped (~ 5 cps)
simultaneously
- serves to provide a modulated signal which, reduces the effect
of extraneous noise, and is less sensitive to drift and
1/frequency noise
- an attenuator is used to equalize the response of the sensors when both
reference and sample cells contain the same non-absorbing gas
- when an IR absorbing gas, e.g., CO2, is present in the sample cell, it absorbs
radiation and the radiation reaching the sensor in the sample beam path is
reduced
- the difference between the radiation reaching the sensor in the reference
beam path and the sample beam path is measured and corresponds to the
amount/concentration of the absorbing gas in the sample cell
- the sensors can be of several types - two widely used sensors are a thermal
sensor and a pneumatic sensor
- in this instrument the sensors act as the discriminating device

13
SECTION D
Attenuated Total Reflection (ATR)
-

when a beam of radiation enters a plate or prism, it will be reflected internally if the
angle of incidence at the interface between sample and plate is greater than the
critical angle (a function of refractive index)
on internal reflection all of the energy of the beam of radiation is reflected
the beam, however appears to penetrate slightly (from a fraction of a wavelength to
several wavelengths) beyond the reflecting surface, and before returning
if a material that can absorb IR radiation is placed on the reflecting surface, it will
absorb IR radiation thus reducing (attenuating) the intensity of the returning beam of
radiation
this attenuated radiation when measured and plotted against wavelength, gives an
absorbance spectrum that is, in fact, the IR spectrum of the material
reflection crystals used in ATR must have a high index of refraction, e.g. AgCl
applications - samples that - cannot be studied by normal transmission methods
- have very strong absorption
- resist preparation as thin films
- are non-transparent
- contain suspended matter
- aqueous solutions can be analysed without having to compensate for
very strong absorption (due to water)