Infrared Spectroscopy

Spectroscopy – Radiation Terminology

Wavenumber (ν)– the number of

waves in a unit of length or
distance per cycle - reciprocal of
the wavelength

ν = 1/λ Where: λ in cm

Wavenumber is directly proportional to

energy – higher number =higher energy

Spectroscopy – Radiation Terminology

Converting wavelength (µ
(µm ) into
wavenumber (cm-1) and reverse

cm-1 = 10,000/µm

µm = 10,000/cm-1

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 Infrared Spectroscopy
Region Wavelength Wavenumber
µm cm-1
Near 0.78 - 2.51 12800 – 4000
Middle 2.5 – 50 4000 – 200
Far 50 - 1000 200 – 10

The most useful IR region lies

between 2.5 to 15 µm or 4000 – 670 cm-1
Below 1500 cm-1 complex spectrum – Fingerprint for
molecule

IR - Applications

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 Infrared Spectroscopy

Low energy – vibrational and rotational states;

change in the dipole moment;
Polar molecules have regular fluctuation in
dipole moment
To interact - radiation frequency have to match
molecule vibrational frequency
When radiation is absorb it changes amplitude
of the molecular vibration
Similarly, the rotation of asymmetric
molecules occur

Infrared Spectroscopy

Rotational transitions – very low energy

required to cause change in rotational level –
corresponds to 100 cm-1 or less (>100 µm)
Gases produce in this region, far-
far-infrared,
discrete and well defined lines (absorption
maxima)
Liquid and solids – continuum; intramolecular
collisions and interactions

Vibrational Bending IR

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 Infrared Spectroscopy

Vibrational – Rotational Transitions

– energy required is within mid-
mid-infrared
region
– Spectrum of gases consists of a series of
closely spaced lines; that are many
rotational energy states for each
vibrational state

Infrared Spectroscopy

™ Rotation is restricted in liquids and

solids
– discrete vibrational/rotational
lines are not present;
- broadened vibrational peaks
only observed

Infrared Spectroscopy

Molecular Vibrations:
Vibrations:
Atoms in molecules fluctuate
continuously
Interaction in complex molecules

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 Infrared Spectroscopy

Vibrations:
Stretching – continuous change
in the distance between atoms
along the bond within
molecule
Bending – change in the angle
between two bonds; types:
scissoring, rocking, wagging
and twisting

Stretching IR

IR Spectroscopy - Absorption

s s
s
s
s

s
s

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 Mid-
Mid-range IR Spectra

Spectroscope Components

Absorption

Fluorescence
Phosphorescence
Scattering

Emission and chemiluminescence

Infrared Spectroscopy
Infrared Source:
™Usually inert solid material electrically heated to
1500 – 2200K; maximum radiation 5000 – 5900 cm-1
(2 to 1.7 µm)
™ Nernst Glower – rare earth oxides formed in to
cylinder – electrically heated to 1200K to
2200K; 1 – 9 µm
™ Globar Source – silicon carbide rod; heated to
1300K to 1500K; spectrum similar to Nernst
with higher energy at the 5 µm
™ Mercury arc – for spectrum > 50 µm
™ Tungsten Filament Lamp – near infrared 2.5 to 0.78
µm

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 Tungsten-
Tungsten-Halogen Lamps for NIR

Spectral Output of IR Radiation Sources

IR Radiation Sources

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 Spectroscopy – Radiation Source

IR – Nernst Glower Energy Spectrum

Radiation Distribution of IR Sources

Blackbody
Radiation
Characteristics

NIR

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 Infrared Spectroscopy

Infrared Transducers (Detectors)

¾ Thermal – thermocouples (10-6K);
bolometers (thermistors)

¾ Photoconducting – semiconductor layer

exposed to IR – change in resistance is
proportional to radiation. Lead sulfite,
cadmium tellurite, indium antimonide

Spectral Response of Various Semiconductor Detectors

Operating temperature in K

Infrared Spectroscopy
¾ Pyroelectric – temperature dependent
capacitors
- Dielectric material, pyroelectric
material such as triglycine sulfate
between electrodes
- One electrode is expose to IR radiation
- Change in temperature change charge
distribution in material and
current is measured
¾ Lasers – monochromatic radiation; tunable
CO2 laser emits at 1100 – 900 cm-1 –
pollution control

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 Spectroscopy – Radiation Source

Infrared Spectroscopy
Instrumentation:

Classic – dispersive – radiation from the

source is passed through the sample
focused on monochromator and dispersed
as continuous spectrum on detector;
difference in intensity is recorded:

T(%) = Is/IR x 100

™ peaks of absorbance

Monochromators

Prism and slit

Prism and filter
Grating and slit
Grating and filter

This type of equipment is called -

Dispersive spectrometer or
spectrophotometer

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 Spectrometers

CO2 and H2O – absorption in IR –

sealed optic compartment – filled or
flush continuously with dry nitrogen
Double beam systems to compensate
Single beam will provide erratic
spectra – humidity and temperature
Mirrors made of polished metals
For spectra moving grating or prisms
Only about 5% of current instruments
are dispersive type

FT – Fourier Transformed

Mathematical transformation
converting the signal measured as
function of time into a function of
reciprocal time – frequency – time
series
Fast algorithm available to apply
this transformation

Interferometer
We can measure the radiation intensity at all
wavelength simultaneously and can reconstruct
it in the form of intensity vs. wavelength
(spectrum). The wavelength have to be
encoded in a well-
well-defined manner as happen in
interferometer. Wavelength and their
corresponding intensities will overlap – the
overlap is used to plot spectrum.
In this case mathematical methods can be
applied to describe spectrum – Fourier analysis
- deconvoluting
An instrument that does this without a
monochromator is called a multiplex
instrument

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 Michelson Interferometer - FTIR
Mirror moves a distance Reference
equal to 1/4λ at constant
speed
ZPD
Zero
Pathlength
Difference

Wave Interaction in Interferometer

Radiation from
splitter Signal at detector
Fix and mobile mirrors
In Phase
are at equal distance from
Constructive
splitter or when the path
Interference
difference is integral
multiple of wavelength

Out of Phase
Mobile mirror moves 1/4λ
Destructive
and beam will be combined
Interference
1800 out of phase

Michelson Interferometer

As the mirror moves, detector sees signal as a

function of path length difference in the form
of cosine curve
The frequency of signal will be:

f = 2ν
2ν/λ
Where: f – frequency
ν – velocity of moving mirror
λ – wavelength of radiation

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 Interferometer
For monochromatic radiation a plot of the
signal (intensity) vs. difference in pathlength
form interferogram and is describe by cosine
function
The interferogram it is a record of the
interference signal at the detector – detector
response in time – time domain
If sample absorbs radiation at a specific
frequency – change of amplitude of
frequency will change

Interferometer Detector Signal

Sampling the Interferogram

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 Interferogram -

Infrared Spectroscopy

Fourier Transform (FTIR)

Advantage
– entire spectrum obtained within a few
milliseconds
– hundreds of complete spectra can be
obtained on a sample
– spectrometer is recording interferograms,
interferograms,
which are later deconvoluted
– Better signal to noise ratios obtained than
in dispersive instruments

Infrared Spectroscopy

Sample Handling
Gases – examined without
preparation; water have to be
eliminated (Pathlength up to 40m
used)

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 Reflectance Cell for IR

To extent radiation
pathlength and attenuate signal

Infrared Spectroscopy
Solid samples:
samples:
– used as solution in compatible solvent
(CCl4; CS2); variety of cells used made
from salts
– Pressed to pellet form with KBr –
scattering – particles; heat and moisture
sensitive material; salts selected based on
absorption – Cut off: KBr 400cm-1; CsI
200cm-1
– Mulling – dispersing substance in small
amount of mineral oil (Nujol
(Nujol)) or
fluorinated hydrocarbons (mull). Mixture
is placed between plates of the cell

Pellet Sample Die for IR

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 IR – Sample Holder

Liquid sample
Cuvette
Card

IR Cuvette

Spectral Cards Absorption Spectra

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 IR – Solvents Limitation
Horizontal Lines Indicates Useful Region

IR Optics Materials – Mid IR

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 Infrared Spectroscopy - Patterns

Infrared Spectroscopy

Coupling of vibrations - bonds at

singular central atom – change in the
characteristics of vibrations

Mid-
Mid-Range IR Spectra

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 Michelson Interferometer

Solvents Properties for IR

Infrared Spectroscopy

™ Instrumentation - Fourier transform

™ Interference pattern – interferogram –
complex waveform that contains
information about all frequencies in the
measured infrared region. Using
mathematical operation termed a Fourier
transform to deconvolute the interferogram
to produce a spectrum in frequency domain;
the same as in dispersive spectrometer

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Interferogram Formation

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