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Infrared (IR) Spectroscopy: Absorption
Infrared (IR) Spectroscopy: Absorption
Another unit commonly used is the wavenumber, which is linear with energy:
Work by Einstein, Planck and Bohr indicated that electromagnetic radiation can be
regarded as a stream of particles or quanta, for which the energy is given by the
Bohr equation:
The Electromagnetic Spectrum
Infrared region
LIMIT OF RED LIGHT: 800 nm, 0.8 m, 12500 cm-1
NEAR INFRARED: 0.8 -2.5 m, 12500 - 4000 cm-1
MID INFRARED: 2.5 - 50 m, 4000 - 200 cm-1
FAR INFRARED: 50 - 1000 m, 200 - 10 cm-1
Using this potential energy function in the Schrdinger equation, the vibrational
frequency can be calculated:
The vibrational spectra appear as bands rather than lines. When vibrational
spectra of gaseous diatomic molecules are observed under high-resolution
conditions, each band can be found to contain a large number of closely
spaced components band spectra. The structure observed is due to that a
single vibrational energy change is accompanied by a number of rotational
energy changes. The form of such a vibration-rotation spectrum can be
predicted from the energy levels of a vibrating-rotating molecule.
> vibrational-rotational bands
P R
Fundamental Vibrations
Vibration Types
IR SAMPLE SAMPLE*
(MOLECULE, GS) (VIB.)
Selection Rules
The energy associated with a quantum of light may be transferred to the
molecule if work can be performed on the molecule in the form of
displacement of charge.
Selection rule:
A molecule will absorb infrared radiation if the change in vibrational
states is associated with a change in the dipole moment ( ) of the
molecule.
= qr
q: electrical charge, r: directed distance of that charge from some
defined origin of coordinates from the molecule.
Dipole moment is greater when electronegativity difference between the
atoms in a bond is greater. Some electronegativity values are:
H 2.2; C 2.55; N 3.04; O 3.44; F 3.98; P 2.19; S 2.58; Cl 3.16
Vibrations which do not change the dipole moment are Infrared Inactive
(homonuclear diatomics).
Why not 3N-6/3N-5 bands in IR spectrum?
The theoretical number of fundamental vibrations (absorption
frequencies) will seldom be observed
> overtones (multiples of a given frequency), combination (sum of
two other vibrations) or difference (the difference of two other
vibrations) tones increase the number of bands
> the following effects will reduce the number of theoretical
bands:
frequencies which fall outside the measured spectral region (400-
4000 cm 1 )
bands which are too weak
bands are too close and coalesce
occurrence of a degenerate band from several absorptions of the
same frequency
lack of change in molecular dipole
Infrared Spectrum
of Carbon Dioxide
Vibrational Modes for a CH2 Group
Absorption Regions Irtutord.exe
Group frequencies
With certain functional or structural groups, it has been found
that their vibrational frequencies are nearly independent of the
rest of the molecule group frequencies.
Carbonyl group 1650 to 1740 cm-1 various aldehydes and ketones
T transmission / transmittance
A = -log T
A absorbance (no units)
B
(both spectra are
recorded with the same
sample)
Instrumentation
Perkin ElmerTM
Spectrum One
BRUKE TENSORTM
Series
Dispersive instruments: with a monochromator to be used in
the mid-IR region for spectral scanning and quantitative
analysis.
Fourier transform IR (FTIR) systems: widely applied and
quite popular in the far-IR and mid-IR spectrometry.
Nondispersive instruments: use filters for wavelength
selection or an infrared-absorbing gas in the detection system
for the analysis of gas at specific wavelength.
Dispersive IR spectrophotometers
Modern dispersive IR spectrophotometers are invariably double-beam
instruments, but many allow single-beam operation via a front-panel
switch.
1. IR source
In one arm of the interferometer, the IR source radiation travels through the beam
splitter to the fixed mirror back to the beam splitter through the sample and to the
detector. In the other arm, the IR source radiation travels to the beam splitter to the
movable mirror, back through the beam splitter to the sample and to the detector. The
difference in pathlengths of the two beams is the retardation . An He-NE laser is used
as a monochromatic reference source. The laser beam is sent through the interferometer
in the opposite direction to that of the IR beam.
Double-beam FTIR
Spectrometer
Interferometer
Michelson interferometer
If moving mirror moves 1/4 (1/2 round-trip) waves are out of phase at beam-
splitting mirror - no signal
If moving mirror moves 1/2 (1 round-trip) waves are in phase at beam-splitting
mirror signal
...
Interferograms
Difference in pathlength called retardation
Plot vs. signal - cosine wave with frequency proportional to light
frequency but signal varies at much lower frequency
One full cycle when mirror moves distance /2 (round-trip = )
Frequency of signal: VMM 2VMM
f
/2 VMM velocity of moving mirror
Rapid (<10 s)
S S S
n n
N ( S Si ) N
2
n # scans
S/N improves with more scans
(noise is random, signal is not!)
Spectrum calibration
For routine instrument calibration, run the spectrum of
polystyrene film (or indene) at resolution 2 cm -1. Band
positions are available in the literature.
Higher resolution calibrations may be made from gas-
phase spectra (e.g. HCl gas).
Sample preparation techniques
Infrared spectra may be obtained for gases, liquids or
solids (neat or in solution)
Almost all FIR studies are now carried out with FTIR
spectrometers.
The far-IR region can provide unique information.
i) The fundamental vibrations of many organometallic and
inorganic molecules fall in this region due to the heavy atoms
and weak bonds in these molecules.
ii) Lattice vibrations of crystalline materials occur in this region,
iii) Electron valence/conduction band transition in
semiconductors often correspond to far-IR wavelengths.
References:
J. Workman, A.W. Springsteen, Applied Spectroscopy, Academic
Press, 1998.
J.M. Hollas, Modern Spectroscopy, John Wiley&Sons, 1996.
B. Stuart, W.O. George, D.J. Ando, Modern Infrared Spectroscopy,
John Wiley&Sons, 1997.
N.N. Colthup, L.H. Daly, S.E. Wiberly, S.E. Wiberly, Introduction to
Infrared and Raman Spectroscopy, Academic Press, 1997.
B. Schrader, D. Bougeard, Infrared and Raman Spectroscopy: Methods
and Applications, John Wiley&Sons, 1995.
Infrared Spectrum of CCl4