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Overview
1. Electromagnetic radiation
2. Vibrations
3. Principle of IR experiment
4. IR spectrum
5. Types of vibration
6. CGF/Fingerprint regions
7. IR activity of vibrations
8. Interpretation of IR spectra
9. Instrumentation
10. Sample preparation
Electromagnetic Radiation
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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:
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
Divisions arise because of different optical materials and
instrumentation.
Molecular spectra
There are three basic types of optical
spectra that we can observe for
molecules:
1.Electronic or vibronic spectra (UVvisible-near IR)
(transitions between a specific vibrational and rotational level
of one electronic state and a vibrational and rotational level of
another electronic state)
2.Vibrational or vibrational-rotational
spectra (IR region)
(transitions from the rotational levels of one vibrational level
to the rotational levels of another vibrational level in the same
electronic state)
The vibrational energy V(r) can be calculated using the (classical) model of
the harmonic oscillator:
Using this potential energy function in the Schrdinger equation, the vibrational
frequency can be calculated:
Fig. 12-1
Molecular vibrations
How many vibrations are possible (=fundamental vibrations)?
A molecule has as many degrees of freedom as the total degree of
freedom of its individual atoms. Each atom has three degrees of freedom
(corresponding to the Cartesian coordinates), thus in an N-atom
molecule there will be 3N degree of freedom.
In molecules, movements of the atoms are constrained by interactions
through chemical bonds.
Translation - the movement of the entire molecule while the positions
of the atoms relative to each other remain fixed: 3 degrees of
translational freedom.
Rotational transitions interatomic distances remain constant but the
entire molecule rotates with respect to three mutually perpendicular
axes: 3 rotational freedom (nonlinear), 2 rotational freedom (linear).
Fundamental Vibrations
Vibration Types
There are two different types of vibrational modes:
Vibrations can either involve a change in bond length
(stretching) or bond angle (bending)
Principle of IR experiments
E-vector in electromagnetic radiation has frequency
Molecular vibrations involving change in dipole moment set up
fluctuating electric field
Vibrational energies: fundamental (= one quantum)
Energy transferred to molecule by resonance when vibration
frequency is the same as that of the electromagnetic radiation
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).
Infrared Spectrum
of Carbon Dioxide
Absorption Regions
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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
Fingerprint region
In the region from 1300 to 400 cm-1, vibrational frequencies are
affected by the entire molecule, as the broader ranges for group
absorptions in the figure below fingerprint region.
Absorption in this fingerprint region is characteristic of the molecule
as a whole. This region finds widespread use for identification purpose
by comparison with library spectra.
Coupled Interactions
When two bond oscillators share a common atom, they seldom behave
as individual oscillators (unless the individual oscillation frequencies are
widely different).
Hydrogen Bonding
A hydrogen bond exists when a hydrogen atom is bonded to two
or more other atoms
> not an ordinary covalent bond, since the hydrogen atom
has only one orbital (1s) to engage in covalent bonding
Typical H-bond: Hydrogen is attached to two very
electronegative atoms, usually in a linear fashion and not
symmetrically:
XHB
=> The s orbital of the proton can effectively overlap with
the p or orbital of the acceptor group.
IR spectrum
y axis is %T or A
x axis is wavenumber (or wavelength)
Io sample I
T = I/Io
%T = 100 I/Io
T transmission / transmittance
A = -log T
A absorbance (no units)
(Note A (but not T) concentration)
Ordinate Scaling
Absorbance spectrum of polystyrene
> generally used for quantitative
work
Abscissa Scaling
There is a substantial difference in appearance, whether the spectrum
is linear in wavenumber (A, standard) or linear in wavelength (B):
B
(both spectra are
recorded with the same
sample)
Instrumentation
Perkin ElmerTM
Spectrum One
BRUKE TENSORTM
Series
Dispersive IR spectrophotometers
Modern dispersive IR spectrophotometers are invariably double-beam
instruments, but many allow single-beam operation via a front-panel
switch.
1-50 m
(mid- to far-IR)
Globar
1-50 m
(mid- to far-IR)
W filament lamp
1100 K
0.78-2.5 m
(Near-IR)
Hg arc lamp
plasma
50 - 300 m
(far-IR)
CO2 laser
9-11 m
2. Detector / transducer
Thermocouple
thermoelectric effect
-dissimilar metal junction
cheap, slow,
insensitive
Bolometer
Ni, Pt resistance
thermometer (thermistor)
Highly sensitive
<400 cm-1
Pyroelectric
3. Optical system
Windows are used for sample cells and to permit various compartment
to be isolated from the environment.
transparent to IR over the wavelength region
inert to the various chemicals analyzed
capable of being shaped, ground, and polished to the desired
optical quality
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 beamsplitting mirror - no signal
If moving mirror moves 1/2 (1 round-trip) waves are in phase at beam-splitting
mirror signal
...
Interferograms
VMM 2VMM
f
/2
2VMM
f
3cm / s
10
f
10
10
3 10 cm / s
Measuring processes
Advantages of FTIR
very high resolution (< 0.1 cm 1 )
Two closely spaced lines only separated if one complete "beat" is recorded. As
lines get closer together, must increase.
(cm1) 1/
Mirror motion is 1/2
Resolution governed by distance movable mirror travels
Rapid (<10 s)
Reproducible and Inexpensive
2
( S Si ) N
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 gasphase spectra (e.g. HCl gas).
Gas samples
A gas sample cell consists of a cylinder of glass or sometimes a metal.
The cell is closed at both ends with an appropriate window materials
(NaCl/KBr) and equipped with valves or stopcocks for introduction of the
sample.
Long pathlength (10 cm) cells used to study dilute (few molecules)
or weakly absorbing samples.
Multipass cells more compact and efficient instead of long-pathlength
cells. Mirrors are used so that the beam makes several passes through
the sample before exiting the cell. (Effective pathlength 10 m).
To resolve the rotational structure of the sample, the cells must be
capable of being evacuated to measure the spectrum at reduced
pressure.
For quantitative determinations with light molecules, the cell is
sometimes pressurized in order to broaden the rotational structure and
all simpler measurement.
Liquid samples
Pure or soluted in transparent solvent not water (attacks windows)
The sample is most often in the form of liquid films (sandwiched
between two NaCl plates)
Adjustable pathlength (0.015 to 1 mm) by Teflon spacer
Solid samples
Spectra of solids are obtained as alkali halide discs (KBr), mulls
(e.g. Nujol, a highly refined mixture of saturated hydrocarbons) and
films (solvent or melt casting)
Alkali halide discs:
1. A milligram or less of the fine ground sample mixed with about
100 mg of dry KBr powder in a mortar or ball mill.
2. The mixture compressed in a die to form transparent disc.
Mulls
1. Grinding a few milligrams of the powdered sample with a mortar
or with pulverizing equipment. A few drops of the mineral oil
added (grinding continued to form a smooth paste).
2. The IR of the paste can be obtained as the liquid sample.
Near-infrared spectrometry
NIR shows some similarities to UV-visible spectrophotometry and
some to mid-IR spectrometry. Indeed the spectrophotometers
used in this region are often combined UV-visible-NIR ones.
The majority of the absorption bands observed are due to
overtones (or combination) of fundamental bands that occur in
the region 3 to 6 m, usually hydrogen-stretching vibrations.
NIR is most widely used for quantitative organic functional-group
analysis. The NIR region has also been used for qualitative
analyses and studies of hydrogen bonding, solute-solvent
interactions, organometallic compounds, and inorganic
compounds.
Far-infrared spectrometry
Almost all FIR studies are now carried out with FTIR
spectrometers.
The far-IR region can provide unique information.
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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.