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Attenuated Total Reflectance (ATR) Fourier Transform-Infrared (FT-IR)
Attenuated Total Reflectance (ATR)
Fourier Transform-Infrared (FT-IR)
Attenuated Total Reflectance (ATR) FT-IR 0.5-5 µm Sample  >  c ATR crystal (high
Attenuated Total Reflectance (ATR) FT-IR
0.5-5 µm
Sample
 >  c
ATR crystal
(high refractive index)
IR beam
n diamond = 2.4; n ZnSe =2.4; n silicon = 3.4
The sample must have good contact with the ATR crystal
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Examples of ATR IR spectra Good contact Bad contact between sample and ATR crystal contact
Examples of ATR IR spectra
Good contact
Bad contact between sample and ATR crystal contact
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ATR vs. Transmission FT-IR Depth of penetration is relative to the wavelength of light 
ATR vs. Transmission FT-IR
Depth of penetration is relative to the wavelength of light
 peaks on the left hand side often appear a little smaller than expected
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ATR vs. Transmission FT-IR of thick samples Transmission ATR 27-Sep-16 98
ATR vs. Transmission FT-IR of thick samples
Transmission
ATR
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Raman spectroscopy
Raman spectroscopy
Scattering Light is randomly deviating in space from specularly reflected or transmitted laser beam 27-Sep-16
Scattering
Light is randomly deviating in space from specularly reflected or
transmitted laser beam
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Rayleigh Scattering •Elastic ( does not change) •Random direction of emission •Little energy loss 27-Sep-16
Rayleigh Scattering
•Elastic ( does not change)
•Random direction of emission
•Little energy loss
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Raman Scattering Rotational Raman Vibrational Raman Electronic Raman Raman scattering: inelastic scattering of light
Raman Scattering
Rotational Raman
Vibrational Raman
Electronic Raman
Raman scattering: inelastic scattering of light with a material
A Raman spectrum is a fingerprint for a material
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Basic theory of Raman effect Raman shift in wavenumbers (cm -1 ): If the bond
Basic theory of Raman effect
Raman shift in wavenumbers (cm -1 ):
If the bond were infrared active, the energy of its absorption would also be E. Thus, the
Raman frequency shift and the infrared absorption peak frequency are identical.
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Some common laser sources for Raman spectroscopy 27-Sep-16 104
Some common laser sources for Raman spectroscopy
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Raman spectrum of CCl 4 Stokes transitions anti-Stokes transitions 27-Sep-16 105
Raman spectrum of CCl 4
Stokes transitions
anti-Stokes transitions
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Raman spectrum of CCl 4 27-Sep-16 106
Raman spectrum of CCl 4
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Raman selection rules • Induced dipole moment of in a molecule by an external (incident)
Raman selection rules
• Induced dipole moment of in a molecule by an external (incident) electric field (E):
µ induced =  E, where  is polarizability of the molecule
The polarizability measures the ease with which the electron cloud around a molecule
can be distorted.
• Selection rule for a Raman-active vibration:
There
must be a change in polarizability during the vibration
The vibrations of a highly polar moiety, such as the O-H bond, are usually
weak.
An external electric field can not induce a large change in the dipole
moment and stretching or bending the bond does not change this.
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Mutual exclusion principle 27-Sep-16 109
Mutual exclusion principle
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Mutual exclusion principle (related to symmetry) 27-Sep-16 110
Mutual exclusion principle (related to symmetry)
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Raman vs IR spectra • Number of peaks related to degrees of freedom 3N -
Raman vs IR spectra
• Number of peaks related to degrees of freedom
3N - 6 (bent) or 3N - 5 (linear) for N atoms
• Energy related to harmonic oscillator
k ( m 1  m 2 )
 or   c
2
m
1 m 2
• Selection rules related to symmetry
Rule of thumb: symmetric=Raman active, asymmetric=IR active
CO 2
H
2 O
Raman: 1335 cm –1
Raman + IR: 3657 cm –1
IR: 2349 cm –1
Raman + IR: 3756 cm –1
IR: 667 cm –1
Raman + IR: 1594 cm –1
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Raman spectra of some materials 27-Sep-16 112
Raman spectra of some materials
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Raman vs IR spectra 27-Sep-16 113 McCreery, R. L., Raman Spectroscopy for Chemical Analysis, 3rd
Raman vs IR spectra
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McCreery, R. L., Raman Spectroscopy for Chemical Analysis, 3rd ed., Wiley, New York: 2000
Common Raman shifts 27-Sep-16 114
Common Raman shifts
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Raman vs IR spectra 27-Sep-16 115
Raman vs IR spectra
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Raman peak intensities The intensity of a normal Raman peak depends on: • polarizability of
Raman peak intensities
The intensity of a normal Raman peak depends on:
• polarizability of the molecule
• intensity of the source
• concentration of the active group
Raman intensities are usually directly proportional to the
concentration of the active species
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Raman vs IR spectra 27-Sep-16 117 McCreery, R. L., Raman Spectroscopy for Chemical Analysis, 3rd
Raman vs IR spectra
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McCreery, R. L., Raman Spectroscopy for Chemical Analysis, 3rd ed., Wiley, New York: 2000
Raman spectroscopy: general comments Raman is a vibrational spectroscopy akin to IR - Good for
Raman spectroscopy: general comments
Raman is a vibrational spectroscopy akin to IR
- Good for fingerprinting, probing molecular symmetry
Scattering-based, not transmission/reflection
- Means no need for fancy sample preparation…gas, liquid, or solid
- Virtually use Stokes lines
You need to pick excitation energy (laser line)
- nm: Lower Raman signal
785
- nm: Resonance more likely; Higher signal
514
Water can be used as solvent.
Few intense overtones and combination bands  few spectral overlaps.
Raman intensities are proportional to concentration and laser power
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Advantages of IR over Raman • Simpler and cheaper instrumentation. • Less instrument dependent than
Advantages of IR over Raman
• Simpler and cheaper instrumentation.
• Less instrument dependent than Raman spectra because IR
spectra are based on measurement of intensity ratio.
• Lower detection limit than (normal) Raman.
• Background fluorescence can overwhelm Raman.
• More suitable for vibrations of bonds with very low polarizability
(e.g. C–F).
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Example
Example

120

Example 120 Flow Field Plate - Graphite  I g     3.98 

Flow Field Plate - Graphite

 I g     3.98  I d 

I g


  3.98

I d

I g     3.98  I d  Nanocrystalline graphite has and disorder

Nanocrystalline graphite has

and disorder (d) peaks. The characteristic dimension of graphitic domains is given by:

graphitic (g)

 I  g  ( Å )  44    I 

I

g
 ( Å )  44



I

d
175 Å

From early literature on graphitic materials Tuinstra and Koenig, J. Chem Phys. 53, 1126 (1970).

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