Attenuated Total Reflectance (ATR)

Fourier Transform-Infrared (FT-IR)

Attenuated Total Reflectance (ATR) FT-IR

0.5-5 m Sample

> c
ATR crystal (high refractive index)
IR beam ndiamond = 2.4; nZnSe =2.4; nsilicon = 3.4

The sample must have good contact with the ATR crystal

27-Sep-16
95

1
 Examples of ATR IR spectra

Good contact

Bad contact between sample and ATR crystal contact

27-Sep-16
96

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

27-Sep-16
97

2
 ATR vs. Transmission FT-IR of thick samples

Transmission

ATR

27-Sep-16
98

Raman spectroscopy

3
 Scattering
Light is randomly deviating in space from specularly reflected or
transmitted laser beam

27-Sep-16
100

Rayleigh Scattering

Elastic ( does not change)

Random direction of emission
Little energy loss

27-Sep-16
101

4
 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

27-Sep-16
102

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.
27-Sep-16
103

5
 Some common laser sources for Raman spectroscopy

27-Sep-16
104

Raman spectrum of CCl4

Stokes transitions

anti-Stokes transitions

27-Sep-16
105

6
 Raman spectrum of CCl4

27-Sep-16
106

27-Sep-16
107

7
 Raman selection rules

Induced dipole moment of in a molecule by an external (incident) electric field (E):

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.

27-Sep-16
108

Mutual exclusion principle

27-Sep-16
109

8
 Mutual exclusion principle (related to symmetry)

27-Sep-16
110

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

c k(m1 m2 )
or
2 m1m 2
Selection rules related to symmetry
Rule of thumb: symmetric=Raman active, asymmetric=IR active

CO2 H2O

Raman: 1335 cm1

Raman + IR: 3657 cm1
IR: 2349 cm1
Raman + IR: 3756 cm1

IR: 667 cm1

Raman + IR: 1594 cm1

27-Sep-16
111

9
 Raman spectra of some materials

27-Sep-16
112

Raman vs IR spectra

27-Sep-16
113 McCreery, R. L., Raman Spectroscopy for Chemical Analysis, 3rd ed., Wiley, New York: 2000

10
 Common Raman shifts

27-Sep-16
114

Raman vs IR spectra

27-Sep-16
115

11
 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

27-Sep-16
116

Raman vs IR spectra

27-Sep-16
117 McCreery, R. L., Raman Spectroscopy for Chemical Analysis, 3rd ed., Wiley, New York: 2000

12
 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 preparationgas, liquid, or solid
- Virtually use Stokes lines

You need to pick excitation energy (laser line)

- 785 nm: Lower Raman signal
- 514 nm: Resonance more likely; Higher signal

Water can be used as solvent.

Few intense overtones and combination bands few spectral overlaps.
Raman intensities are proportional to concentration and laser power
27-Sep-16
118

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. CF).

27-Sep-16
119

13
 Example

Flow Field Plate - Graphite

Ig
3.98
Id Nanocrystalline graphite has graphitic (g)
and disorder (d) peaks. The characteristic
dimension of graphitic domains is given by:

I
() 44 g
Id

175

From early literature on graphitic materials

Tuinstra and Koenig, J. Chem Phys. 53, 1126 (1970).
27-Sep-16
120

14