Raman Spectroscopy

1923 Inelastic light scattering is predicted by A. Smekel

1928 Landsberg and Mandelstam see unexpected
frequency shifts in scattering from quartz
1928 C.V. Raman and K.S. Krishnan see feeble
fluorescence from neat solvents
First Raman Spectra:
Filtered Hg arc
lamp spectrum:
C6H6
Scattering

http://www.springerlink.com/content/u4d7aexmjm8pa1fv/fulltext.pdf

Raman Spectroscopy
1923 Inelastic light scattering is predicted by A. Smekel
1928 Landsberg and Mandelstam see unexpected
frequency shifts in scattering from quartz
1928 C.V. Raman and K.S. Krishnan see feeble
fluorescence from neat solvents
1930 C.V. Raman wins Nobel Prize in Physics
1961 Invention of laser makes Raman experiments
reasonable
1977 Surface-enhanced Raman scattering (SERS) is
discovered
1997 Single molecule SERS is possible

Rayleigh Scattering

Elastic ( does not change)

Random direction of emission
Little energy loss

8 4 ( ') 2 (1 + cos 2 ) E0
( Esc ) =
4d 2

Eugene Hecht, Optics, Addison-Wesley, Reading, MA, 1998.

Raman Spectroscopy
1 in 107 photons is scattered inelastically

Scattered

Excitation

virtual
state

Rotational Raman
Vibrational Raman
Electronic Raman
v = 1
v = 0

Infrared

Raman

(absorption)

(scattering)

Classical Theory of Raman Effect

ind = E
polarizability

Colthup et al., Introduction to Infrared and Raman Spectroscopy, 3rd ed., Academic Press, Boston: 1990

Photon-Molecule Interactions

When light interacts with a vibrating diatomic molecule, the induced

dipole moment has 3 components:

equil
z (t ) zz Emax cos 2 0t +
Rayleigh scatter

1 d zz
rmax Emax cos 2 ( 0 + vib )t +
Anti-Stokes Raman scatter
2 dr

1 d zz
Stokes Raman scatter
rmax Emax cos 2 ( 0 vib )t
2 dr
Kellner et al., Analytical Chemistry

Raman Scattering
Selection rule: v = 1
Overtones: v = 2, 3,

z (t ) Emax cos 2 0t +

1 d zz
rmax Emax cos 2 ( 0 + vib )t +
2 dr

1 d zz
rmax Emax cos 2 ( 0 vib )t
2 dr
equil
zz

Must also have a change in polarizability

Classical Description does not suggest any difference
between Stokes and Anti-Stokes intensities
h
vib
N1
= e kT
N0
www.andor.com

Are you getting the concept?

Calculate the ratio of Anti-Stokes to Stokes scattering
intensity when T = 300 K and the vibrational frequency
is 1440 cm-1.
h = 6.63 x 10-34 Js
k = 1.38 x 10-23 J/K

Presentation of Raman Spectra

ex = 1064 nm = 9399 cm-1
Breathing mode:
9399 992 = 8407 cm-1
Stretching mode:
9399 3063 = 6336 cm-1

Mutual Exclusion Principle

For molecules with a center of symmetry, no IR active
transitions are Raman active and vice versa
Symmetric molecules
IR-active vibrations are not Raman-active.
Raman-active vibrations are not IR-active.
O=C=O
Raman active
IR inactive

O=C=O
Raman inactive
IR active

Raman vs IR Spectra

Ingle and Crouch, Spectrochemical Analysis

Raman vs Infrared Spectra

McCreery, R. L., Raman Spectroscopy for Chemical Analysis, 3rd ed., Wiley, New York: 2000

Raman vs Infrared Spectra

McCreery, R. L., Raman Spectroscopy for Chemical Analysis, 3rd ed., Wiley, New York: 2000

Raman Intensities
Radiant power of Raman scattering:

R ( ex ) E0 ni e
4
ex

Ei
kT

(ex) Raman scattering cross-section (cm2)

ex excitation frequency
E0 incident beam irradiance
ni number density in state i
exponential Boltzmann factor for state i
(ex) - target area presented by a molecule for
scattering

Raman Scattering Cross-Section

d scattered flux/unit solid angle
=
d indident flux/unit solid angle
d
= d
d

Process
Cross-Section of
absorption
UV
absorption
IR
emission
Fluorescence
scattering
Rayleigh
scattering
Raman
scattering
RR
scattering
SERRS
scattering
SERS

(cm2)
(ex) - target area
-18
10
presented by a
-21
10
molecule for scattering
10-19
10-26
10-29
10-24
10-15
Table adapted from Aroca, Surface Enhanced
10-16
Vibrational Spectroscopy, 2006

Raman Scattering Cross-Section

ex (nm) ( x 10-28 cm2)

532.0
0.66
435.7
1.66
368.9
3.76
355.0
4.36
319.9
7.56
282.4
13.06
Table adapted from Aroca, Surface Enhanced
Vibrational Spectroscopy, 2006

CHCl3:
C-Cl stretch at 666 cm-1

Advantages of Raman over IR

Water can be used as solvent.
Very suitable for biological samples in native state
(because water can be used as solvent).
Although Raman spectra result from molecular
vibrations at IR frequencies, spectrum is obtained using
visible light or NIR radiation.
=>Glass and quartz lenses, cells, and optical fibers
can be used. Standard detectors can be used.
Few intense overtones and combination bands => few
spectral overlaps.
Totally symmetric vibrations are observable.
Raman intensities to concentration and laser power.

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).

Raman and Fraud

Lewis, I. R.; Edwards, H. G. M., Handbook of Raman Spectroscopy: From the Research Laboratory to
the Process Line, Marcel Dekker, New York: 2001.0

Ivory or Plastic?

Lewis, I. R.; Edwards, H. G. M., Handbook of Raman Spectroscopy: From the Research
Laboratory to the Process Line, Marcel Dekker, New York: 2001.

The Vinland Map: Genuine or Forged?

Brown, K. L.; Clark, J. H. R., Anal. Chem. 2002, 74,3658.

The Vinland Map: Forged!

Brown, K. L.; Clark, J. H. R., Anal. Chem. 2002, 74,3658.

Resonance Raman
Raman signal intensities can be enhanced by resonance
by factor of up to 105 => Detection limits 10-6 to 10-8 M.
Typically requires tunable laser as light source.

Kellner et al., Analytical Chemistry

Resonance Raman Spectra

Ingle and Crouch, Spectrochemical Analysis

Resonance Raman Spectra

ex = 441.6 nm

ex = 514.5 nm

http://www.photobiology.com/v1/udaltsov/udaltsov.htm

Raman Instrumentation

Tunable Laser System

Versatile Detection System

Dispersive and
FT-Raman
Spectrometry

McCreery, R. L., Raman

Spectroscopy for Chemical
Analysis, 3rd ed., Wiley, New
York: 2000

Spectra from Background Subtraction

McCreery, R. L., Raman Spectroscopy for Chemical Analysis, 3rd ed., Wiley, New York:
2000

Rotating Raman Cells

Rubinson, K. A., Rubinson, J. F., Contemporary Instrumental Analysis, Prentice Hall, New
Jersey: 2000

Raman Spectroscopy: PMT vs CCD

McCreery, R. L., Raman Spectroscopy for Chemical Analysis, 3rd ed., Wiley, New York:
2000

Fluorescence Background in Raman

Scattering

McCreery, R. L., Raman Spectroscopy for Chemical Analysis, 3rd ed., Wiley, New York:
2000

Confocal Microscopy Optics

McCreery, R. L., Raman Spectroscopy for Chemical Analysis, 3rd ed., Wiley, New York: 2000

Confocal Aperture and Field Depth

McCreery, R. L., Raman Spectroscopy for Chemical Analysis, 3rd ed., Wiley, New York:
2000 and http://www.olympusfluoview.com/theory/confocalintro.html

Confocal Aperture and Field Depth

McCreery, R. L., Raman Spectroscopy for Chemical Analysis, 3rd ed., Wiley, New York: 2000