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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
8 4 ( ') 2 (1 cos 2 ) E0
( Esc )
4d 2
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)
ind = E
polarizability
Colthup et al., Introduction to Infrared and Raman Spectroscopy, 3rd ed. , Academic Press, Boston:
Photon-Molecule Interactions
Raman Scattering
Selection rule: v = 1
Overtones: v = 2, 3,
r
z (t ) Emax cos 2 0t
r
1 d zz
rmax Emax cos 2 ( 0 vib )t
2 dr
r
1 d zz
rmax Emax cos 2 ( 0 vib )t
2 dr
equil
zz
O=C=O
Raman inactive
IR active
Raman vs IR Spectra
McCreery, R. L., Raman Spectroscopy for Chemical Analysis, 3rd ed. , Wiley, New York: 2000
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
Cross-Section of (cm2)
absorption
UV
10-18
Process
absorption
IR
10-21
emission
Fluorescence
10-19
scattering
Rayleigh
10-26
scattering
Raman
10-29
scattering
RR
10-24
scattering
SERRS
10-15
scattering
SERS
10-16
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
CHCl3:
C-Cl stretch at 666 cm-1
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.
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.
ex = 514.5 nm
http://www.photobiology.com/v1/udaltsov/udaltsov.htm
Raman Instrumentation
Dispersive and
FT-Raman
Spectrometry
McCreery, R. L., Raman Spectroscopy for Chemical Analysis, 3rd ed., Wiley, New York:
2000
Rubinson, K. A., Rubinson, J. F., Contemporary Instrumental Analysis, Prentice Hall, New
Jersey: 2000
McCreery, R. L., Raman Spectroscopy for Chemical Analysis, 3rd ed., Wiley, New York:
2000
McCreery, R. L., Raman Spectroscopy for Chemical Analysis, 3rd ed., Wiley, New York:
2000
McCreery, R. L., Raman Spectroscopy for Chemical Analysis, 3rd ed. , Wiley, New York: 2000
McCreery, R. L., Raman Spectroscopy for Chemical Analysis, 3rd ed., Wiley, New York:
2000 and http://www.olympusfluoview.com/theory/confocalintro.html
McCreery, R. L., Raman Spectroscopy for Chemical Analysis, 3rd ed. , Wiley, New York: 2000