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
virtual
state

Scattered
Excitation
Rotational Raman
Vibrational Raman
Electronic Raman
v” = 1

v” = 0
Infrared Raman
(absorption) (scattering)
 Classical Theory of Raman Effect

mind = 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:
m z (t )   zzequil 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
rmax Emax cos 2 ( 0  vib )t Stokes Raman scatter
2 dr
Kellner et al., Analytical Chemistry
 Raman Scattering

Selection rule: v = ±1
Overtones: v = ±2, ±3, …
m z (t )   zzequil 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

Must also have a change in polarizability

Classical Description does not suggest any difference

between Stokes and Anti-Stokes intensities
h
N1  vib
 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 O=C=O

Raman active Raman inactive

IR 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:
 Ei
 R α s ( ex ) E0 ni e
4
ex
kT

s(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

s(ex) - target area presented by a molecule for

scattering
 Raman Scattering Cross-Section
ds scattered flux/unit solid angle

d  indident flux/unit solid angle
ds
s   d
d

Process Cross-Section of s (cm2)

-18 s(ex) - target area
absorption UV 10
presented by a
absorption IR 10-21 molecule for scattering
emission Fluorescence 10-19
scattering Rayleigh 10-26
scattering Raman 10-29
scattering RR 10-24
scattering SERRS 10-15
scattering SERS 10-16 Table adapted from Aroca, Surface Enhanced
Vibrational Spectroscopy, 2006
 Raman Scattering Cross-Section

ex (nm) s ( x 10-28 cm2)

CHCl3:
532.0 0.66 C-Cl stretch at 666 cm-1
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
 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. C–F).
 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