Sir Chandrasekhara Venkata Raman, född 1888 i

Tiruchirapalli, död 1970. Indisk vetenskapsman och

Raman spectroscopy fysiker. Tilldelades Nobelpiset 1930 för sin upptäckt
av ljusets oelastiska spridning (Ramaneffekten)

A short introduction

Nobelpriset i fysik
1930
Umeå 2006-04-10 Bo Karlberg

It was the first time that an Indian scholar who studied wholly
in India received the Nobel Prize. An interesting anecdote goes
that he was offered a toast during the Nobel function. Being a
strict teetotaller he responded,"Sir!You have seen the Raman
effect on alcohol! Please do not try to see the alcohol effect on
Raman."
Raman discovered that
- the wavelength of a small fraction of
the emitted light changed in comparison
with the wavelength of the incoming light
- this wavelength shift was independent of
the wavelength from the light source
- this wavelength shift was dependent on
the structure of the radiated molecule

Raman spectroscopy
Transparent medium

ν(out)
‰The difference in wavelength
between incoming light and the ν(in) ν(out) =
ν(in)
Raman shifted light is in the mid-IR
region
‰IR spectra and Raman spectra are
similar but there are important Elastic collisions between photons and
molecules = Rayleigh scattering – this
differences occurs when the molecule is smaller than
the wavelength, λ

1
 Raman Three types of light are spread by
the radiated molecule
The radiated molecule acts as a
monochromator!

ν(in) = νR
‰ Stokes longer wavelength
ν(in) νStokes
‰ Rayleigh same wavelength
νantiStokes
‰ anti-Stokes shorter wavelength

ν(in) = νR ν(in) = νR

Virtual state
Assumed state of a photon and a molecule
during an intefesimal (short) time period Since the Raman effect depends upon
the polarizability of the molecule, it can
be observed for molecules which have
Rule: no net dipole moment.
A molecule will emit monochromatic light
and produce Raman shifted lines (Stokes
and anti-Stokes) only when the molecule
vibrates so that the polarizability is
changed during the vibration

Polarizability??
- H C C H
O

C+ Let us consider the dipole moment,

µ, induced in an atom placed in an
CH3 CH3 H C C H electrical field, E*.

Polar molecule Polarizable molecule

; NIR, IR ; Raman

2
 Polarizability is α in the
following formula:
µ
µ = α E*

+ + - µ is the dipole moment and

+ E* is the electrical field

E*

Do not confuse polarizability

and polarization!
The three basic dimensions of light (and of all
electromagnetic radiation) are:
‰Intensity (or brilliance or amplitude perceived by Polarization of
humans as the brightness of the light), light
‰Frequency (or wavelength, perceived by humans
as the color of the light), and
‰Polarization (or angle of vibration and not
perceivable by humans under ordinary
circumstances)

Stokes-lines Virtual state anti-Stokes-lines Virtual state

Stokes line anti-Stokes line

h(νL-ν1) h(νL+ν1)
Rayleigh line
n=1 n=1

hν1 Rayleigh line hν1

n=0 n=0

3
 Lasers for Raman spectroscopy Sensitivity for
”normal” Raman
- Ar-ion 488/514.5 nm
> 0.1 M
- He/Ne 632.8 nm
- Nd:YAG 1064 nm

Summary,
”normal” Raman Resonance Raman
Condition:
‰ The wavelength shift is found in the mid-IR
region The laser light wavelength must be close
‰ Water does not interfere – aqueous to the absorbance maximum of the
samples are OK molecule (tunable lasers preferred)
‰ Glass, quarts not interfering
Sensitivity increase:
‰ Fluorescense is a problem 102 - 106 times
‰ Intensity: Raman <<< Rayleigh; <0.001%

SERS
Surface Enhanced Raman Spectroscopy
SERS + RR
Analyte molecule + colloid Ag, Au or
Cu-particles This combination can enable
detection in the
“For reasons not fully understood, the 10-9 to 10-12 M range!
Raman lines of the adsorbed molecule
are often enhanced by a factor of 103
to 106”

4
 FIA+SERS
SERS
S Bubble removal

How to perform a measurement

Detection cell
AgNO3
based on SERS? NaBH4 Argon laser 514.5

PMT
Photon
counter
To waste

SERS SERS
Special-made vials Sol-gel
Raman
scattering out
Special-made vials

Analyte in
the
Laser light in
plasmon
field

Ag

Comparison between Raman and NIR/IR

SUMMARY
Property/compound Raman NIR/IR
symmetric vibrations strong weak
‰ SERS develops rapidly now, more than
6300 publications already (2005) asymmetric vibrations weak strong
polar bindings weak strong
‰ SERS is a sensitive technique
unpolar bindings strong weak
‰ FIA or SIA + SERS = the ideal aromatic compounds strong weak
logistic solution? selectivity high low
penetration depth core surface

5
 D(+)-Glucopyranose Me-a-D-Glucopyranoside

FT-Raman Applications from Thermo

Analysis of Darkly Colored Samples

Paper Industry applications
Qualitative Analysis and Structural Confirmation of
Surfacants
Disposal of Unknown Waste Chemicals
Chemometric Procedures in the Analysis of
Pharmaceuticals
Chemometric Procedures in the Analysis of Polymers
Study of Formulated Pharmaceuticals using FT-Raman
Microscopic Sturctural Studies on Polymer Surfaces

Me-b-D-Glucopyranoside