History

1928 first discovered by C.V. Raman and K.F. Krishnan

When radiation passes through a transparent medium, the species present scatter a
fraction of the beam in all directions.
Two significant observations:
1. visible wavelength of a small fraction of the radiation scattered by certain
molecules differs from that of the incident beam
2. shifts in wavelength depend upon the chemical structure of the molecules
responsible for the scattering
1930 C.V Raman was awarded the Nobel Prize in Physics for this discovery
Advantage: Nondestructive chemical analysis
Challenges: lack of good Raman source
Lack of good detector
Interference from fluorescence
1960 Lasers as source for Raman
1986 Fourier-transform (FT) Raman instrumentation was developed
(overcome problems with fluorescence)
1990 Dispersive Raman instrumentation was developed
Compact near-IR (NIR) lasers as source
Multichannel detectors

Rayleigh Scattering Raman scattering

- No change in vibrational state - Change in vibrational state

(ground to higher state: STOKE)
(higher to ground state: ANTISTOKE)

- No induced nuclear motion - Induced nuclear motion

ELASTIC scattering of light INELASTIC scattering of light

- Dominant process - Weak process

( 1 out of 106 photons is Raman scattered
 Advantages of using Raman
- non-destructive (in general)
- little to no sample preparation
- water does not cause interference (Raman spectra can be obtained from
aqueous solutions)
- sample holder: transparent containers (plastic, glass, jars, cuvettes) (avoid
inconvenience of working with NaCl or atmospherically unstable window
materials)
- selective: can differentiate molecules (structure)
- fast analysis time
- insensitive to aqueous absorption bands
- molecular fingerprint: unique Raman spectrum for each molecule or specie
o structural information
o identification or verification of unknowns
4

Raman
- form of molecular spectroscopy which involves scattering of electromagnetic
radiation by atoms or molecules
- probes the vibrational modes of molecules
- inelastic scattering of light

Consider Raman Scattering: Classical Wave Interpretation

- electromagnetic radiation has an electric field
- the electric field interact with the molecules in sample through polarization
o polarizability related to the ability of electronic clouds surrounding
the molecule to interact with an electric field

Consider Raman Scattering: Quantum-Particle Interpretation

- light as being composed of particles (photons)
- photons are directed toward a sample
- photons will hit a molecule and bounce off
- weak technique: 1/10million will be Raman-scattered
Three types of scattered radiation

Stokes scattering: ground vibrational state virtual state excited vibrational state
Antistokes scattering: excited vibrational state virtual state ground vibrational
state
Power of Raman/ Efficiency of Raman
- directly proportional to the intensity of incident light
- inversely proportional to the excitation wavelength to the fourth power ( 4)
o the more energetic the wavelength (shorter wavelength), the more
Raman scatter will be observed
Fluorescence
- fluorescence region: 275 975 nm
- Use of shorter wavelength may promote fluorescence
- Fluorescence interfere with Raman signal

Raman Spectrometer
- Laser
o Narrow linewidth
o Small form factor
o Low power consumption
o Stable power/wavelength output
- Spectrometer
o High resolution
o Low noise
o Small form factor
o Low power consumption
UV excitation: photomultiplier tube (PMT) or CCD
Vis excitation: CCD
NIR excitation: Indium gallium arsenide (InGaAS) array

- Sampling interface
o Fiber optic probe: very flexible
High optical density Raman cutoff

Theory
- results from the same type of quantized vibrational changes that are
associated with infrared absorption
- difference in wavelength between the incident and scattered visible radiation
corresponds to wavelengths in the mid-infrared region
- Raman scattering spectrum and infrared absorption spectrum for a given
species often resemble one another quite closely

- Raman spectra are acquired by irradiating a sample with a powerful laser

source of visible or near-infrared monochromatic radiation
 - During irradiation, the spectrum of the scattered radiation is measured at
some angle (often 90 deg) with a suitable spectrometer

- At the very most, the intensities of Raman lines are 0.001 % of the intensity
of the source; as a consequence, their detection and measurement are
somewhat more difficult than are infrared spectra.

Information about spectra

- The abscissa of Raman spectrum is the wavenumber shift , which is defined

as the difference in wavenumbers (cm -1) between the observed radiation and
that of the source
- Anti-Stokes lines are appreciably less intense that the corresponding Stokes
lines. For this reason, only the Stokes part of a spectrum is generally used.
- The magnitude of Raman shifts are independent of the wavelength of
excitation.
Intro:
- Types of measurement of electromagnetic radiation as analyzing a particular
sample
Absorption spectroscopy absorbed light

History
3 types of scattering