Chapter 18
Raman Spectrometry
Theory of Raman Spectroscopy
q Radiation scattered by certain molecules differs from that of the
incident beam
q The Raman shits depend upon the chemical structure of the molecules
q Raman was awarded the 1931 Nobel Prize in physics.
q Important advantage of Raman over Infrared
- water does not cause interference
- glass or quartz cells can be employed (avoiding the inconvenience of
working with atmospherically unstable window materials)
q Raman spectroscopy was not widely used until 1960s.
- inherent low intensity (0.001 % of intensity of the source)
- interference by fluorescence
- largely overcome by the use of near-infrared laser sources
Excitation of Raman Spectra
Rayleigh scattering
Mechanism of Raman & Rayleigh Scattering
q Rayleigh scattering:
- no energy lost
- elastic collision b/w photon
and molecule (99.999%)
q Stokes and anti-Stokes emission
- frequency changes
q Stokes shift is more favored than
anti-Stokes shirt
- molecular population
- probability
Raman VS. Infrared
Identical q Basic mechanisms are different
q Infrared
- vibrational mode: change in
dipole moment
q Raman
- involve momentary distortion
of electrons around a bond
- reemission of the radiation
as the bond returns to its
normal state
- temporarily polarized
q Polarizability
Raman Active Modes
Dipole Moment : separation of positive and negative charges. when this
separation changes during the vibrational motion of a
molecule it is IR active. if there is no permanent dipole
moment, there is no IR activity (e.g. N2, O2, H2).
Polarizability : the relative tendency of a charge distribution, to be
distorted from its normal shape by an external electric
field, which may be caused by the presence of a nearby
ion or dipole
IR: inactive IR: active
Raman: active Raman: inactive
Distinguishing IR, Raman Active Modes
q Homonuclear molecules (N2, Cl2, H2)
- IR inactive: no dipole moment change
- Raman active: polarizability of bond varies periodically by stretching
vibrations
q CO2
(1) symmetric stretching vibration mode
- IR inactive: no dipole moment change
- Raman active: polarizability of bond varies periodically
(2) asymmetric stretching vibration mode
- IR active: dipole moment change
- Raman inactive: no net change in polarizability of bond
(polarizability increases as lengthens of one of the
bonds + polarizability of the other decreases = total zero)
Raman-active and Non-Raman-active
Vibrations (III)
Symmetric Stretching of CS2
n1 S=C=S
No change in dipole moment – non-IR activity
Change in polarizability – Raman activity
Raman-active and Non-Raman-active
Vibrations (III)
Asymmetric Stretching of CS2
n2 S=C=S
Change so much in dipole moment – IR activity
Non-change in polarizability – Raman inactivity
Raman-active and Non-Raman-active
Vibrations (III)
Bending of CS2
n3 S=C=S
Change so much in dipole moment – IR activity
Non-change in polarizability – Raman inactivity
Intensity of Normal Raman Peaks
(1)Polarizability of the molecule
(2) Intensity of sources
(3) Concentration of active group in the molecule
(4) Excitation wavelength
(proportional to 4th power of frequency)
(5) Positions of the Raman signals are independent of
the excitation wavelength.
Instrumentation
q Light source: laser ( high power & polarized)
q Intensity of Raman ~ frequency4
- Ar ion laser produce 3X more intense Raman peak than He/Ne
- Sample decomposition & Fluorescence background
q Near-IR laser (Diode laser, Nd/YAG)
- Operating at much high power
w/o sample decomposition
- Applicable for bio-sample
- No or less fluorescence
Instrumentation
Ar-ion laser (488 nm) q Removal of fluorescence
background using NIR source
- strong fluorescence
background signal
- almost no fluorescence
with IR source
Nd-YAG laser
(1064 nm)
Instrumentation (general design)
Scattering (360o)
Instrumentation (Optical Fiber)
q Optical Fiber system
- remote analysis
- applicable for
on-line analysis
- input / collection
fibers
Instrumentation (FT-Raman System)
Quantitative Applications
q Less cluttered with peaks than infrared
spectra
q Peak overlap in mixtures is less likely;
quantitation is simple but……..
- high cost relative to that of absorption
instrumentation
- No background correction
- Fluctuation in laser intensity
q Wide Area Coverage Raman
Spectroscopy
Resonance Raman Spectroscopy
q Raman intensities are greatly enhanced
by excitation with electronic absorption
peak of an analyte
q Enhanced by a factor of 102 to 106
q Time scales
- Resonance Raman: 10-14 s
- Fluorescence: 10-6 ~ 10-8 s
q Important applications
- biological molecules
- presence of water & low conc. levels
q Limitation: interference by fluorescence
Surface Enhanced Raman Scattering
(SERS)
q Samples that are adsorbed on the surface of colloidal metal particles
(usually silver, gold, or copper)
q Enhanced by a factor of 103 to 106 (detection limit: 10-9 ~ 10-12 M)
q Multi-analyte targeting
Surface Enhanced Raman Scattering
(SERS)