Raman

Spectroscopy
Laser 4880
Raman
Spectroscopy
Selection Rules
Infrared: Intensity of a peak is related to the change in the dipole
moment associated in going from the ground state to an excited
state; the principle vibrational quantum number changes by 1
Raman: Intensity of a peak is related to the polarizabilityof the
stretch. Non-polar bonds are usually more easily polarized than
polar bonds.
Comparison of IR and Raman Spectroscopy
1. Bands that are intense in the IR are usually weak in the Raman.
The spectral interference associated with hydrogen bonding is
greatly reduced. Similar reduction in interference can also be
obtain by examining gas phase spectra. Water is a useful solvent
in Raman whereas water is a poor solvent for IR studies. The
optics in Raman are made from glass or quartz instead of salts
(NaCl, KBr, CsI).
NH
2
CH
2
CH
2
OH
Liquid film
KBr
Comparison of IR and Raman Spectroscopy
1. Bands that are intense in the IR are usually weak in the Raman. The
spectral interference associated with hydrogen bonding is greatly
reduced. Similar reduction in interference can also be obtain by
examining gas phase spectra. Water is a useful solvent in Raman
whereas water is a poor solvent for IR studies. The optics in Raman
are made from glass or quartz instead of salts (NaCl, KBr, CsI).
2. Molecules with a center of symmetry have no coincident IR and
Raman bands. Thus a comparison of the two spectra can provide
structural information.
3. Raman spectra are generally simpler that IR spectra. Overtones and
combination bands frequent in IR are less common.
KBr
powder
powder
KBr
Comparison of IR and Raman Spectroscopy
1. Bands that are intense in the IR are usually weak in the Raman.
The spectral interference associated with hydrogen bonding is greatly
reduced. Similar reduction in interference can also be obtain by
examining gas phase spectra. Water is a useful solvent in Raman
whereas water is a poor solvent for IR studies. The optics in Raman are
made from glass or quartz instead of salts (NaCl, KBr, CsI).
2. Molecules with a center of symmetry have no coincident IR and
Raman bands. Thus a comparison of the two spectra can provide
structural information.
3. Raman spectra are generally simpler that IR spectra.
Overtones and combination bands frequent in IR are less common.
Comparison of IR and Raman Spectroscopy
2. Molecules with a center of symmetry have no coincident IR and
Raman bands. Thus a comparison of the two spectra can provide
structural information.
3. Raman spectra are generally simpler that IR spectra. Overtones and
combination bands frequent in IR are less common.
4. The entire IR range can be covered by Raman spectroscopy since
a laser, usually in the visible region is used and the spectrum is
obtained by looking at the frequency differences from the
incident frequency. In IR, different optics and beam-splitters are
needed to cover the entire useful range from the near IR to the
far IR.
Comparison of IR and Raman Spectroscopy
5. IR spectrometers are less expensive and more sensitive
instruments. Intensity measurement in Raman are very sensitive
to laser power, and cell geometry, and are less reproducible than
IR spectra.
6. A small fraction of the incident photons in Raman are scattered, (e. g.
10
-8
). Broadband fluorescence can obscure the Raman signals.
7. As a result of the simplification in the spectra, Raman spectroscopy
provides less structural information.
Liquid film
liquid
D serine
DL