Resonance Raman Spectroscopy - History

History

Raman spectroscopy utilizes the phenomenon of scattering. When light passes through a transparent sample, a fraction of the light is scattered in all directions. Most of the scattered photons are of the same wavelength of the incident light. This is known as Rayleigh scattering. However, in 1928, physicists C.V. Raman and K.S. Krishnan, and independently Grigory Landsberg and Leonid Mandelstam discovered that a small fraction of the scattered light had a different wavelength. Furthermore, this difference depended on the molecules present in the sample. For these observations, and his explanation of the phenomenon, Raman was awarded the 1930 Nobel Prize in physics. His explanation is now known as the theory of Raman scattering.

In the years following its discovery, Raman spectroscopy was used to provide the first catalog of molecular vibrational frequencies. Originally, heroic measures were required to obtain Raman spectra due to the low sensitivity of the technique. Typically, the sample was held in a long tube and illuminated along its length with a beam of filtered monochromatic light generated by a gas discharge lamp. The photons that were scattered by the sample were collected through an optical flat at the end of the tube. To maximize the sensitivity, the sample was highly concentrated (1 M or more) and relatively large volumes (5 mL or more) were used. Consequently, the use of Raman spectroscopy dwindled when commercial IR spectrophotometers became available in the 1940s. However, the advent of the laser in the 1960s resulted in simplified Raman spectroscopy instruments and also boosted the sensitivity of the technique. This has revived the use of Raman spectroscopy as a common analytical technique.