Polarizability theory and sum rules

✍ Scribed by Soo-Y. Lee; Richard A. Mathies

• Publisher: Elsevier Science
• Year: 1988
• Tongue: English
• Weight: 291 KB
• Volume: 151
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(88)80059-9

✦ Synopsis

We derive a result from the polarizability theory of Raman scattering that unifies existing r&s for preresonancc and rcsonancc Raman scattering. It states that for resonance Raman scattering the O-.n Raman amplitude is the avcragc of the nth dcrivativc of the polarizabihty contributed by the resonant excited electrontc state over the ground vibrational state probability. By assuming a large energy denominator in the polarizability, it leads to the sum rule obtained by Harris, Mathies and Myers ( 1983) for preresonance Kaman scattermg. It 1s also shbwn that by a series expansion of the potential energy surfaces about the ground state equilibrium geometry, it leads to the simple sum rules for fundamental and overtone intensities derived by Heller, Sundberg and Tannor (1982).