Time Reversal and the Law of Reciprocity in Raman Scattering

Abstract

Employing exact energy operators for the construction of effective polarizability operators, the previously derived approximate relationship (8ub)mn = (8,&,,gm between a complex transition polarizability and the corresponding transition polarizability with time-reversed initial and final molecular states has been found to represent an exact identity for a single microscopic Raman scattering event. Based on this result and the associated time ordered diagrams, macroscopic pictorial arguments are used to generalize the law of reciprocity to cover Raman scattering, thereby eliminating the prejudice that it applies only to Rayleigh scattering. Our predictions accord with the results of recent Stokes and anti-Stokes resonance Raman experiments.