Inclusion of frequency shifts with electronic excitation in the calculation of multiple-order resonance Raman profile line shapes from optical absorption data

Abstract

A previously discussed exact relation which allows one to compute first-order resonance Raman intensity profile line shapes directly from optical absorption data within well-defined assumptions is generalized to approximately include vibrational frequency shifts with electronic excitation and is extended to profiles of higher order. For a large class of optical absorption line shapes and sufficiently small frequency shifts and temperatures, the generalization is found to be quite simple. We demonstrate its usefulness and the importance of including frequency shifts by using optical absorption data to compute first-, second-, and third-order profile line shapes for the KClO4:MnO−4 impurity system and comparing the results with measured profiles.