The roles of vibronic coupling and the Duschinsky effect in resonance Raman scattering

In most vibronic treatments of resonance Raman scattering it is assumed that the normal coordinates of electronically excited states are not rotated relative to those of the ground state, i.e., the Duschinsky effect is neglected. In the present paper this assumption is critically examined for the case of resonance Raman scattering by a non-totally symmetric vibrational mode. For consistency also the second-order Herzberg-Teller coupling is considered. It is shown that these second-order couplings introduce asymmetry in the excitation profile of appearance similar to that due to nonadiabatic coupling. Also it is shown that even small rotations give rise to noticeable effects in the polarization dispersion curve. Analytical formulas for the Franck-Condon factors and for the Raman tensor (valid for an arbitrary number of normal modes) for the case of small rotations are given, and illustrative calculations of excitation and polarization dispersion curves for a two mode system are presented and discussed.