Uniform semiclassical expansions for the direct part of Franck-Condon transitions

Abstract

Semiclassical expansions for traces involving Green's functions receive two contributions, one from the periodic or recurrent orbits of the classical system and one from the phase space volume, i.e., the paths of infinitesimal length. Quantitative calculations require the control of both terms. Here we discuss the contribution from paths of zero length with an emphasis on the application to Franck-Condon transitions. The expansion in the energy representation is asymptotic and a critical parameter is identified. In the time domain, a series expansion of the logarithm of the propagator gives very good results. The expansions are illustrated for transitions onto a linear potential and onto a harmonic oscillator.