Anharmonic Electron−Phonon Coupling in Condensed Media: 1. Formalism

Abstract

Three different schemes for calculating anharmonic line shape functions are reported and discussed for the first time in this article using eigenstate representation. First, the linear dipole-moment time correlation function (DMTCF), homogeneous (single-site) absorption line shape function, and the respective Franck-Condon factors (FCF) are derived and explored as a molecule makes a transition from a harmonic to an anharmonic (Morse potential) electronic state. Second, the linear DMTCF, homogeneous absorption line shape function, and FCFs are also derived as a molecule makes a transition from one anharmonic to another linearly displaced anharmonic state; FCFs in this case are reported in an exact closed-form expressed in terms of Appell's hypergeometric function. Third, same as the latter set of results are reported but with both linearly displaced and distorted shape of the upper Morse potential. FCFs of the zero-phonon line in all three cases are reported. The first case is rather mathematically complex as a result of taking the overlap integral of the Morse oscillator eigenfunctions, whose spatial decay is a simple exponential, with those of harmonic oscillator, whose decay is a Gaussian. This form of a functional disparity gives rise to some challenges. Model calculations are presented and discussed.