Title: A surface-hopping method for semiclassical calculations of cross sections for radiative association with electronic transitions,
Abstract: A semicalssical method based on surface-hopping techniques is developed to
model the dynamics of radiative association with electronic transitions in
arbitrary polyatomic systems. It can be proven that our method is an extension
of the established semiclassical formula used in the characterization of
diatomic molecule- formation. Our model is tested for diatomic molecules. It
gives the same cross sections as the former semiclassical formula, but contrary
to the former method it allows us to follow the fate of the trajectories after
the emission of a photon. This means that we can characterize the rovibrational
states of the stabilized molecules: using semiclassial quantization we can
obtain quantum state resolved cross sections or emission spectra for the
radiative association process. The calculated semiclassical state resolved
spectra show good agreement with the result of quantum mechanical perturbation
theory. Furthermore our surface-hopping model is not only applicable for the
description of radiative association but it can be use for semiclassical
characterization of any molecular process where spontaneous emission occurs.