Transient anisotropy in degenerate systems: A semi-classical approach

Abstract

Abstract A semi-classical model for transient anisotropy in degenerate excited states is developed on the basis of a more general ansatz presented recently (O. Schalk and A.-N. Unterreiner, Phys. Chem. Chem. Phys. 12, 655 (2010)). This is the first model that can treat both rotational dephasing and the dynamics in degenerate systems, which is a prerequisite for a comprehensive theory to describe gas phase anisotropy experiments in small, highly symmetric systems. In the present contribution, it is shown that this model covers most of the features of the full quantum dynamical treatment and helps to give insights into the physical processes that are underlying these dynamics.