Alignment Effects in Electronic Energy Transfer and Reactive Events

Abstract

The rates of electronic curve crossing processes depend critically on the alignment of atomic orbitals, which determine the symmetries of the electronic potentials participating in the reaction or energy transfer event. Recent work from our laboratory is presented on the effect of orbital alignment in near resonant energy transfer processes of electronically excited Ca and Sr atoms. Several energy transfer events are carried out on aligned p-states in collisions with rare gases. The simplicity of the rare gas systems in terms of their symmetry and nonreactive nature is advantageous for comparison to accurate theoretical treatment. In the context of understanding chemical phenomena, collisions of these atoms with molecular partners are also investigated. This opens the possibility to study the correlation of alignment dependent effects in competing reactive and energy transfer pathways. Remarkably state-specific alignment effects are also observed when two or more independent energy transfer pathways are accessible.