Molecules in external fields: a semiclassical analysis

Abstract

We undertake a semiclassical analysis of the spectral properties (modulations of photoabsorption spectra, energy level statistics) of a simple Rydberg molecule in static fields within the framework of Closed-Orbit/Periodic-Orbit theories. We conclude that in addition to the usual classically allowed orbits one must consider classically forbidden diffractive paths. Further, the molecule brings in a new type of 'inelastic' diffractive trajectory, different from the usual 'elastic' diffractive orbits encountered in previous studies of atomic and analogous systems such as billiards with point-scatterers. The relative importance of inelastic versus elastic diffraction is quantified by merging the usual Closed Orbit theory framework with molecular quantum defect theory.