Rydberg Molecules in External Fields: A Semiclassical Analysis

We analyze the spectra of simple Rydberg molecules in static fields within the framework of closed/periodic-orbit theories. We conclude that in addition to the usual classical orbits one must consider classically forbidden diffractive paths. Further, the molecule brings in a new type of “inelastic” diffractive trajectory in addition to the usual “elastic” diffractive orbits encountered in systems 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.