Closed-orbit theory for molecules in fields

Closed-orbit theory was initially developed as a qualitative and quantitative tool to interpret the dynamics of excited hydrogen in static external fields: the modulations in the photoabsorption spectrum were explained in terms of classical orbits closed at the nucleus. We consider the closed-orbit theory formalism appropriate for molecules in fields. The theoretical extensions are described, and semiclassical calculations based on this formalism are undertaken and compared to quantum R-matrix calculations for model molecules in a static magnetic field. We find that the spectral modulations can be analyzed simply in terms of the scattering of the excited electron on the molecular core. In addition to elastic scattering, modulations produced by inelastic scattering are essential to account for the photoabsorption spectrum. Through this process, an electron along a closed orbit in the classically chaotic regime exchanges energy with the core and comes out along an orbit in the near integrable regime. The relative importance of elastic and inelastic scattering depends on the molecular quantum defects.