Nuclear-Electronic Wave-Packet Dynamics in Perturbed Rydberg States of Molecular Hydrogen

Abstract

We use a time-dependent multichannel quantum defect theory to calculate wave packets in perturbed predissociated Rydberg states of molecular hydrogen. The calculations are ab initio in that they are based solely on known electronic energy curves $U(R)$ dependent on the internuclear distance $R$ and calculated by quantum chemical methods. The correlated motions of the nuclear and electronic wave packets are treated in a unified way which allows for nonadiabatic exchange of energy between them. We predict that the energy flow from the initially excited perturbed Rydberg levels to the fragmentation channels characteristically reflects the interactions between Rydberg channels.