Journal of Chemical Physics, Vol.106, No.16, 6588-6595, 1997
Rovibrational and Rotational Autoionization Dynamics of Rydberg Electron Wavepackets in H-2 - A Time-Dependent Multichannel Quantum-Defect Theory Approach
The rovibrational and rotational autoionization dynamics of a Rydberg electron wavepacket in para-H-2 has been investigated using time-dependent multichannel quantum-defect theory (MQDT). In the case of rovibrational autoionization, rotational channel interactions are shown to introduce a phase shift to the electron wavepacket proportional to the strength of the configuration interaction. In the case of pure rotational autoionization, the electron wavepacket is observed to remain trapped in the Coulombic potential of the rotating molecule following rotational relaxation, thus increasing the autoionization lifetime.