Theoretical study of photodetachment processes of anionic boron clusters. II. Dynamics

Abstract

Photodetachment bands of anionic boron clusters, B n (n = 4,5) are theoretically examined here. The model Hamiltonians developed through extensive ab initio quantum chemistry calculations in Paper I are employed for the required nuclear dynamics study. While the precise location of vibronic lines and progression of vibrational modes within a given electronic band is derived from time-independent quantum mechanical studies, the broadband spectral envelopes and the nonradiative decay rate of electronic states are calculated by propagating wave packets in a time-dependent quantum mechanical framework. The theoretical results are in good accord with the experiment to a large extent. The discrepancies between the two can be partly attributed to the inadequate energy resolution of the experimental results and also to the neglect of dynamic spin-orbit interactions and computational difficulty related with detachment channels involving multi-electron transitions in the theoretical formalism. © 2012 American Institute of Physics.