Intramolecular Energy Transfer Rates and Pathways for Vinyl Bromide

Abstract

The dynamics of intramolecular energy transfer in vinyl bromide are investigated using projection methods and results obtained from classical trajectories. The method is based on the calculation of the temporal variation of a diagonal kinetic energy matrix. Energy transfer rates and pathways are extracted from the envelope functions of this temporal variation. Average mode energies are also obtained from these data using the virial theorem. Total energy decay rates and the pathways of energy flow for initial excitation of each of the 12 vibrational modes in the equilibrium configuration and in initial configurations corresponding to points in the near vicinity of the minumum-energy structure on the optimum dividing surfaces for three-center H2 and HBr elimination are reported. The results for the equilibrium structure show that the total relaxation rate for each mode can be characterized with fair accuracy by a first-order rate law. The minimum decay rate among the 12 modes is at least 3.1 times larger th...