The Study of Variational Transition State Theory on the Reactions, Cl+HBr, Cl+DBr, Br+HI and Br+DI

Variational transition state theory is used to study the dynamics of Cl+HBr, Cl+DBr, Br+HI and Br+DI reactions on several extended-LEPS surfaces, which were obtained by Persky et al recently. Rate constants, kinetic features on the bottleneck of the PES and kinetic isotopic effects are calculated for the title reactions. Our results for Cl+HBr and Cl+DBr are in good agreement with those of QCT calculations performed by Persky et al on the same surface, and available experiments, thus this surface is recommended to be used in further dynamical calculations. However, our results for Br+HI and Br+DI can’t match the QCT calculations and experiments. We think that the divergency between them comes from the possibility that the PES for Br+HI may not reproduce the realistic one exactly in the vicinity of the saddle point and some additional work about this surface is required.