Journal of Chemical Physics, Vol.113, No.9, 3633-3640, 2000
Reactive excitation functions for F plus p-H-2/n-H-2/D-2 and the vibrational branching for F+HD
Complementary to our recent report on the F+HD reaction, the reactive excitation functions for the other isotopomers are presented. Through analysis of the differential cross section data, the collisional energy dependencies of product vibrational branchings for F+HD are also reported here. Several important conclusions can be drawn from this work. First, the transition-state properties, in particular the barrier height, of this reaction are well-characterized by the SW PES, despite its neglect of spin-orbit couplings. Second, contrary to the theoretical conclusion in recent literatures, an experimental observation is presented which seems to suggest that a resonance may indeed exist for the F+H-2 reaction in support of the original interpretation proposed by Lee and co-workers. Third, the vibrational branching for the F+HD --> HF+D reaction elucidates another facet of resonance effects in the integral cross sections. Finally, the nonadiabatic reactivity of the spin-orbit excited F*(P-2(1/2)) atom is found to be small, which is in line with the conclusion inferred from a most recent, full quantum mechanical multisurface calculation.