Semiclassical transition state theory. A new perspective

Abstract

The semiclassical transition state theory (SCTST) introduced by Miller, Hernandez, Handy, Jayatilaka and Willetts requires the inversion of an (effectively integrable ) Hamiltonian with respect to the action of the reactive coordinate. It is shown that the inversion may be avoided in computing the thermal rate constant; the resulting expression also provides an appealing link to conventional transition state theory. This reformulation of the SCTST rate is illustrated by application to the bimolecular reaction, H + H 2→H 2 + H, and to the unimolecular dissociation, D 2CO→D 2 + CO.