An Alternative Derivation of Quantum Mechanical Transition State Reaction Rate Theory

Abstract

The quantum mechanical transition state reaction rates for both microcanonical and macrocanonical expressions are derived from a recently developed classical reaction rate theory. The newly derived quantum transition-state-like rates are good for both unimolecular reaction and bimolecular reaction depending on the choices of the transition state dividing surfaces. In a special choice of the transition dividing surface for bimolecular reaction, the macrocanonic rate derived in this paper is reduced to the flux-flux autocorrelation formalism derived from quantum bimolecular reactive scattering by Miller and to those obtained by Yamamoto using Kuto linear response analysis.