On bimolecular kinetics, the Bloch equation and Wigner path integrals

摘要

We continue our study of Wigner path integrals. We first define a Wigner path integral for the kernel of the Wignerndash;Bloch equation, solve it for the free particle and harmonic oscillator cases, discuss the physical interpretation which is new and then we apply it (along with the path integral representation of the Liouville equation) to obtain a path integral representation in phase space of the quantum transition state theory of Miller. We also obtain an expression involving products of Wigner kernels for the correlation function form of the exact bimolecular rate constant.