Kinetics of Unimolecular Breakdown. I. The Formal Solution

Abstract

A quantum‐mechanical discussion of the kinetics of unimolecular breakdown is presented using the Green's operator formalism. Experimentally, chemical reactions are characterized by their products and the theoretical discussion starts from this fact in an attempt to define the activated state. A scheme is indicated for the calculation of experimental results such as rate constants or yields of products. The concept of a natural line shape of a process is employed in discussing the separation of excitation and breakdown stages and the limitations on such a description are noted. Applications are made to model theories of chemical reaction rates and to results of computer simulation studies.