On transition-state theory and the classical mechanics of collinear collisions

Abstract

We consider classical transition‐state theory of collinear atom‐diatom reactions. There are (many) potential surfaces for which this theory is exact provided all trajectories with energy above some fixed value are disregarded; the energy cutoff of course depends on the surface. We develop a simple criterion for recognizing or constructing such surfaces, and discuss examples. We also show that if a surface has a proper transition state, as defined below, then transition‐state theory is exact unless collision complexes exist.