Local regularity and non-recrossing path in transition state—a new strategy in chemical reaction theories

Abstract

We analyze local regularities in the regions of transition states of a 6-atom Lennard-Jones cluster to demonstrate how one can choose a non-recrossing reaction path in phase space along which the transmission coefficient for the classical reaction path is unity from threshold up to a moderately high energy, above which the transition state is chaotic, and how one can picture the nonlinear, full-phase-space character of the dividing hypersurface by projecting it into spaces of only a few dimensions. These overcome one of the long-standing ambiguities in chemical reaction theories, the recrossing problem, up to moderately high energies, and make transition state theory more generalized, applicable even in cases in which apparent recrossings spoil the conventional theory.