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

We analyze local regularities in the regions of transition states of a 6-at om 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 pictu re the nonlinear, full-phase-space character of the dividing hypersurface b y projecting it into spaces of only a few dimensions. These overcome one of the long-standing ambiguities in chemical reaction theories, the recrossin g problem, up to moderately high energies, and make transition state theory more generalized, applicable even in cases in which apparent recrossings s poil the conventional theory. (C) 2000 Elsevier Science B.V. All rights res erved.