Long-range transition state theory

Abstract

The implementation of variational transition state theory (VTST) for long-range asymptotic potential forms is considered, with particular emphasis on the energy and total angular momentum resolved (μJ-VTST) implementation. A long-range transition state approximation yields a remarkably simple and universal description of the kinetics of reactions governed by long-range interactions. The resulting (μJ-VTST) implementation is shown to yield capture-rate coefficients that compare favorably with those from trajectory simulations (deviating by less than 10%) for a wide variety of neutral and ionic long-range potential forms. Simple analytic results are derived for many of these cases. A brief comparison with a variety of low-temperature experimental studies illustrates the power of this approach as an analysis tool. The present VTST approach allows for a simple analysis of the applicability conditions for some related theoretical approaches. It also provides an estimate of the temperature or energy at which the “long-range transition state” moves to such short separations that short-range effects, such as chemical bonding, steric repulsion, and electronic state selectivity, must be considered.