Low barrier kinetics: dependence on observables and free energy surface.

Dynamics on free energy surfaces with high activation barriers are usually treated by few-state kinetics models, yielding characteristic rate coefficients and amplitudes depending on the connectivity of the states. When the barriers are low (< 3 kT), the assumption of instantaneous equilibration of the transition state, and hence, the few-state kinetics treatment, break down. Langevin dynamics is used here to explore the characteristic trends that occur in such cases, as a function of barrier height, number of barriers, dimensionality of the free energy surface, and switching functions that describe how spectroscopic probes vary from reactant to product. The result is a systematic phenomenological description of low barrier kinetics and dynamics. Copyright 2005 Wiley Periodicals, Inc.