Low barrier kinetics: Dependence on observables and free energy surface

✍ Scribed by Hairong Ma; Martin Gruebele

• Publisher: John Wiley and Sons
• Year: 2005
• Tongue: English
• Weight: 422 KB
• Volume: 27
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/jcc.20311

✦ Synopsis

Abstract

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. © 2005 Wiley Periodicals, Inc. J Comput Chem 27: 125–134, 2006