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Low barrier kinetics: Dependence on observables and free energy surface
Author(s) -
Ma Hairong,
Gruebele Martin
Publication year - 2005
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.20311
Subject(s) - observable , kinetics , surface (topology) , energy (signal processing) , chemistry , statistical physics , physics , mathematics , classical mechanics , quantum mechanics , geometry
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