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Detecting reaction pathways and computing reaction rates in condensed phase

Consta, S. 2006. Detecting reaction pathways and computing reaction rates in condensed phase. THEORETICAL CHEMISTRY ACCOUNTS 116 (1-3): 373-382.
Author Full Name(s): Consta, Styliani

Keywords Plus:
TRANSITION-STATE THEORY; NONEQUILIBRIUM SOLVATION DYNAMICS; REACTION COORDINATE DYNAMICS; TIME-CORRELATION FUNCTIONS; CHEMICAL-REACTIONS; FREE-ENERGY; STATISTICAL-MECHANICS; MOLECULAR-DYNAMICS; AQUEOUS CLUSTERS; BROWNIAN-MOTION

Abstract:
Methods for the computation of rate constants that characterize classical reactions occurring in the condensed phase are discussed. While microscopic expressions for these transport properties are well known, their computation presents challenges for simulation since reactive events often occur rarely, and the long time scales that are typical for reactive processes are not accessible using simple molecular dynamics methods. Furthermore, the underlying free energy surface is very complex with many saddle points that prevent sampling of possible reaction pathways. As a result, the reaction coordinate may be a complex many-body function of the system's degrees of freedom. Since there is not an a priori way to define a "good" reaction coordinate, methods are being developed to assist in a systematic construction of a reaction coordinate. These methods are reviewed and examples of non-trivial reaction coordinates are presented.