화학공학소재연구정보센터
Journal of Chemical Physics, Vol.105, No.24, 10812-10818, 1996
A Position-Dependent Friction Model for Solution Reactions in the High Friction Regime - Proton-Transfer in Triosephosphate Isomerase (Tim)
A position dependent friction model based on Grote-Hynes theory is developed to describe activated rate processes in the high friction regime. The model is employed to determine the transmission coefficient, which corrects the transition state theory rate constant for recrossing of the transition state. A simple expression is derived for the transmission coefficient in the limit of a slow response of the thermal bath. The model is applied to the initial proton transfer step in the reaction catalyzed by triosephosphate isomerase, for which the standard Grote-Hynes theory was found to be inappropriate. The predictions of the position dependent friction model are in a good agreement with results of detailed molecular dynamics simulations. The method used to determine the transmission coefficient should be generally applicable to reactions that are strongly coupled to a slow thermal bath.