Ensemble-averaged variational transition state theory with optimized multidimensional tunneling for enzyme kinetics and other condensed-phase reactions

被引：110

作者：

Truhlar, DG

Gao, JL

Garcia-Viloca, M

Alhambra, C

Corchado, J

Sanchez, ML

Poulsen, TD

机构：

[1] Univ Minnesota, Dept Chem, Minneapolis, MN 55455 USA

[2] Univ Minnesota, Inst Supercomp, Minneapolis, MN 55455 USA

来源：

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY | 2004年 / 100卷 / 06期

关键词：

combined quantum mechanical/molecular mechanical method; hydride transfer; kinetic isotope effects; potential of mean force; proton transfer; quantized vibrations; quantum mechanical dynamics; rate constants; semiclassical theory of tunneling; statistical theory;

D O I：

10.1002/qua.20205

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

This paper provides an overview of a new method developed to include quantum mechanical effects and free energy sampling in calculations of reaction rates in enzymes. The paper includes an overview of variational transition state theory with optimized multidimensional tunneling for simple gas-phase reactions and then shows how this is extended to incorporate free energy effects and to include protein motions in the reaction coordinate by ensemble averaging. Finally we summarize recent comparisons to experiment for primary and secondary kinetic isotope effects for proton and hydride transfer reactions catalyzed by enzymes. (C) 2004 Wiley Periodicals, Inc.

引用

页码：1136 / 1152

页数：17

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[32] Direct dynamics for free radical kinetics in solution: Solvent effect on the rate constant for the reaction of methanol with atomic hydrogen [J].