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Ensemble‐averaged variational transition state theory with optimized multidimensional tunneling for enzyme kinetics and other condensed‐phase reactions
Author(s) -
Truhlar Donald G.,
Gao Jiali,
GarciaViloca Mireia,
Alhambra Cristobal,
Corchado Jose,
Luz Sanchez Maria,
Poulsen Tina D.
Publication year - 2004
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.20205
Subject(s) - quantum tunnelling , reaction coordinate , kinetic isotope effect , chemistry , transition state theory , quantum , kinetic energy , transition state , statistical physics , kinetics , proton , phase transition , thermodynamics , computational chemistry , quantum mechanics , physics , reaction rate constant , catalysis , biochemistry , deuterium
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. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2004