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

Authors

  • Donald G. Truhlar,

    Corresponding author
    1. Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant St., S.E., Minneapolis, Minnesota 55455-0431, USA
    • Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant St., S.E., Minneapolis, Minnesota 55455-0431, USA
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  • Jiali Gao,

    1. Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant St., S.E., Minneapolis, Minnesota 55455-0431, USA
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  • Mireia Garcia-Viloca,

    1. Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant St., S.E., Minneapolis, Minnesota 55455-0431, USA
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  • Cristobal Alhambra,

    1. Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant St., S.E., Minneapolis, Minnesota 55455-0431, USA
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  • Jose Corchado,

    1. Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant St., S.E., Minneapolis, Minnesota 55455-0431, USA
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  • Maria Luz Sanchez,

    1. Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant St., S.E., Minneapolis, Minnesota 55455-0431, USA
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  • Tina D. Poulsen

    1. Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant St., S.E., Minneapolis, Minnesota 55455-0431, USA
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Abstract

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

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