Calculation of the transition state theory rate constant for a general reaction coordinate: Application to hydride transfer in an enzyme

James B. Watney, Alexander V. Soudackov, Kim F. Wong, Sharon Hammes-Schiffer

Research output: Contribution to journalArticlepeer-review

26 Scopus citations

Abstract

An expression for the transition state theory rate constant is provided in terms of the potential of mean force for a general reaction coordinate and the mass-weighted gradient of this reaction coordinate. The form of the rate constant enables the straightforward calculation of rates for infrequent events with conventional umbrella sampling and free energy perturbation methods. The approach is illustrated by an application to hydride transfer in the enzyme dihydrofolate reductase using a hybrid quantum/classical molecular dynamics method. Inclusion of the nuclear quantum effects of the transferring hydrogen increases the transition state theory rate constant by a factor of 244.

Original languageEnglish (US)
Pages (from-to)268-271
Number of pages4
JournalChemical Physics Letters
Volume418
Issue number1-3
DOIs
StatePublished - Jan 25 2006
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • General Physics and Astronomy
  • Physical and Theoretical Chemistry

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