Divided saddle theory: A new idea for rate constant calculation

János Daru, András Stirling

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9 Citations (Scopus)

Abstract

We present a theory of rare events and derive an algorithm to obtain rates from postprocessing the numerical data of a free energy calculation and the corresponding committor analysis. The formalism is based on the division of the saddle region of the free energy profile of the rare event into two adjacent segments called saddle domains. The method is built on sampling the dynamics within these regions: auxiliary rate constants are defined for the saddle domains and the absolute forward and backward rates are obtained by proper reweighting. We call our approach divided saddle theory (DST). An important advantage of our approach is that it requires only standard computational techniques which are available in most molecular dynamics codes. We demonstrate the potential of DST numerically on two examples: rearrangement of alanine-dipeptide (CH3CO-Ala-NHCH3) conformers and the intramolecular Cope reaction of the fluxional barbaralane molecule.

Original languageEnglish
Pages (from-to)1121-1127
Number of pages7
JournalJournal of chemical theory and computation
Volume10
Issue number3
DOIs
Publication statusPublished - Mar 11 2014

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ASJC Scopus subject areas

  • Computer Science Applications
  • Physical and Theoretical Chemistry

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