Nonergodic activated kinetics in polar media

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15 Scopus citations

Abstract

A theoretical formulation is developed for the activated kinetics when some subset of nuclear modes of the thermal bath is slower than the reaction and ergodicity of the thermal bath is not maintained. Nonergodic free energy profiles along the reaction coordinate are constructed by using restricted canonical ensembles with the phase space available to the system found by solving a self-consistent kinetic equation. The resulting activation barrier incorporates not only thermodynamic parameters but also dynamical information from the time autocorrelation function of the solute-solvent interaction energy. The theory is applied to the reactions of solvolysis and charge transfer in polar media.

Original languageEnglish (US)
Article number164522
JournalJournal of Chemical Physics
Volume130
Issue number16
DOIs
StatePublished - 2009

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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