Testing transition state theory on kac-Zwanzig model

Research output: Contribution to journalArticle

Abstract

A variant of the Kac-Zwanzig model is used to test the prediction of transition state theory (TST) and variational transition state theory (VTST). The model describes the evolution of a distinguished particle moving in a double-well external potential and coupled to N free particles through linear springs. While the Kac-Zwanzig model is deterministic, under appropriate choice of the model parameters the evolution of the distinguished particle can be approximated by a two-state Markov chain whose transition rate constants can be computed exactly in suitable limit. Here, these transition rate constants are compared with the predictions of TST and VTST. It is shown that the application of TST with a naive (albeit natural) choice of dividing surface leads to the wrong prediction of the transition rate constants. This is due to crossings of the dividing surface that do not correspond to actual transition events. However, optimizing over the dividing surface within VTST allows one to eliminate completely these spurious crossings, and therefore derive the correct transition rate constants for the model. The reasons why VTST is successful in this model are discussed, which allows one to speculate on the reliability of VTST in more complicated systems.

Original languageEnglish (US)
Pages (from-to)43-73
Number of pages31
JournalJournal of Statistical Physics
Volume126
Issue number1
DOIs
StatePublished - Jan 2007

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Transition State
Testing
Rate Constant
Model
Prediction
predictions
Markov chain
Eliminate
Markov chains

Keywords

  • Effective dynamics
  • Harmonic oscillators
  • Heat bath
  • Metastability
  • Stochastic equation
  • Transition rates
  • Transition state theory

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Statistical and Nonlinear Physics
  • Mathematical Physics

Cite this

Testing transition state theory on kac-Zwanzig model. / Ariel, G.; Vanden Eijnden, Eric.

In: Journal of Statistical Physics, Vol. 126, No. 1, 01.2007, p. 43-73.

Research output: Contribution to journalArticle

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