Dynamics of reactions involving diffusive barrier crossing

Klaus J Schulten, Zaida Ann Luthey-Schulten, Attila Szabo

Research output: Contribution to journalArticle

Abstract

We develop a first passage time description for the kinetics of reactions involving diffusive barrier crossing in a bistable (and also in a more general) potential, a situation realized, for example, in some photoisomerization processes. In case the reactant is in thermal equilibrium, the first passage times account well for the reaction dynamics as shown by comparison with exact numerical calculations. A simple integral expression for the rate constants is presented. For a case involving a reactant initially far off equilibrium, a two relaxation time description for the particle number N(t) is derived and compared with the results of an "exact" calculation. This description results from a knowledge of N(t=0), N(t=0), ∫0dt N(t), i.e., the first passage time, and ∫0dt t N(t).

Original languageEnglish (US)
Pages (from-to)4426-4432
Number of pages7
JournalThe Journal of Chemical Physics
Volume74
Issue number8
DOIs
StatePublished - Jan 1 1981

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Photoisomerization
Relaxation time
Rate constants
Kinetics
relaxation time
kinetics
Hot Temperature

ASJC Scopus subject areas

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

Cite this

Dynamics of reactions involving diffusive barrier crossing. / Schulten, Klaus J; Luthey-Schulten, Zaida Ann; Szabo, Attila.

In: The Journal of Chemical Physics, Vol. 74, No. 8, 01.01.1981, p. 4426-4432.

Research output: Contribution to journalArticle

Schulten, Klaus J ; Luthey-Schulten, Zaida Ann ; Szabo, Attila. / Dynamics of reactions involving diffusive barrier crossing. In: The Journal of Chemical Physics. 1981 ; Vol. 74, No. 8. pp. 4426-4432.
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