Non-ergodic electron transfer in mixed-valence charge-transfer complexes

Research output: Contribution to journalArticle

7 Citations (Scopus)

Abstract

Theories of activated transitions traditionally separate the dynamics and statistics of the thermal bath in the reaction rate into the preexponential frequency factor for the dynamics and a Boltzmann factor for the statistics. When the reaction rate is comparable to relaxation frequencies of the medium, the statistics loses ergodicity and the activation barrier becomes dependent on the medium dynamics. This scenario is realized for mixed-valence self-exchange electron transfer at temperatures near the point of solvent crystallization. These complexes, studied by Kubiak and coworkers, display anti-Arrhenius temperature dependence on lowering temperature when approaching crystallization; that is, the reaction rate increases nonlinearly in Arrhenius coordinates. Accordingly, the solvent relaxation slows down following a power temperature law. With this functional form for the relaxation time, nonergodic reaction kinetics accounts well for the observations.

Original languageEnglish (US)
Pages (from-to)1644-1648
Number of pages5
JournalJournal of Physical Chemistry Letters
Volume3
Issue number12
DOIs
StatePublished - Jun 21 2012

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Charge transfer
electron transfer
reaction kinetics
charge transfer
Reaction rates
valence
Electrons
Statistics
statistics
Crystallization
crystallization
Temperature
Reaction kinetics
Relaxation time
temperature
baths
relaxation time
Chemical activation
activation
temperature dependence

ASJC Scopus subject areas

  • Materials Science(all)

Cite this

Non-ergodic electron transfer in mixed-valence charge-transfer complexes. / Matyushov, Dmitry.

In: Journal of Physical Chemistry Letters, Vol. 3, No. 12, 21.06.2012, p. 1644-1648.

Research output: Contribution to journalArticle

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