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

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8 Scopus citations


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
Issue number12
StatePublished - Jun 21 2012

ASJC Scopus subject areas

  • General Materials Science
  • Physical and Theoretical Chemistry


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