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 language | English (US) |
|---|---|
| Pages (from-to) | 1644-1648 |
| Number of pages | 5 |
| Journal | Journal of Physical Chemistry Letters |
| Volume | 3 |
| Issue number | 12 |
| DOIs | |
| State | Published - Jun 21 2012 |
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ASJC Scopus subject areas
- Materials Science(all)
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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 journal › Article
}
TY - JOUR
T1 - Non-ergodic electron transfer in mixed-valence charge-transfer complexes
AU - Matyushov, Dmitry
PY - 2012/6/21
Y1 - 2012/6/21
N2 - 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.
AB - 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.
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U2 - 10.1021/jz300630t
DO - 10.1021/jz300630t
M3 - Article
AN - SCOPUS:84863673996
VL - 3
SP - 1644
EP - 1648
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
SN - 1948-7185
IS - 12
ER -