Marcus Bell-Shaped Electron Transfer Kinetics Observed in an Arrhenius Plot

Morteza M. Waskasi, Gerdenis Kodis, Ana L Moore, Thomas A Moore, John Devens Gust, Dmitry V. Matyushov

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

The Marcus theory of electron transfer predicts a bell-shaped dependence of the reaction rate on the reaction free energy. The top of the "inverted parabola" corresponds to zero activation barrier when the electron-transfer reorganization energy and the reaction free energy add up to zero. Although this point has traditionally been reached by altering the chemical structures of donors and acceptors, the theory suggests that it can also be reached by varying other parameters of the system including temperature. We find here dramatic evidence of this phenomenon from experiments on a fullerene-porphyrin dyad. Following photoinduced electron transfer, the rate of charge recombination shows a bell-shaped dependence on the inverse temperature, first increasing with cooling and then decreasing at still lower temperatures. This non-Arrhenius rate law is a result of a strong, approximately hyperbolic temperature variation of the reorganization energy and the reaction free energy. Our results provide potentially the cleanest confirmation of the Marcus energy gap law so far since no modification of the chemical structure is involved.

Original languageEnglish
Pages (from-to)9251-9257
Number of pages7
JournalJournal of the American Chemical Society
Volume138
Issue number29
DOIs
Publication statusPublished - Jul 27 2016

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Arrhenius plots
Electrons
Free energy
Kinetics
Temperature
Fullerenes
Energy Transfer
Porphyrins
Energy transfer
Genetic Recombination
Reaction rates
Energy gap
Chemical activation
Cooling
Experiments

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Marcus Bell-Shaped Electron Transfer Kinetics Observed in an Arrhenius Plot. / Waskasi, Morteza M.; Kodis, Gerdenis; Moore, Ana L; Moore, Thomas A; Gust, John Devens; Matyushov, Dmitry V.

In: Journal of the American Chemical Society, Vol. 138, No. 29, 27.07.2016, p. 9251-9257.

Research output: Contribution to journalArticle

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