The inverted regime photoinduced electron transfer kinetics of betaine‐30 have been investigated over a broad temperature range, revealing very little temperature dependence. For example, for betaine‐30 in a polystyrene film, the electron transfer rate constant, kET, changes by less than a factor of 3 from T=293 K to T=34 K. The results are in striking contrast to predictions of contemporary electron transfer theories which employ classical nuclear modes to accept some or all of the energy of the electron transfer event. The comparison of theory and experiment for the betaines demonstrates that a full quantum mechanical theory is necessary to accurately describe the electron transfer kinetics of the betaines in environments with slow dielectric relaxation. The conclusions drawn for the betaines may also apply to other molecular examples of inverted regime electron transfer in slowly relaxing environments.
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15 May 1992
Letter|
May 15 1992
Temperature dependence of the inverted regime electron transfer kinetics of betaine‐30 and the role of molecular modes Available to Purchase
Eva Åkesson;
Eva Åkesson
Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455
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Alan E. Johnson;
Alan E. Johnson
Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455
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Nancy E. Levinger;
Nancy E. Levinger
Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455
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Gilbert C. Walker;
Gilbert C. Walker
Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455
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Thomas P. DuBruil;
Thomas P. DuBruil
Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455
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Paul F. Barbara
Paul F. Barbara
Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455
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Eva Åkesson
Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455
Alan E. Johnson
Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455
Nancy E. Levinger
Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455
Gilbert C. Walker
Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455
Thomas P. DuBruil
Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455
Paul F. Barbara
Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455
J. Chem. Phys. 96, 7859–7862 (1992)
Article history
Received:
June 06 1991
Accepted:
July 22 1991
Citation
Eva Åkesson, Alan E. Johnson, Nancy E. Levinger, Gilbert C. Walker, Thomas P. DuBruil, Paul F. Barbara; Temperature dependence of the inverted regime electron transfer kinetics of betaine‐30 and the role of molecular modes. J. Chem. Phys. 15 May 1992; 96 (10): 7859–7862. https://doi.org/10.1063/1.462384
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