Impact of Temperature and Non-Gaussian Statistics on Electron Transfer in Donor–Bridge–Acceptor Molecules

Waskasi, Morteza M.; Newton, Marshall D.; Matyushov, Dmitry V.

doi:10.1021/acs.jpcb.7b00140

Title: Impact of Temperature and Non-Gaussian Statistics on Electron Transfer in Donor–Bridge–Acceptor Molecules

Journal Article · Mon Mar 06 00:00:00 EST 2017 · Journal of Physical Chemistry. B

DOI:https://doi.org/10.1021/acs.jpcb.7b00140· OSTI ID:1349132

Waskasi, Morteza M. ^[1]; Newton, Marshall D. ^[2];

^[3]

School of Molecular Sciences, Arizona State University, P.O. Box 871604, Tempe, Arizona 85287-1604, United States
Chemistry Department, Brookhaven National Laboratory, Box 5000, Upton, New York 11973-5000, United States
School of Molecular Sciences, Arizona State University, P.O. Box 871604, Tempe, Arizona 85287-1604, United States, Department of Physics, Arizona State University, P.O. Box 871504, Tempe, Arizona 85287-1504, United States

A combination of experimental data and theoretical analysis provides evidence of a bell-shaped kinetics of electron transfer in the Arrhenius coordinates ln k vs 1/T. This kinetic law is a temperature analogue of the familiar Marcus bell-shaped dependence based on ln k vs the reaction free energy. Our results were obtained for reactions of intramolecular charge shift between the donor and acceptor separated by a rigid spacer studied experimentally by Miller and co-workers. The non-Arrhenius kinetic law is a direct consequence of the solvent reorganization energy and reaction driving force changing approximately as hyperbolic functions with temperature. Furthermore, the reorganization energy decreases and the driving force increases when temperature is increased. The point of equality between them marks the maximum of the activationless reaction rate. In reaching the consistency between the kinetic and thermodynamic experimental data requires the non-Gaussian statistics of the donor–acceptor energy gap described by the Q-model of electron transfer. The theoretical formalism combines the vibrational envelope of quantum vibronic transitions with the Q-model describing the classical component of the Franck–Condon factor and a microscopic solvation model of the solvent reorganization energy and the reaction free energy.

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Research Organization:: Arizona State Univ., Tempe, AZ (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: SC0015641; SC00112704

OSTI ID:: 1349132

Alternate ID(s):: OSTI ID: 1345668; OSTI ID: 1349562

Report Number(s):: BNL-113671-2017-JA

Journal Information:: Journal of Physical Chemistry. B, Journal Name: Journal of Physical Chemistry. B Vol. 121 Journal Issue: 12; ISSN 1520-6106

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 11 works

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