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

Abstract

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.

Authors:
 [1];  [2]; ORCiD logo [3]
+ Show Author Affiliations
  1. School of Molecular Sciences, Arizona State University, P.O. Box 871604, Tempe, Arizona 85287-1604, United States
  2. Chemistry Department, Brookhaven National Laboratory, Box 5000, Upton, New York 11973-5000, United States
  3. 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
Publication Date:
Research Org.:
Arizona State Univ., Tempe, AZ (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1349132
Alternate Identifier(s):
OSTI ID: 1345668; OSTI ID: 1349562
Report Number(s):
BNL-113671-2017-JA
Journal ID: ISSN 1520-6106
Grant/Contract Number:  
SC0015641; SC00112704
Resource Type:
Published Article
Journal Name:
Journal of Physical Chemistry. B
Additional Journal Information:
Journal Name: Journal of Physical Chemistry. B Journal Volume: 121 Journal Issue: 12; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
59 BASIC BIOLOGICAL SCIENCES; electron transfer; bell-shaped kinetic law; Arrhenius coordinates; polar solvation; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Waskasi, Morteza M., Newton, Marshall D., and Matyushov, Dmitry V. Impact of Temperature and Non-Gaussian Statistics on Electron Transfer in Donor–Bridge–Acceptor Molecules. United States: N. p., 2017. Web. doi:10.1021/acs.jpcb.7b00140.
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Waskasi, Morteza M., Newton, Marshall D., & Matyushov, Dmitry V. Impact of Temperature and Non-Gaussian Statistics on Electron Transfer in Donor–Bridge–Acceptor Molecules. United States. https://doi.org/10.1021/acs.jpcb.7b00140
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Waskasi, Morteza M., Newton, Marshall D., and Matyushov, Dmitry V. Mon . "Impact of Temperature and Non-Gaussian Statistics on Electron Transfer in Donor–Bridge–Acceptor Molecules". United States. https://doi.org/10.1021/acs.jpcb.7b00140.
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@article{osti_1349132,
title = {Impact of Temperature and Non-Gaussian Statistics on Electron Transfer in Donor–Bridge–Acceptor Molecules},
author = {Waskasi, Morteza M. and Newton, Marshall D. and Matyushov, Dmitry V.},
abstractNote = {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.},
doi = {10.1021/acs.jpcb.7b00140},
journal = {Journal of Physical Chemistry. B},
number = 12,
volume = 121,
place = {United States},
year = {Mon Mar 06 00:00:00 EST 2017},
month = {Mon Mar 06 00:00:00 EST 2017}
}
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https://doi.org/10.1021/acs.jpcb.7b00140
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