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:
-
- 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
- Publication Date:
- Research Org.:
- Arizona State Univ., Tempe, AZ (United States); Brookhaven National Lab. (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:
- Journal Article: Published Article
- Journal Name:
- Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
- Additional Journal Information:
- Journal Name: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry 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.
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
Waskasi, Morteza M., Newton, Marshall D., and Matyushov, Dmitry V. 2017.
"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.
@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},
url = {https://www.osti.gov/biblio/1349132},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
issn = {1520-6106},
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}
}
Web of Science
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