Electron transfer in nonpolar media
Abstract
The Marcus theory of electron transfer views fluctuating orientations of permanent dipoles as the nuclear mode bringing the donor and acceptor into the tunneling resonance. Electronic polarization of the solvent is excluded as the fast mode adiabatically following the electronic density. This view, valid for solids, does not apply to molecular liquids where molecular translations (density fluctuations) modulate the induction interaction of the donor-acceptor complex with the solvent. This mechanism of promoting radiation-less electronic transitions is considered here in the framework of the perturbation liquid-state theory. The reorganization energy of electron transfer in nonpolar solvents is nonzero and reaches the values of 0.1–0.3 eV for typical molecular sizes and solvents used in applications. The reorganization energy scales quadratically with the molecular polarizability of the solvent and decays as the inverse fifth power with the size of the donor and acceptor. The combination of the entropic character of the density fluctuations, driven by re-packing of molecular cores, with the short range of induction solute–solvent interactions leads to the violation of the fluctuation–dissipation theorem for the variance of the donor-acceptor energy gap. An explicit, approximately hyperbolic, dependence of the reorganization energy on temperature is predicted. It leads to a non-Arrhenius kinetic lawmore »
- Authors:
-
- Arizona State Univ., Tempe, AZ (United States). Dept. of Physics and School of Molecular Sciences
- Publication Date:
- Research Org.:
- Arizona State Univ., Tempe, AZ (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1593352
- Alternate Identifier(s):
- OSTI ID: 1582686
- Grant/Contract Number:
- SC0015641
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Chemistry Chemical Physics. PCCP
- Additional Journal Information:
- Journal Volume: 22; Journal Issue: 19; Journal ID: ISSN 1463-9076
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 74 ATOMIC AND MOLECULAR PHYSICS
Citation Formats
Matyushov, Dmitry V. Electron transfer in nonpolar media. United States: N. p., 2020.
Web. doi:10.1039/C9CP06166E.
Matyushov, Dmitry V. Electron transfer in nonpolar media. United States. https://doi.org/10.1039/C9CP06166E
Matyushov, Dmitry V. Thu .
"Electron transfer in nonpolar media". United States. https://doi.org/10.1039/C9CP06166E. https://www.osti.gov/servlets/purl/1593352.
@article{osti_1593352,
title = {Electron transfer in nonpolar media},
author = {Matyushov, Dmitry V.},
abstractNote = {The Marcus theory of electron transfer views fluctuating orientations of permanent dipoles as the nuclear mode bringing the donor and acceptor into the tunneling resonance. Electronic polarization of the solvent is excluded as the fast mode adiabatically following the electronic density. This view, valid for solids, does not apply to molecular liquids where molecular translations (density fluctuations) modulate the induction interaction of the donor-acceptor complex with the solvent. This mechanism of promoting radiation-less electronic transitions is considered here in the framework of the perturbation liquid-state theory. The reorganization energy of electron transfer in nonpolar solvents is nonzero and reaches the values of 0.1–0.3 eV for typical molecular sizes and solvents used in applications. The reorganization energy scales quadratically with the molecular polarizability of the solvent and decays as the inverse fifth power with the size of the donor and acceptor. The combination of the entropic character of the density fluctuations, driven by re-packing of molecular cores, with the short range of induction solute–solvent interactions leads to the violation of the fluctuation–dissipation theorem for the variance of the donor-acceptor energy gap. An explicit, approximately hyperbolic, dependence of the reorganization energy on temperature is predicted. It leads to a non-Arrhenius kinetic law for the rate constant of electron transfer in nonpolar liquid solvents.},
doi = {10.1039/C9CP06166E},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 19,
volume = 22,
place = {United States},
year = {Thu Jan 02 00:00:00 EST 2020},
month = {Thu Jan 02 00:00:00 EST 2020}
}
Web of Science
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