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Title: 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 » for the rate constant of electron transfer in nonpolar liquid solvents.« less

Authors:
ORCiD logo [1]
  1. 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) (SC-22)
OSTI Identifier:
1593352
Alternate Identifier(s):
OSTI ID: 1582686
Grant/Contract Number:  
SC0015641
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); 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. doi:10.1039/C9CP06166E.
Matyushov, Dmitry V. Thu . "Electron transfer in nonpolar media". United States. doi:10.1039/C9CP06166E.
@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 (Print)},
number = ,
volume = ,
place = {United States},
year = {2020},
month = {1}
}

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