skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

This content will become publicly available on October 8, 2020

Title: Rate versus Free Energy Change for Attaching Highly Mobile Electrons to Molecules in Nonpolar Liquids

Abstract

The inverted region of the Marcus theory, usually absent for bimolecular electron transfer reactions, is clearly observed for electron attachment reactions to molecules in nonpolar fluids. Application of pressure increased the energies of the solvated electron reactants letting us continuously adjust the free energy change. Inverted behavior is enabled by the very high mobilities of the solvated electrons which raise the diffusion-controlled encounter rates so high that they do not limit the reaction rates. The nonpolar media used in these experiments reduce reorganization energies, enhancing inverted behavior. Still, for every case showing an inverted region, the presence of low-lying excited states in the product radical anions led to regions of increasing rate constants that began at the energies of excited states of –0.54 to –1.2 eV. Here, while continuum models predict no solvent reorganization energy in nonpolar liquids, fits to the data found solvent reorganization energies of 0.05–0.4 eV supporting ideas advanced in theories of Matyushov.

Authors:
 [1]; ORCiD logo [1]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1572366
Report Number(s):
BNL-212236-2019-JAAM
Journal ID: ISSN 1520-6106
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Volume: 123; Journal Issue: 43; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; electron transfer; radiation chemistry

Citation Formats

Holroyd, Richard A., and Miller, John R. Rate versus Free Energy Change for Attaching Highly Mobile Electrons to Molecules in Nonpolar Liquids. United States: N. p., 2019. Web. doi:10.1021/acs.jpcb.9b07845.
Holroyd, Richard A., & Miller, John R. Rate versus Free Energy Change for Attaching Highly Mobile Electrons to Molecules in Nonpolar Liquids. United States. doi:10.1021/acs.jpcb.9b07845.
Holroyd, Richard A., and Miller, John R. Tue . "Rate versus Free Energy Change for Attaching Highly Mobile Electrons to Molecules in Nonpolar Liquids". United States. doi:10.1021/acs.jpcb.9b07845.
@article{osti_1572366,
title = {Rate versus Free Energy Change for Attaching Highly Mobile Electrons to Molecules in Nonpolar Liquids},
author = {Holroyd, Richard A. and Miller, John R.},
abstractNote = {The inverted region of the Marcus theory, usually absent for bimolecular electron transfer reactions, is clearly observed for electron attachment reactions to molecules in nonpolar fluids. Application of pressure increased the energies of the solvated electron reactants letting us continuously adjust the free energy change. Inverted behavior is enabled by the very high mobilities of the solvated electrons which raise the diffusion-controlled encounter rates so high that they do not limit the reaction rates. The nonpolar media used in these experiments reduce reorganization energies, enhancing inverted behavior. Still, for every case showing an inverted region, the presence of low-lying excited states in the product radical anions led to regions of increasing rate constants that began at the energies of excited states of –0.54 to –1.2 eV. Here, while continuum models predict no solvent reorganization energy in nonpolar liquids, fits to the data found solvent reorganization energies of 0.05–0.4 eV supporting ideas advanced in theories of Matyushov.},
doi = {10.1021/acs.jpcb.9b07845},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 43,
volume = 123,
place = {United States},
year = {2019},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on October 8, 2020
Publisher's Version of Record

Save / Share: