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Title: Understanding attenuated solvent reorganization energies near electrode interfaces

Abstract

In this manuscript, we examine the role of image charge effects on the electrostatic potential fluctuations experienced by ionic species in the vicinity of an electrode surface. We combine simulation and theory to quantify these fluctuations and how they vary with distance from the electrode surface. We observe that the potential distribution narrows significantly for species within a few electrolyte screening lengths of the electrode. We attribute this narrowing to the effects of image charge fluctuations originating from the polarization response of the electrode. We show that the physical consequences of these image charge effects can be captured in the context of a simple analytical field theory with anti-symmetric boundary conditions. We contextualize these results by discussing their implications for rates of Marcus-like outer-sphere interfacial electron transfer.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
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  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Publication Date:
Research Org.:
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1803240
Alternate Identifier(s):
OSTI ID: 1605300
Grant/Contract Number:  
SC0018094
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 152; Journal Issue: 11; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; Physics

Citation Formats

Limaye, Aditya M., Ding, Wendu, and Willard, Adam P. Understanding attenuated solvent reorganization energies near electrode interfaces. United States: N. p., 2020. Web. doi:10.1063/5.0003428.
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Limaye, Aditya M., Ding, Wendu, & Willard, Adam P. Understanding attenuated solvent reorganization energies near electrode interfaces. United States. https://doi.org/10.1063/5.0003428
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Limaye, Aditya M., Ding, Wendu, and Willard, Adam P. Wed . "Understanding attenuated solvent reorganization energies near electrode interfaces". United States. https://doi.org/10.1063/5.0003428. https://www.osti.gov/servlets/purl/1803240.
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@article{osti_1803240,
title = {Understanding attenuated solvent reorganization energies near electrode interfaces},
author = {Limaye, Aditya M. and Ding, Wendu and Willard, Adam P.},
abstractNote = {In this manuscript, we examine the role of image charge effects on the electrostatic potential fluctuations experienced by ionic species in the vicinity of an electrode surface. We combine simulation and theory to quantify these fluctuations and how they vary with distance from the electrode surface. We observe that the potential distribution narrows significantly for species within a few electrolyte screening lengths of the electrode. We attribute this narrowing to the effects of image charge fluctuations originating from the polarization response of the electrode. We show that the physical consequences of these image charge effects can be captured in the context of a simple analytical field theory with anti-symmetric boundary conditions. We contextualize these results by discussing their implications for rates of Marcus-like outer-sphere interfacial electron transfer.},
doi = {10.1063/5.0003428},
journal = {Journal of Chemical Physics},
number = 11,
volume = 152,
place = {United States},
year = {Wed Mar 18 00:00:00 EDT 2020},
month = {Wed Mar 18 00:00:00 EDT 2020}
}
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https://doi.org/10.1063/5.0003428
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