Water molecules mute the dependence of the double-layer potential profile on ionic strength
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D3FD00114H.pdf
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1.05 MB
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Checksum (MD5)
77b9c17d5b769fe342e2ec72267ab1a3
Author(s)
Limaye, Aditya
Suvlu, Dylan
Willard, Adam P.
Date Issued
2024
Journal
Faraday Discussions
Publisher
Royal Society of Chemistry
Citation
Limaye, Aditya, Suvlu, Dylan and Willard, Adam P. 2024. "Water molecules mute the dependence of the double-layer potential profile on ionic strength." Faraday Discussions, 249.
Version
Final published version
Abstract
We present the results of molecular dynamics simulations of a nanoscale electrochemical cell. The simulations include an aqueous electrolyte solution with varying ionic strength (i.e., concentrations ranging from 0–4 M) between a pair of metallic electrodes held at constant potential difference. We analyze these simulations by computing the electrostatic potential profile of the electric double-layer region and find it to be nearly independent of ionic concentration, in stark contrast to the predictions of standard continuum-based theories. We attribute this lack of concentration dependence to the molecular influences of water molecules at the electrode–solution interface. These influences include the molecular manifestation of water’s dielectric response, which tends to drown out the comparatively weak screening requirement of the ions. To support our analysis, we decompose water’s interfacial response into three primary contributions: molecular layering, intrinsic (zero-field) orientational polarization, and the dipolar dielectric response.
Subjects
Physical and Theoretical Chemistry
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
Terms of Use
Creative Commons Attribution
Persistent DSpace Link
DOI of Published Version
https://doi.org/10.1039/d3fd00114h
