Electric Double-Layer Structure in Primitive Model Electrolytes. Comparing Molecular Dynamics with Local-Density Approximations

Giera, Brian; Henson, Neil; Kober, Edward M.; Shell, M. Scott; Squires, Todd M.

doi:10.1021/la5048936

Title: Electric Double-Layer Structure in Primitive Model Electrolytes. Comparing Molecular Dynamics with Local-Density Approximations

Journal Article · Fri Feb 27 00:00:00 EST 2015 · Langmuir

DOI:https://doi.org/10.1021/la5048936· OSTI ID:1235740

Giera, Brian ^[1]; Henson, Neil ^[2]; Kober, Edward M. ^[2]; Shell, M. Scott ^[3]; Squires, Todd M. ^[3]

Univ. of California, Santa Barbara, CA (United States); Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Univ. of California, Santa Barbara, CA (United States)

We evaluate the accuracy of local-density approximations (LDAs) using explicit molecular dynamics simulations of binary electrolytes comprised of equisized ions in an implicit solvent. The Bikerman LDA, which considers ions to occupy a lattice, poorly captures excluded volume interactions between primitive model ions. Instead, LDAs based on the Carnahan–Starling (CS) hard-sphere equation of state capture simulated values of ideal and excess chemical potential profiles extremely well, as is the relationship between surface charge density and electrostatic potential. Excellent agreement between the EDL capacitances predicted by CS-LDAs and computed in molecular simulations is found even in systems where ion correlations drive strong density and free charge oscillations within the EDL, despite the inability of LDAs to capture the oscillations in the detailed EDL profiles.

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Research Organization:: Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC52-07NA27344; AC52-06NA25396

OSTI ID:: 1235740

Report Number(s):: LA-UR-14-28921; TRN: US1600408

Journal Information:: Langmuir, Vol. 31, Issue 11; ISSN 0743-7463

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 48 works

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Multiionic effects on the capacitance of porous electrodes Jiménez, M. L.; Ahualli, S.; Arenas-Guerrero, P. Physical Chemistry Chemical Physics, Vol. 20, Issue 7 https://doi.org/10.1039/c7cp06778j	journal	January 2018
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