Electric Double-Layer Structure in Primitive Model Electrolytes. Comparing Molecular Dynamics with Local-Density Approximations
Abstract
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.
- Authors:
-
- 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)
- Publication Date:
- Research Org.:
- Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1235740
- Report Number(s):
- LA-UR-14-28921
Journal ID: ISSN 0743-7463; TRN: US1600408
- Grant/Contract Number:
- AC52-07NA27344; AC52-06NA25396
- Resource Type:
- Journal Article: Accepted Manuscript
- Journal Name:
- Langmuir
- Additional Journal Information:
- Journal Volume: 31; Journal Issue: 11; Journal ID: ISSN 0743-7463
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 74 ATOMIC AND MOLECULAR PHYSICS; 25 ENERGY STORAGE; 36 MATERIALS SCIENCE; Double layer; capacitance; electrolyte structure
Citation Formats
Giera, Brian, Henson, Neil, Kober, Edward M., Shell, M. Scott, and Squires, Todd M. Electric Double-Layer Structure in Primitive Model Electrolytes. Comparing Molecular Dynamics with Local-Density Approximations. United States: N. p., 2015.
Web. doi:10.1021/la5048936.
Giera, Brian, Henson, Neil, Kober, Edward M., Shell, M. Scott, & Squires, Todd M. Electric Double-Layer Structure in Primitive Model Electrolytes. Comparing Molecular Dynamics with Local-Density Approximations. United States. https://doi.org/10.1021/la5048936
Giera, Brian, Henson, Neil, Kober, Edward M., Shell, M. Scott, and Squires, Todd M. 2015.
"Electric Double-Layer Structure in Primitive Model Electrolytes. Comparing Molecular Dynamics with Local-Density Approximations". United States. https://doi.org/10.1021/la5048936. https://www.osti.gov/servlets/purl/1235740.
@article{osti_1235740,
title = {Electric Double-Layer Structure in Primitive Model Electrolytes. Comparing Molecular Dynamics with Local-Density Approximations},
author = {Giera, Brian and Henson, Neil and Kober, Edward M. and Shell, M. Scott and Squires, Todd M.},
abstractNote = {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.},
doi = {10.1021/la5048936},
url = {https://www.osti.gov/biblio/1235740},
journal = {Langmuir},
issn = {0743-7463},
number = 11,
volume = 31,
place = {United States},
year = {Fri Feb 27 00:00:00 EST 2015},
month = {Fri Feb 27 00:00:00 EST 2015}
}
Web of Science
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