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Title: Atomistic and molecular effects in electric double layers at high surface charges

Abstract

Here, the Poisson–Boltzmann theory for electrolytes near a charged surface is known to be invalid due to unaccounted physics associated with high ion concentration regimes. In order to investigate this regime, fluids density functional theory (f-DFT) and molecular dynamics (MD) simulations were used to determine electric surface potential as a function of surface charge. Based on these detailed computations, for electrolytes with nonpolar solvent, the surface potential is shown to depend quadratically on the surface charge in the high charge limit. We demonstrate that modified Poisson–Boltzmann theories can model this limit if they are augmented with atomic packing densities provided by MD. However, when the solvent is a highly polar molecule water an intermediate regime is identified in which a constant capacitance is realized. Simulation results demonstrate the mechanism underlying this regime, and for the salt water system studied here, it persists throughout the range of physically realistic surface charge densities so the potential’s quadratic surface charge dependence is not obtained.

Authors:
 [1];  [1];  [2]
  1. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
  2. Stanford Univ., Stanford, CA (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1235288
Report Number(s):
SAND-2015-0060J
Journal ID: ISSN 0743-7463; 558321
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Accepted Manuscript
Journal Name:
Langmuir
Additional Journal Information:
Journal Volume: 31; Journal Issue: 27; Journal ID: ISSN 0743-7463
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats

Templeton, Jeremy Alan, Lee, Jonathan, and Mani, Ali. Atomistic and molecular effects in electric double layers at high surface charges. United States: N. p., 2015. Web. doi:10.1021/acs.langmuir.5b00215.
Templeton, Jeremy Alan, Lee, Jonathan, & Mani, Ali. Atomistic and molecular effects in electric double layers at high surface charges. United States. doi:10.1021/acs.langmuir.5b00215.
Templeton, Jeremy Alan, Lee, Jonathan, and Mani, Ali. Tue . "Atomistic and molecular effects in electric double layers at high surface charges". United States. doi:10.1021/acs.langmuir.5b00215. https://www.osti.gov/servlets/purl/1235288.
@article{osti_1235288,
title = {Atomistic and molecular effects in electric double layers at high surface charges},
author = {Templeton, Jeremy Alan and Lee, Jonathan and Mani, Ali},
abstractNote = {Here, the Poisson–Boltzmann theory for electrolytes near a charged surface is known to be invalid due to unaccounted physics associated with high ion concentration regimes. In order to investigate this regime, fluids density functional theory (f-DFT) and molecular dynamics (MD) simulations were used to determine electric surface potential as a function of surface charge. Based on these detailed computations, for electrolytes with nonpolar solvent, the surface potential is shown to depend quadratically on the surface charge in the high charge limit. We demonstrate that modified Poisson–Boltzmann theories can model this limit if they are augmented with atomic packing densities provided by MD. However, when the solvent is a highly polar molecule water an intermediate regime is identified in which a constant capacitance is realized. Simulation results demonstrate the mechanism underlying this regime, and for the salt water system studied here, it persists throughout the range of physically realistic surface charge densities so the potential’s quadratic surface charge dependence is not obtained.},
doi = {10.1021/acs.langmuir.5b00215},
journal = {Langmuir},
number = 27,
volume = 31,
place = {United States},
year = {2015},
month = {6}
}

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