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

Templeton, Jeremy Alan; Lee, Jonathan; Mani, Ali

doi:10.1021/acs.langmuir.5b00215

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

Journal Article · Tue Jun 16 00:00:00 EDT 2015 · Langmuir

DOI:https://doi.org/10.1021/acs.langmuir.5b00215· OSTI ID:1235288

Templeton, Jeremy Alan ^[1]; Lee, Jonathan ^[1]; Mani, Ali ^[2]

Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Stanford Univ., Stanford, CA (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-CA), Livermore, CA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC04-94AL85000

OSTI ID:: 1235288

Report Number(s):: SAND--2015-0060J; 558321

Journal Information:: Langmuir, Journal Name: Langmuir Journal Issue: 27 Vol. 31; ISSN 0743-7463

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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