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Charge neutrality breakdown in confined aqueous electrolytes: Theory and simulation

2016/09/02 by Thiago Colla, Matheus Girotto, Alexandre P. dos Santos +1 · 1 citation
Chemical Engineering · Chemistry · Mathematics · Physics and Astronomy · #Aqueous solution #Charge (physics) #Charge density #Chemical and Physical Properties in Aqueous Solutions #Chemical physics #Chemistry #Computational chemistry #Computer science #Counterion #Density functional theory #Electrode #Electrolyte #Electrostatics #Electrostatics and Colloid Interactions #Ion #Ionic bonding #Materials science #Mathematics #Monte Carlo method #Organic chemistry #Physical chemistry #Physics #Planar #Quantum mechanics #Spectroscopy and Quantum Chemical Studies #cond-mat.soft

paper · pdf · doi:10.1063/1.4962198

arxiv created 2016/09/02 · openalex publication_date 2016/09/07 · arxiv updated 2016/09/21 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/05

Abstract

We study, using Density Functional theory (DFT) and Monte Carlo simulations, aqueous electrolyte solutions between charged infinite planar surfaces, in contact with a bulk salt reservoir. In agreement with recent experimental observations [Z. Luo et al., Nat. Commun. 6, 6358 (2015)], we find that the confined electrolyte lacks local charge neutrality. We show that a DFT based on a bulk-HNC expansion properly accounts for strong electrostatic correlations and allows us to accurately calculate the ionic density profiles between the charged surfaces, even for electrolytes containing trivalent counterions. The DFT allows us to explore the degree of local charge neutrality violation, as a function of plate separation and bulk electrolyte concentration, and to accurately calculate the interaction force between the charged surfaces.

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