Numerical study of density functional theory with mean spherical approximation for ionic condensation in highly charged confined electrolytes

We investigate numerically a Density Functional Theory (DFT) for strongly confined ionic solutions in the Canonical Ensemble by comparing predictions of ionic concentration profiles and pressure for the double-layer configuration to those obtained with Monte Carlo (MC) simulations and the simpler Poisson--Boltzmann (PB) approach. The DFT consists of a bulk (ion-ion) and an ion-solid part. The bulk part includes nonideal terms accounting for long-range electrostatic and short-range steric correlations between ions and is evaluated with the Mean Spherical Approximation and the Local Density Approximation. The ion-solid part treats the ion-solid interactions at the mean-field level through the solution of a Poisson problem. The main findings are that ionic concentration profiles are generally better described by PB than by DFT, although DFT captures the non-monotone co-ion profile missed by PB. Instead, DFT yields more accurate pressure predictions than PB, showing in particular that nonideal effects are important to describe highly confined ionic solutions. Finally, we present a numerical methodology capable of handling nonconvex minimization problems so as to explore DFT predictions when the reduced temperature falls below the critical temperature.

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Source ISSN: 1539-3755
Author Joubaud, Rémi, Bernard, Olivier, Delville, Alfred, Ern, Alexandre, Rotenberg, Benjamin, Turq, Pierre
Maintainer CCSD
Last Updated May 5, 2026, 11:01 (UTC)
Created May 5, 2026, 11:01 (UTC)
Identifier hal-00992323
Language en
Rights https://about.hal.science/hal-authorisation-v1/
contributor Centre d'Enseignement et de Recherche en Mathématiques et Calcul Scientifique (CERMICS) ; École nationale des ponts et chaussées (ENPC)
creator Joubaud, Rémi
date 2014-06-10T00:00:00
harvest_object_id 2896ac10-6e52-4053-ad5b-a9b685875d66
harvest_source_id 3374d638-d20b-4672-ba96-a23232d55657
harvest_source_title test moissonnage SELUNE
metadata_modified 2026-01-28T00:00:00
relation info:eu-repo/semantics/altIdentifier/doi/10.1103/PhysRevE.89.062302
set_spec type:ART