On the molecular correlations that result in field-dependent conductivities in electrolyte solutions - Université de Pau et des Pays de l'Adour Accéder directement au contenu
Article Dans Une Revue Journal of Chemical Physics Année : 2021

On the molecular correlations that result in field-dependent conductivities in electrolyte solutions

Résumé

Employing recent advances in response theory and nonequilibrium ensemble reweighting, we study the dynamic and static correlations that give rise to an electric field-dependent ionic conductivity in electrolyte solutions. We consider solutions modeled with both implicit and explicit solvents, with different dielectric properties, and at multiple concentrations. Implicit solvent models at low concentrations and small dielectric constants exhibit strongly field-dependent conductivities. We compared these results to the Onsager-Wilson theory of the Wien effect, which provides a qualitatively consistent prediction at low concentrations and high static dielectric constants, but is inconsistent away from these regimes. The origin of the discrepancy is found to be increased ion correlations under these conditions. Explicit solvent effects act to suppress nonlinear responses, yielding a weakly field-dependent conductivity over the range of physically realizable field strengths. By decomposing the relevant time correlation functions, we find that the insensitivity of the conductivity to the field results from the persistent frictional forces on the ions from the solvent. Our findings illustrate the utility of nonequilibrium response theory in rationalizing nonlinear transport behavior.
Fichier principal
Vignette du fichier
Lesnicki et al. - 2021 - On the molecular correlations that result in field.pdf (3.49 Mo) Télécharger le fichier
Origine : Fichiers produits par l'(les) auteur(s)

Dates et versions

hal-03289900 , version 1 (19-07-2021)

Identifiants

Citer

Dominika Lesnicki, Chloe y Gao, David T Limmer, Benjamin Rotenberg. On the molecular correlations that result in field-dependent conductivities in electrolyte solutions. Journal of Chemical Physics, 2021, 155 (1), pp.014507. ⟨10.1063/5.0052860⟩. ⟨hal-03289900⟩
106 Consultations
40 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More