期刊
JOURNAL OF CHEMICAL PHYSICS
卷 155, 期 1, 页码 -出版社
AIP Publishing
DOI: 10.1063/5.0052860
关键词
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资金
- French Agence Nationale de la Recherche (ANR) [ANR-17-CE09-0046-02]
- H2020-FETOPEN project NANOPHLOW [766972]
- European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program [863473]
- LDRD program at LBNL under the U. S. Department of Energy Office of Science, Office of Basic Energy Sciences [DE-AC02-05CH11231]
- Agence Nationale de la Recherche (ANR) [ANR-17-CE09-0046] Funding Source: Agence Nationale de la Recherche (ANR)
This study investigates the dynamic and static correlations contributing to electric field-dependent ionic conductivity in electrolyte solutions using response theory and nonequilibrium ensemble reweighting. It is found that increased ion correlations under certain conditions result in insensitivity of the conductivity to the field.
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 compare these results to 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. Published under an exclusive license by AIP Publishing.
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