Frequency-Dependent Conductivity of Concentrated Electrolytes: A Stochastic Density Functional Theory

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Main Authors: Bonneau, Haggai, Avni, Yael, Andelman, David, Orland, Henri
Format: Preprint
Published: 2024
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author Bonneau, Haggai
Avni, Yael
Andelman, David
Orland, Henri
author_facet Bonneau, Haggai
Avni, Yael
Andelman, David
Orland, Henri
contents The response of ionic solutions to time-varying electric fields, quantified by a frequency-dependent conductivity, is essential in many electrochemical applications. Yet, it constitutes a challenging problem due to the combined effect of Coulombic interactions, hydrodynamics, and thermal fluctuations. Here, we study the frequency-dependent conductivity of ionic solutions using a stochastic density functional theory. In the limit of small concentrations, we recover the classical Debye and Falkenhagen (DF) result, predicting an increase in conductivity with field frequency. At higher concentrations, we use a modified Coulomb interaction potential that accounts for the hard-core repulsion between the ions, which was recently employed in the zero-frequency case. Consequently, we extend the DF result to concentrated electrolytes. We discuss experimental and numerical studies and the complexity of observing the DF effect in such setups.
format Preprint
id arxiv_https___arxiv_org_abs_2408_17427
institution arXiv
publishDate 2024
record_format arxiv
spellingShingle Frequency-Dependent Conductivity of Concentrated Electrolytes: A Stochastic Density Functional Theory
Bonneau, Haggai
Avni, Yael
Andelman, David
Orland, Henri
Soft Condensed Matter
Statistical Mechanics
Chemical Physics
The response of ionic solutions to time-varying electric fields, quantified by a frequency-dependent conductivity, is essential in many electrochemical applications. Yet, it constitutes a challenging problem due to the combined effect of Coulombic interactions, hydrodynamics, and thermal fluctuations. Here, we study the frequency-dependent conductivity of ionic solutions using a stochastic density functional theory. In the limit of small concentrations, we recover the classical Debye and Falkenhagen (DF) result, predicting an increase in conductivity with field frequency. At higher concentrations, we use a modified Coulomb interaction potential that accounts for the hard-core repulsion between the ions, which was recently employed in the zero-frequency case. Consequently, we extend the DF result to concentrated electrolytes. We discuss experimental and numerical studies and the complexity of observing the DF effect in such setups.
title Frequency-Dependent Conductivity of Concentrated Electrolytes: A Stochastic Density Functional Theory
topic Soft Condensed Matter
Statistical Mechanics
Chemical Physics
url https://arxiv.org/abs/2408.17427