Stochastic Density Functional Theory for Ions in a Polar Solvent

In recent years, the theoretical description of electrical noise and fluctuation-induced effects in electrolytes has gained renewed interest, enabled by stochastic field theories like stochastic density functional theory (SDFT). Such models, however, treat solvents implicitly, ignoring their generally polar nature. In the present study, starting from microscopic principles, we derive a fully explicit SDFT theory that applies to ions in a polar solvent. These equations are solved to compute observables like dynamic charge structure factors and dielectric susceptibilities. We unveil the relative importance of the different contributions (solvent, ions, cross terms) to the dynamics of electrolytes, which are key to understand the couplings between ions and the fluctuations of their microscopic environment.

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Publication Details

Journal
Physical Review Letters
Published
2024-12-27
DOI
https://doi.org/10.1103/physrevlett.133.268002
Citations
9
Primary Topic
Spectroscopy and Quantum Chemical Studies
Type
article
Field-Weighted Citation Impact
3.04

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article

Stochastic Density Functional Theory for Ions in a Polar Solvent

Pierre Illien, Antoine Carof, Benjamin Rotenberg
9 citations
Physical Review Letters
Spectroscopy and Quantum Chemical Studies
3.04
article

Stochastic Density Functional Theory for Ions in a Polar Solvent

Pierre Illien, Antoine Carof, Benjamin Rotenberg
article en
9 citations

Abstract

In recent years, the theoretical description of electrical noise and fluctuation-induced effects in electrolytes has gained renewed interest, enabled by stochastic field theories like stochastic density functional theory (SDFT). Such models, however, treat solvents implicitly, ignoring their generally polar nature. In the present study, starting from microscopic principles, we derive a fully explicit SDFT theory that applies to ions in a polar solvent. These equations are solved to compute observables like dynamic charge structure factors and dielectric susceptibilities. We unveil the relative importance of the different contributions (solvent, ions, cross terms) to the dynamics of electrolytes, which are key to understand the couplings between ions and the fluctuations of their microscopic environment.

Physical Review LettersVol. 133(26)
Sorbonne Université (FR), Réseau sur le Stockage Electrochimique de l'énergie (FR), PHENIX laboratory (FR), Laboratoire de Physique et Chimie Théoriques, Laboratoire Médiations (FR), Université de Lorraine (FR)
European Commission, Horizon 2020 Framework Programme, European Research Council
Openalex Percentile: Top 8%
Spectroscopy and Quantum Chemical Studies
3.04
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Stochastic Density Functional Theory for Ions in a Polar Solvent — Pierre Illien, Antoine Carof, et al. · Physical Review Letters (2024) | TGRS Research Map | TGRS