Solvent-induced memory effects in a model electrolyte

TL;DR

This paper develops a mesoscopic stochastic density functional theory model to understand ion fluctuations and solvent memory effects in electrolytes, validated by simulations.

Contribution

It introduces a generalized Langevin equation for ionic charge density that explicitly includes solvent-mediated memory effects, advancing theoretical understanding.

Findings

Derived simple expressions for dynamical charge structure factors.

Predicted two-step relaxation in ionic dynamics for slow solvents.

Validated theoretical predictions with Brownian dynamics simulations.

Abstract

The fluctuations of ions in polar solvents remain poorly understood theoretically due to the complex coupling between ionic motion and solvent polarization. Indeed, while all-atom resolution can be achieved in numerical simulations, analytical approaches require suitable levels of coarse-graining. In this work, we describe ions and solvent molecules as interacting Brownian particles and use stochastic density functional theory to derive a generalized Langevin equation for the ionic charge density, explicitly accounting for solvent-mediated memory effects. In the regime where there is a clear timescale separation between fast solvent and slow ion dynamics, we obtain simple expressions for dynamical charge structure factors, which are validated by BD simulations. For slow solvents, we predict an emerging two-step relaxation in ionic dynamics. These results provide a mesoscopic approach for ion-solvent dynamics and open pathways to study fluctuation-induced phenomena in electrolytes.