Effect of a Temperature Gradient on the Screening Properties of Ionic Fluids

TL;DR

This paper develops an analytical theory to describe how temperature gradients affect electrostatic screening in ionic fluids, revealing a transition between screening regimes and emphasizing the importance of non-equilibrium effects.

Contribution

It introduces a novel analytical framework for non-equilibrium electrostatic screening in ionic fluids under temperature gradients, extending equilibrium theories to out-of-equilibrium conditions.

Findings

Transition from monotonic to oscillatory screening regimes due to temperature gradients

Deviation from equilibrium screening effects is larger than thermodiffusion influences

Quantitative analysis of charged surface screening in aqueous electrolytes

Abstract

The electrostatic screening properties of ionic fluids are of paramount importance in countless physical processes. Yet, the behavior of ionic conductors out of thermal equilibrium has to date mainly been studied in the context of thermodiffusion phenomena by virtue of direct extensions of Debye-H\"uckel theories. We investigate how the static response of a symmetric ionic fluid is influenced by the presence of a thermal gradient by introducing a theory of electrostatic screening under a stationary temperature profile. By borrowing mathematical methods commonly used in the semiclassical approximation of quantum particles, we find analytical solutions to the asymptotic decay of the charge density which can be used to describe the non-equilibrium response of the system to external charge perturbations and for arbitrary ionic concentrations. Notably, a transition between monotonic and oscillatory screening regimes is observed as an effect of the temperature variation which generalizes known results of thermal equilibrium to out of equilibrium conditions. A final quantitative example on the screening of charged surfaces in aqueous electrolytes shows that the deviation from thermal equilibrium predicted by our solutions is generally larger than thermodiffusion effects, and should therefore be taken into account for a comprehensive description of the electrical double layer. Our findings pave the way to the rigorous treatment of non-equilibrium steady states in ionic systems with potential applications to the study of energy materials, nanostructured systems and waste-heat-recovery technologies.