2022/12/23 by Andrea Grisafi, Grisafi, Andrea, Federico Grasselli +1
Chemical Engineering · Engineering · Physics and Astronomy · #Advanced Thermodynamics and Statistical Mechanics #Chemical and Physical Properties in Aqueous Solutions #FOS: Physical sciences #Field-Flow Fractionation Techniques #Statistical Mechanics (cond-mat.stat-mech)
paper · pdf · doi:10.48550/arxiv.2212.12233
openalex publication_date 2022/12/23 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28
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-Hückel 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.