Transient fluctuation-induced forces in driven electrolytes after an electric field quench

Abstract

Understanding how electrolyte solutions behave out of thermal equilibrium is a long-standing endeavor in many areas of chemistry and biology. Although mean-field theories are widely used to model the dynamics of electrolytes, it is also important to characterize the effects of fluctuations in these systems. In a previous work, we showed that the dynamics of the ions in a strong electrolyte that is driven by an external electric field can generate long-ranged correlations manifestly different from the equilibrium screened correlations; in the nonequilibrium steady state, these correlations give rise to a novel long-range fluctuation-induced force (FIF). Here, we extend these results by considering the dynamics of the strong electrolyte after it is quenched from thermal equilibrium upon the application of a constant electric field. We show that the asymptotic long-distance limit of both charge and density correlations is generally diffusive in time. These correlations give rise to long-ranged FIFs acting on the neutral confining plates with long-time regimes that are governed by power-law temporal decays toward the steady-state value of the force amplitude. These findings show that nonequilibrium fluctuations have nontrivial implications on the dynamics of objects immersed in a driven electrolyte, and they could be useful for exploring new ways of controlling long-distance forces in charged solutions.

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• Frequency-Dependent Conductivity of Concentrated Electrolytes: A Stochastic Density Functional Theory
• Algebraic depletion interactions in two-temperature mixtures