Solving Lyapunov equations for electrically driven ternary electrolytes -- application to long-range van der Waals interactions

TL;DR

This paper develops a method to simplify Lyapunov equations in electrolyte models, enabling the calculation of long-range van der Waals interactions in ternary electrolytes under electric fields, revealing their out-of-equilibrium nature.

Contribution

It introduces a reduction technique for Lyapunov equations in ternary electrolytes, facilitating analytical computation of electrostatic interactions in complex electrolyte systems.

Findings

Lyapunov equations can be reduced to linear equations for electrolytes.

Van der Waals interactions depend on ionic diffusion coefficients in ternary electrolytes.

Interactions are inherently out of equilibrium, unlike binary cases.

Abstract

Stochastic density functional theory (SDFT) has been widely used to study the out of equilibrium properties of electrolyte solutions. Examples include investigations of electrical conductivity -- both within and beyond linear response -- and modifications of thermal van der Waals interactions in driven electrolytes. Within the approximation scheme derived from linearizing SDFT for fluctuations around mean densities, the steady state correlation functions between the $N$ ionic species are governed by linear Lyapunov equations of degree $N(N+1)/2$. Consequently, the system's complexity increases significantly when transitioning from binary to ternary electrolytes, and few analytical results exist for the latter. In this paper, we demonstrate how -- for the specific case of electrolytes -- the Lyapunov equations can be reduced to a system of $N$ linear equations. We apply this reduction to compute the long-range component of the van der Waals interaction between two slabs containing a ternary electrolyte under an applied electric field parallel to the slabs. Unlike the binary electrolyte case, we show that the resulting van der Waals interaction for a ternary electrolyte depends on the ionic species' diffusion coefficients, highlighting its inherently out of equilibrium nature.