Modified Poisson-Boltzmann equations and macroscopic forces in inhomogeneous ionic fluids

TL;DR

This paper develops a comprehensive field-theoretical framework to derive modified Poisson-Boltzmann equations and stress tensors for inhomogeneous ionic fluids, enabling better estimation of macroscopic forces on immersed bodies.

Contribution

It introduces a novel variational approach based on thermodynamic perturbation theory to derive generalized equations and stress tensors for various ionic fluid models.

Findings

Derived a general mean-field stress tensor consistent with modified Poisson-Boltzmann equations.

Formulated expressions for macroscopic forces and disjoining pressure in ionic fluids.

Applied the formalism to nonpolarizable, polarizable, and ion-dipole mixture models.

Abstract

We propose a field-theoretical approach based on the thermodynamic perturbation theory and within it derive a grand thermodynamic potential of the inhomogeneous ionic fluid as a functional of electrostatic potential for an arbitrary reference fluid system. We obtain a modified Poisson-Boltzmann equation as the Euler-Lagrange equation for the obtained functional. Applying Noether's theorem to this functional, we derive a general mean-field expression for the stress tensor consistent with the respective modified Poisson-Boltzmann equation. We derive a general expression for the macroscopic force acting on the dielectric or conductive body immersed in an ionic fluid. In particular, we derive a general mean-field expression for the disjoining pressure of an ionic fluid in a slit pore. We apply the developed formalism to describe three ionic fluid models of practical importance: nonpolarizable models (including the well-known Poisson-Boltzmann and Poisson-Fermi equations), polarizable models (ions carry nonzero permanent dipole or static polarizability), and models of ion-dipole mixtures (including the well-known Poisson-Boltzmann-Langevin equation). For these models, we obtain modified Poisson-Boltzmann equations and respective stress tensors, which could be valuable for different applications, where it is necessary to estimate the macroscopic forces acting on the dielectric or conductive bodies (electrodes, colloids, membranes, {\it etc}.) together with the local electrostatic potential (field) and ionic concentrations.