On the equilibrium of the Poisson-Nernst-Planck-Bikermann model equipping with the steric and correlation effects

TL;DR

This paper analyzes the Poisson-Nernst-Planck-Bikermann model incorporating steric and correlation effects, establishing its mathematical properties, well-posedness, and numerical schemes to explore parameter influences on ionic solutions.

Contribution

It provides a rigorous mathematical analysis of the PNPB model, including properties like self-adjointness, positivity, and convexity, and develops an energy-preserving numerical scheme.

Findings

The model's equilibrium solutions are well-posed and mathematically justified.

The finite volume scheme preserves energy dissipation at the semi-discrete level.

Numerical results show how parameters influence the steric effects in ionic solutions.

Abstract

The Poisson-Nernst-Planck-Bikermann (PNPB) model, in which the ions and water molecules are treated as different species with non-uniform sizes and valences with interstitial voids, can describe the steric and correlation effects in ionic solution neglected by the Poisson-Nernst-Planck and Poisson-Boltzmann theories with point charge assumption. In the PNPB model, the electric potential is governed by the fourth-order Poisson-Bikermann (4PBik) equation instead of the Poisson equation so that it can describe the correlation effect. What's more, the steric potential is included in the ionic and water fluxes as well as the equilibrium Fermi-like distributions which characterizes the steric effect quantitatively. In this work, after doing a nondimensionalization step, we analyze the self-adjointness and the kernel of the fourth-order operator of the 4PBik equation. Also, we show the positivity of the void volume function and the convexity of the free energy. Following these properties, the well-posedness of the PNPB model in equilibrium is given. Furthermore, because the PNPB model has an energy dissipated structure, we adopt a finite volume scheme which preserves the energy dissipated property at the semi-discrete level. After that, various numerical investigations are given to show the parameter dependence of the steric effect to the steady state.