A Maxwell–Ampère Nernst–Planck framework for modeling charge dynamics

Abstract

Understanding the properties of charge dynamics is crucial to many practical applications, such as electrochemical energy devices and transmembrane ion channels. This work proposes a Maxwell-Ampére Nernst-Planck (MANP) framework for the description of charge dynamics. The MANP model with a curl-free condition on the electric displacement is shown to be energy dissipative with respect to a convex free-energy functional, and demonstrated to be equivalent to the Poisson-Nernst-Planck model. By the energy dissipation law, the steady state of the MANP model reproduces the charge conserving Poisson-Boltzmann (PB) theory, providing an alternative energy stable approach to study the PB theory. In order to achieve the curl-free condition, a companion local curl-free relaxation algorithm, which is shown to naturally preserve the discrete Gauss's law and converge robustly with linear computational complexity, is developed for the MANP model. One of the main advantages of our development is that it can efficiently deal with space-dependent permittivity instead of solving the variable-coefficient Poisson's equation. Many-body effects such as ionic steric effects and Coulomb correlations can be incorporated within the MANP framework to derive modified MANP models for problems in which the mean-field approximation fails. Numerical results on the charge dynamics with such beyond mean-field effects in inhomogeneous dielectric environments are presented to demonstrate the performance of the MANP models in the description of charge dynamics, illustrating that the proposed MANP model provides a general framework for modeling charge dynamics.