A Conservative Finite Difference Scheme for Poisson-Nernst-Planck Equations

A macroscopic model to describe the dynamics of ion transport in ion channels is the Poisson-Nernst-Planck(PNP) equations. In this paper, we develop a finite-difference method for solving PNP equations, which is second-order accurate in both space and time. We use the physical parameters specifically suited toward the modelling of ion channels. We present a simple iterative scheme to solve the system of nonlinear equations resulting from discretizing the equations implicitly in time, which is demonstrated to converge in a few iterations. We place emphasis on ensuring numerical methods to have the same physical properties that the PNP equations themselves also possess, namely conservation of total ions and correct rates of energy dissipation. We describe in detail an approach to derive a finite-difference method that preserves the total concentration of ions exactly in time. Further, we illustrate that, using realistic values of the physical parameters, the conservation property is critical in obtaining correct numerical solutions over long time scales

A study of electrochemical transport and diffuse charge dynamics using a Langevin equation

This thesis aims to develop new numerical and computational tools to study electrochemical transport and diffuse charge dynamics at small scales. Previous efforts at modeling electrokinetic phenomena at scales where the noncontinuum effects become significant have included continuum models based on the Poisson-Nernst-Planck equations and atomic simulations using molecular dynamics algorithms. Neither of them is easy to use or conducive to electrokinetic transport modeling in strong confinement or over long time scales. This work introduces a new approach based on a Langevin equation for diffuse charge dynamics in nanofluidic devices, which incorporates features from both continuum and atomistic methods. The model is then extended to include steric effects resulting from finite ion size, and applied to the phenomenon of double layer charging in a symmetric binary electrolyte between parallel-plate blocking electrodes, between which a voltage is applied. Finally, the results of this approach are compared to those of the continuum model based on the Poisson-Nernst-Planck equations

Modeling transport of charged species in pore networks: solution of the Nernst-Planck equations coupled with fluid flow and charge conservation equations

A pore network modeling (PNM) framework for the simulation of transport of charged species, such as ions, in porous media is presented. It includes the Nernst-Planck (NP) equations for each charged species in the electrolytic solution in addition to a charge conservation equation which relates the species concentration to each other. Moreover, momentum and mass conservation equations are adopted and there solution allows for the calculation of the advective contribution to the transport in the NP equations. The proposed framework is developed by first deriving the numerical model equations (NMEs) corresponding to the partial differential equations (PDEs) based on several different time and space discretization schemes, which are compared to assess solutions accuracy. The derivation also considers various charge conservation scenarios, which also have pros and cons in terms of speed and accuracy. Ion transport problems in arbitrary pore networks were considered and solved using both PNM and finite element method (FEM) solvers. Comparisons showed an average deviation, in terms of ions concentration, between PNM and FEM below $5\%$ with the PNM simulations being over ${10}^{4}$ times faster than the FEM ones for a medium including about ${10}^{4}$ pores. The improved accuracy is achieved by utilizing more accurate discretization schemes for both the advective and migrative terms, adopted from the CFD literature. The NMEs were implemented within the open-source package OpenPNM based on the iterative Gummel algorithm with relaxation. This work presents a comprehensive approach to modeling charged species transport suitable for a wide range of applications from electrochemical devices to nanoparticle movement in the subsurface