Local Structure-Preserving Relaxation Method for Equilibrium of Charged Systems on Unstructured Meshes

SIAM Journal on Scientific Computing, Volume 46, Issue 4, Page A2248-A2269, August 2024.
Abstract. This work considers charged systems described by the modified Poisson–Nernst–Planck (PNP) equations, which incorporate ionic steric effects and the Born solvation energy for dielectric inhomogeneity. Solving the equilibrium of modified PNP equations poses numerical challenges due to the emergence of sharp boundary layers caused by small Debye lengths, particularly when local ionic concentrations reach saturation. To address this, we first reformulate the problem as a constraint optimization, where the ionic concentrations on unstructured Delaunay nodes are treated as fractional particles moving along edges between nodes. The electric fields are then updated to minimize the objective free energy while satisfying the discrete Gauss law. We develop a local relaxation method on unstructured meshes that inherently respects the discrete Gauss law, ensuring curl-free electric fields. Numerical analysis demonstrates that the optimal mass of the moving fractional particles guarantees the positivity of both ionic and solvent concentrations. Additionally, the free energy of the charged system consistently decreases during successive updates of ionic concentrations and electric fields. We conduct numerical tests to validate the expected numerical accuracy, positivity, free-energy dissipation, and robustness of our method in simulating charged systems with sharp boundary layers.