Modified Poisson-Nernst-Planck model with Coulomb and hard-sphere correlations

Abstract

We develop a modified Poisson-Nernst-Planck model which includes both the long-range Coulomb and short-range hard-sphere correlations in its free energy functional such that the model can accurately describe the ion transport in complex environment and under a nanoscale confinement. The Coulomb correlation including the dielectric polarization is treated by solving a generalized Debye-Hückel equation which is a Green's function equation with the correlation energy of a test ion described by the self Green's function. The hard-sphere correlation is modeled through the modified fundamental measure theory. The resulting model is available for problems beyond the mean-field theory such as problems with variable dielectric media, multivalent ions, and strong surface charge density. We solve the generalized Debye-Hückel equation by the Wentzel-Kramers-Brillouin approximation, and study the electrolytes between two parallel dielectric surfaces. In comparison to other modified models, the new model is shown more accurate in agreement with particle-based simulations and capturing the physical properties of ionic structures near interfaces.

22 pages, 7 figures

References in corpus (4)

• Electrolytes between dielectric charged surfaces: Simulations and theory
• Self-energy-modified Poisson-Nernst-Planck equations: WKB approximation and finite-difference approaches
• Density functional formulation of the Random Phase Approximation for inhomogeneous fluids: application to the Gaussian core and Coulomb particles
• Mean-field electrostatics beyond the point-charge description