Electric field based Poisson-Boltzmann: Treating mobile charge as polarization

Abstract: Mobile charge in an electrolytic solution can in principle be represented as the divergence of ionic polarization. After adding explicit solvent polarization a finite volume of electrolyte can then be treated as a composite non-uniform dielectric body. Writing the electrostatic interactions as an integral over electric field energy density we show that the Poisson-Boltzmann functional in this formulation is convex and can be used to derive the equilibrium equations for electric potential and ion concentration by a variational procedure developed by Ericksen for dielectric continua (Arch. Rational Mech. Anal. 2007, 183, 299-313). The Maxwell field equations are enforced by extending the set of variational parameters by a vector potential representing the dielectric displacement which is fully transverse in a dielectric system without embedded external charge. The electric field energy density in this representation is a function of the vector potential and the sum of ionic and solvent polarization making the mutual screening explicit.