Electric-field-based Poisson-Boltzmann theory: 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 an electrolyte can then be treated as a composite nonuniform 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 [J.L. Ericksen, Arch. Rational Mech. Anal. 183, 299 (2007)AVRMAW0003-952710.1007/s00205-006-0042-4]. 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. Transverse polarization is accounted for by construction, lifting the restriction to longitudinal polarization inherent in the electrostatic potential based formulation of Poisson-Boltzmann mean field theory.