Primitive model electrolytes in the modified Poisson–Boltzmann theory

Abstract

A symmetric formulation of the modified Poisson–Boltzmann theory is applied to study the thermodynamics and structure of single primitive model electrolytes. Comparisons are made with Monte Carlo simulations for 1 : 1, 2 : 1, 3 : 1 and 2 : 2 electrolytes. Good agreement is found with the thermodynamic properties using the coupling parameter technique. The structural results are generally very good, with discrepancies occurring only at high concentrations for unsymmetrical valences or at high concentrations for large variations in ion size. The results are comparable in accuracy to those of the hypernetted chain (HNC) theory.