Debye-Hückel Theory of Weakly Curved Macroions: Implementing Ion Specificity through a Composite Coloumb-Yukawa Interaction Potential

Abstract

The free energy of a weakly curved, isolated macroion embedded in a symmetric 1:1 electrolyte solution is calculated on the basis of linear Debye-Hückel theory, thereby accounting for non-electrostatic Yukawa pair interactions between the mobile ions and of the mobile ions with the macroion surface, present in addition to the electrostatic Coulomb potential. The Yukawa interactions between anion-anion, cation-cation, and anion-cation pairs are independent from each other and serve as a model for solvent-mediated ion-specific effects. We derive expressions for the free energy of a planar surface, the spontaneous curvature, the bending stiffness, and the Gaussian modulus. It is shown that a perturbation expansion, valid if the Yukawa interactions make a small contribution to the overall free energy, yields simple analytic results that exhibit good agreement with the general free energy over the range of experimentally relevant interaction parameters.

25 pages, 4 figures. Published in Physical Review E. Copyright 2018 by the American Physical Society