Debye-H\"uckel Theory of Weakly Curved Macroions: Implementing Ion Specificity through a Composite Coloumb-Yukawa Interaction Potential

TL;DR

This paper extends Debye-Hückel theory to include ion-specific effects via a composite Coulomb-Yukawa potential, providing analytic expressions for macroion free energy and curvature properties.

Contribution

It introduces a perturbation approach to incorporate ion-specific Yukawa interactions into Debye-Hückel theory for weakly curved macroions.

Findings

Analytic expressions for free energy and curvature moduli.

Good agreement with experimental parameters.

Perturbation expansion simplifies complex interactions.

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-H\"uckel 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.