Pimples reduce and dimples enhance flat dielectric surface image repulsion

TL;DR

This paper derives analytical formulas for the self-energy and ion-surface interactions near deformed dielectric interfaces, revealing how surface curvature influences ion repulsion and attraction.

Contribution

It provides the first-order perturbation theory results for ion self-energy near sinusoidally deformed interfaces, extending the image charge method to complex geometries.

Findings

Convex surface regions reduce ion repulsion.

Concave surface regions increase ion repulsion.

Dimpled surfaces are more repulsive than pimples.

Abstract

Near solid-liquid or liquid-liquid interfaces with dielectric contrast, charged particles interact with the induced polarization charge of the interface. These interactions contribute to an effective self-energy of the bulk ions and mediate ion-ion interactions. For flat interfaces, the self-energy and the mediated interaction are neatly constructed by the image charge method. For other geometries, explicit results are scarce and the problem must be treated via approximations or direct computation. This article provides analytical results, valid to first order in perturbation theory, for the self-energy of particles near a deformed near-flat interface. Explicit formulas are provided for the case of a sinusoidal deformation; generic deformations can then be treated by superposition. In addition to results for the self-energy, the surface polarization charge due to a single ion is presented as a quadrature. The interaction between an ion and the deformed surface is modified by the change in relative distance as well as by the curvature of the surface. Solid walls with a lower dielectric constant than the liquid repel all ions. We show here, however, that the repulsion is reduced by local convexity and enhanced by concavity; dimples are more repulsive than pimples.