Macroscopic surface charges from microscopic simulations

TL;DR

This paper demonstrates that applying an electric displacement field in molecular simulations enables accurate determination of macroscopic surface charges at charged interfaces, overcoming limitations of traditional methods and slab thickness effects.

Contribution

It introduces a method to determine surface charge densities using electric displacement field in simulations, applicable to various interfaces and overcoming previous limitations.

Findings

Displacement field D determines integrated surface charge density.

Yeh-Berkowitz and mirrored slab methods impose zero surface charge.

Method works for rocksalt and kaolinite interfaces.

Abstract

Attaining accurate average structural properties in a molecular simulation should be considered a prerequisite if one aims to elicit meaningful insights into a system's behavior. For charged surfaces in contact with an electrolyte solution, an obvious example is the density profile of ions along the direction normal to the surface. Here we demonstrate that, in the slab geometry typically used in simulations, imposing an electric displacement field $D$ determines the integrated surface charge density of adsorbed ions at charged interfaces. This allows us to obtain macroscopic surface charge densities irrespective of the slab thickness used in our simulations. We also show that the commonly used Yeh-Berkowitz method and the 'mirrored slab' geometry both impose vanishing integrated surface charge density. We present results both for relatively simple rocksalt (111) interfaces, and the more complex case of kaolinite's basal faces in contact with aqueous electrolyte solution.