A molecular perspective on induced charges on a metallic surface

TL;DR

This study compares continuum electrostatics and molecular dynamics simulations to understand induced charges on metallic surfaces, revealing their similarities and limitations in different conditions, and informing better interface models.

Contribution

It demonstrates the effectiveness and limitations of continuum electrostatics versus molecular simulations in modeling induced charges on metallic electrodes.

Findings

Continuum electrostatics aligns with molecular simulations in vacuum and far from the surface.

Limitations include neglecting solvent-induced charges and screening effects.

Results inform the development of improved implicit solvent models.

Abstract

Understanding the response of the surface of metallic solids to external electric field sources is crucial to characterize electrode-electrolyte interfaces. Continuum electrostatics offer a simple description of the induced charge density at the electrode surface. However, such a simple description does not take into account features related to the atomic structure of the solid and to the molecular nature of the solvent and of the dissolved ions. In order to illustrate such effects and assess the ability of continuum electrostatics to describe the induced charge distribution, we investigate the behaviour of a gold electrode interacting with sodium or chloride ions fixed at various positions, in vacuum or in water, using all-atom constant-potential classical molecular dynamics simulations. Our analysis highlights important similarities between the two approaches, especially in vacuum conditions and when the ion is sufficiently far from the surface, as well as some limitations of the continuum description, namely neglecting the charges induced by the adsorbed solvent molecules and the screening effect of the solvent when the ion is close to the surface. While the detailed features of the charge distribution are system-specific, we expect some of our generic conclusions on the induced charge density to hold for other ions, solvents and electrode surfaces. Beyond this particular case, the present study also illustrates the relevance of such molecular simulations to serve as a reference for the design of improved implicit solvent models of electrode-electrolyte interfaces.