A molecular perspective on induced charges on a metallic surface

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.

References in corpus (9)

• The electric double layer has a life of its own
• Molecular Simulation of Electrode-Solution Interfaces
• Size-dependence of hydrophobic hydration at electrified gold/water interfaces
• Effect of the metallicity on the capacitance of gold - aqueous sodium chloride interfaces
• Efficient molecular density functional theory using generalized spherical harmonics expansions
• Non-Reciprocal Interactions Induced by Water in Confinement
• Capacitance and Structure of Electric Double Layers: Comparing Brownian Dynamics and Classical Density Functional Theory
• Simulations of ionic liquids confined by metal electrodes using periodic Green functions
• A molecular perspective on induced charges on a metallic surface

Cited by in corpus (2)

• Frequency-dependent impedance of nanocapacitors from electrode charge fluctuations as a probe of electrolyte dynamics
• A molecular perspective on induced charges on a metallic surface