Macroscopic surface charges from microscopic simulations

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.

Main paper: 8 pages; 4 figures. Supporting Info: 2 pages; 2 figures

References in corpus (19)

• Ice Formation on Kaolinite: Insights from Molecular Dynamics Simulations
• Simulating electrochemical systems by combining the finite field method with a constant potential electrode
• The Microscopic Features of Heterogeneous Ice Nucleation May Affect the Macroscopic Morphology of Atmospheric Ice Crystals
• Computing the dielectric constant of liquid water at constant dielectric displacement
• Coupling of surface chemistry and electric double layer at TiO${}_2$ electrochemical interfaces
• Rigorous definition of oxidation states of ions in solids
• Measuring surface charge: why experimental characterization and molecular modeling should be coupled
• Finite Field Methods for the Supercell Modelling of Charged Insulator-Electrolyte Interfaces
• Note: On the dielectric constant of nanoconfined water
• Dielectric response with short-ranged electrostatics
• Finite electric displacement simulations of polar ionic solid-electrolyte interfaces: Application to NaCl(111)/aqueous NaCl solution
• Stabilization of AgI's polar surfaces by the aqueous environment, and its implications for ice formation
• Finite field formalism for bulk electrolyte solutions
• Charge compensation at the interface between the polar NaCl(111) surface and a NaCl aqueous solution
• Non-equilibrium simulations of thermally induced electric fields in water
• Interfacial ion solvation: Obtaining the thermodynamic limit from molecular simulations
• Analytic Theory of Finite-size Effects in Supercell Modelings of Charged Interfaces
• Electromechanics of the liquid water vapour interface
• Computing the Helmholtz Capacitance of Charged Insulator-Electrolyte Interfaces from the Supercell Polarization

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