Finite Field Methods for the Supercell Modelling of Charged Insulator-Electrolyte Interfaces

Abstract

Surfaces of ionic solids interacting with an ionic solution can build up charge by exchange of ions. The surface charge is compensated by a strip of excess charge at the border of the electrolyte forming an electric double layer. These electric double layers are very hard to model using the supercells methods of computational condensed phase science. The problem arises when the solid is an electric insulator (as most ionic solids are) permitting a finite interior electric field over the width of the slab representing the solid in the supercell. The slab acts as a capacitor. The stored charge is a deficit in the solution failing to compensate fully for the solid surface charge. Here we show how these problems can be overcome using the finite field methods developed by Stengel, Spaldin and Vanderbilt [Nat. Phys. {\bf 5}, 304, (2009)]. We also show how the capacitance of the double layer can be computed once overall electric neutrality of the double layer is restored by application of a finite macroscopic field $\mathbf{E}$ or alternatively by zero electric displacement $\mathbf{D}$. The method is validated for a classical model of a solid-electrolyte interface using the finite temperature molecular dynamics adaptation of the constant field method presented previously [Phys. Rev. B, 2016, 93, 144201]. Because ions in electrolytes can diffuse across supercell boundaries, this application turns out to be a critical illustration of the multivaluedness of polarization in periodic systems.

arXiv comment19 pages, 11 figures

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• Universal Machine Learning for the Response of Atomistic Systems to External Fields
• Computational Amperometry of Nanoscale Capacitors in Molecular Simulations
• Finite electric displacement simulations of polar ionic solid-electrolyte interfaces: Application to NaCl(111)/aqueous NaCl solution
• Finite field formalism for bulk electrolyte solutions
• Stabilization of AgI's polar surfaces by the aqueous environment, and its implications for ice formation
• Charge compensation at the interface between the polar NaCl(111) surface and a NaCl aqueous solution
• Learning classical density functionals for ionic fluids
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• Analytic Theory of Finite-size Effects in Supercell Modelings of Charged Interfaces
• Electromechanics of the liquid water vapour interface
• Macroscopic surface charges from microscopic simulations
• Computing the Helmholtz Capacitance of Charged Insulator-Electrolyte Interfaces from the Supercell Polarization
• Electric Double Layer at the Metal-Oxide/Electrolyte Interface
• Static Dielectric Permittivity Profiles and Coarse-graining Approaches for Water in Graphene Slit Pores
• A theory for the stabilization of polar crystal surfaces by a liquid environment
• Comment on "Macroscopic surface charges from microscopic simulations" [J. Chem. Phys. 153, 164709 (2020)]