Finite electric displacement simulations of polar ionic solid-electrolyte interfaces: Application to NaCl(111)/aqueous NaCl solution

TL;DR

This paper introduces a method using finite electric displacement fields in molecular dynamics simulations to accurately model polar ionic solid-electrolyte interfaces, enabling better understanding of charge compensation phenomena.

Contribution

It extends previous electric field methods by applying a conjugate displacement field D, improving convergence and allowing DFT-based simulations of polar interfaces.

Findings

Displacement field D speeds up polarization convergence.

The method accurately models charge compensation at ionic interfaces.

Application to NaCl(111)/aqueous NaCl shows effective stabilization of polar surfaces.

Abstract

Tasker type III polar terminations of ionic crystals carry a net surface charge as well as a dipole moment and are fundamentally unstable. In contact with electrolytes, such polar surfaces can be stabilized by adsorption of counter ions from solution to form electric double layers (EDLs). In a previous work (J. Chem. Phys 147, 104702 (2017)) we reported on a classical force field based molecular dynamics study of a prototype model system namely a NaCl(111) slab interfaced with an aqueous NaCl solution on both sides. A serious hurdle in the simulation is that the finite width of the slab admits an electric field in the solid perturbing the theoretical charge balance at the interface of semi-infinite systems (half the surface charge density for NaCl(111)). It was demonstrated that the application of a finite macroscopic field $E$ cancelling the internal electric field can recover the correct charge compensation at the interface. In the present work, we expand this method by applying a conjugate electric displacement field $D$. The benefits of using $D$ instead of $E$ as the control variable are two fold: it does not only speed up the convergence of the polarization in the simulation but also leads to a succinct expression for the biasing displacement field involving only structural parameters which are known in advance. This makes it feasible to study the charge compensating phenomenon of this prototype system with density functional theory based molecular dynamics (DFTMD), as shown in this work.