Computing the Helmholtz Capacitance of Charged Insulator-Electrolyte Interfaces from the Supercell Polarization

TL;DR

This paper introduces a new formula to accurately compute the Helmholtz capacitance of charged insulator-electrolyte interfaces using supercell polarization at zero electric field, validated by atomistic simulations and independent of supercell size.

Contribution

A novel formula based on supercell polarization at zero electric field for calculating Helmholtz capacitance, simplifying the process and applicable to standard molecular dynamics simulations.

Findings

Formula validated with atomistic simulations

Capacitance calculation independent of supercell size

Applicable to standard Ewald-based molecular dynamics codes

Abstract

Supercell modelling of an electrical double layer (EDL) at electrified solid-electrolyte interfaces is a challenge. The net polarization of EDLs arising from the fixed chemical composition setup leads to uncompensated EDLs under periodic boundary condition and convolutes the calculation of the Helmholtz capacitance [Zhang and Sprik, Phys. Rev. B, 94, 245309 (2016)]. Here we provide a new formula based on the supercell polarization at zero electric field $\bar{E} = 0$ (i.e. standard Ewald boundary condition) to calculate the Helmholtz capacitance of charged insulator-electrolyte interfaces and validate it using atomistic simulations. Results are shown to be independent of the supercell size. This formula gives a shortcut to compute the Helmholtz capacitance without locating the zero net charge state of EDL and applies directly to any standard molecular dynamics code where the electrostatic interactions are treated by the Ewald summation or its variants.