Fully Periodic, Computationally Efficient Constant Potential Molecular Dynamics Simulations of Ionic Liquid Supercapacitors

TL;DR

This paper introduces a fully periodic boundary condition approach for constant potential molecular dynamics simulations of ionic liquid supercapacitors, significantly reducing computational costs while maintaining accuracy.

Contribution

It demonstrates how to implement fully periodic CPM MD simulations using a doubled cell approach, achieving nearly double the speed of traditional non-periodic methods.

Findings

Fully periodic CPM MD simulations are comparable in accuracy to traditional methods.

The new approach achieves nearly double the computational speed.

Periodic CPM MD can be faster than non-periodic fixed-charge simulations.

Abstract

Molecular dynamics (MD) simulations of complex electrochemical systems, such as ionic liquid supercapacitors, are increasingly including the constant potential method (CPM) to model conductive electrodes at specified potential difference, but the inclusion of CPM can be computationally expensive. We demonstrate the computational savings available in CPM MD simulations of ionic liquid supercapacitors when the usual non-periodic slab geometry is replaced with fully periodic boundary conditions. We show how a doubled cell approach, previously used in non-CPM MD simulations of charged interfaces, can be used to enable fully periodic CPM MD simulations. Using either a doubled cell approach, or a finite field approach previously reported by others, fully periodic CPM MD simulations produce comparable results to the traditional slab geometry simulations with a nearly double speed-up in computational time. Indeed, these savings can offset the additional cost of the CPM algorithm, resulting in periodic CPM MD simulations that are faster than the non-periodic, fixed-charge equivalent simulations for the ionic liquid supercapacitors studied here.