Constant Potential and Constrained Charge Ensembles for Simulations of Conductive Electrodes

TL;DR

This paper extends the constant potential molecular dynamics method to control total electrode charge, establishing a new thermodynamic ensemble that improves simulation efficiency and broadens application possibilities.

Contribution

It introduces a theoretical framework for fixed total charge ensembles in CPM MD, linking them to fixed potential difference ensembles and demonstrating their practical advantages.

Findings

The new ensemble is thermodynamically distinct but related to fixed potential ensembles.

Simulations show faster equilibration in the fixed total charge ensemble.

Application to ionic liquid supercapacitors validates the approach.

Abstract

Constant potential method molecular dynamics simulation (CPM MD) enables the accurate modelling of atomistic electrode charges when studying the electrode-electrolyte interface at the nanoscale. Here we extend the theoretical framework of CPM MD to the case in which the total charge of each conductive electrode is controlled, instead of their potential differences. We show that the resulting thermodynamic ensemble is distinct from that sampled in with a fixed potential difference, but rigorously related as conjugate ensembles. This theoretical correspondence, which we demonstrate using simulations of an ionic liquid supercapacitor, underpins the success of recent studies with fixed total charges on the electrodes. We show that equilibration is usefully sped up in this ensemble and outline some potential applications of these simulations in future.