Widom insertion method in simulations with Ewald summation

TL;DR

This paper explores two methods for calculating ionic chemical potentials in simulations with Ewald summation, comparing their accuracy and agreement with grand canonical Monte Carlo results.

Contribution

It introduces and compares two approaches for Widom insertion in charged systems with Ewald summation, highlighting the improved accuracy of the second method.

Findings

The second approach yields better agreement with grand canonical Monte Carlo results.

Introducing a neutralizing background improves the accuracy of chemical potential calculations.

Both methods are applicable, but the second is more reliable for ionic systems.

Abstract

We discuss the application of Widom insertion method for calculation of the chemical potential of individual ions in computer simulations with Ewald summation. Two approaches are considered. In the first approach, an individual ion is inserted into a periodically replicated overall charge neutral system representing an electrolyte solution. In the second approach an inserted ion is also periodically replicated, leading to the violation of the overall charge neutrality. This requires an introduction of an additional neutralizing background. We find that the second approach leads to a much better agreement with the results of grand canonical Monte Carlo simulation for the total chemical potential of a neutral ionic cluster.