Widom insertion method in simulations with Ewald summation

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.

References in corpus (5)

• Application of Ewald summations to long-range dispersion forces
• Simulations of Coulomb systems with slab geometry using an efficient 3d Ewald summation method
• Note: A pairwise form of the Ewald sum for non-neutral systems
• Pair interactions between complex mesoscopic particles from Widom's particle-insertion method
• Adsorption of polyelectrolytes on charged microscopically patterned surfaces