Electrochemical potentials in the grand canonical ensemble: Some formal and numerical results for confined ionic systems

The grand canonical ensemble has been used to study electrochemical potentials in confined ionic systems. Grand canonical ensemble Monte Carlo calculations for the primitive model of electrolyte solutions are presented for spherical systems, and the evaluation of single ion activity coefficients by such calculations is discussed. It is also shown that the introduction of finite, confined systems resolves a well-known problem associated with the application of the Kirkwood-Buff theory to ionic systems.