Size Effect in Grand-canonical Monte-Carlo Simulation of Solutions of Electrolyte

Abstract

Abstract: A Grand-canonical Monte-Carlo simulation method is investigated. Due to charge neutrality requirement of electrolyte solutions, ions must be added to or removed from the system in groups. It is then implemented to simulate solution of 1:1, 2:1 and 2:2 salts at different concentrations using the primitive ion model. We investigate how the finite size of the simulation box can influence statistical quantities of the salt system. Remarkably, the method works well down to a system as small as one salt molecule. Although the fluctuation in the statistical quantities increases as the system gets smaller, their average values remain equal to their bulk value within the uncertainty error. Based on this knowledge, the osmotic pressures of the electrolyte solutions are calculated and shown to depend linearly on the salt concentrations within the concentration range simulated. Chemical potential of ionic salt that can be used for simulation of these salts in more complex system are calculated.

Keywords: GCMC, electrolyte solution simulation, primitive ion model, finite size effect.

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