Monte Carlo Simulations of Primitive Model (PM) Electrolytes in Non-Euclidean Geometries

Abstract

Monte Carlo canonical ensemble (NVT) simulations of unrestricted primitive model electrolytes (PM) on the 3D “surface” of a 4D hypersphere are reported here. The effects of concentration, ionic charge and/or ionic radii on the mean internal energy (⟨U⟩), individual and mean ionic activities (⟨γ ⁺⟩, ⟨γ ^-⟩ or ⟨γ ^±⟩) and the mean net charge density distributions were studied. Our results showed that either higher charge, higher concentration or smaller ionic radii favoured ion–ion aggregation. The individual ionic activity coefficients of ions with different radii and/or charge differed significantly at higher concentrations. We also compared mean ionic activity coefficients for aqueous KCl and NaBr from simulations with reported experimental values in the literature and the agreement within 0.7–10%, depending upon concentration were found.

Keywords:

• Monte Carlo simulations
• Primitive model (PM) electrolytes
• Non-Euclidean
• Spherical boundary conditions
• Hyperspherical and individual ionic activity coefficient

Notes

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