Grand Canonical Ensemble Monte Carlo Simulations of Donnan Potentials, Nonelectroneutrality, Activity Coefficients and Excess Energy in Spherical Charged or Uncharged Pores with Restricted Primitive Model Electrolytes

Abstract

Abstract A great number of Grand Canonical Ensemble simulations have been performed for restricted primitive model electrolytes in spherical hard-wall pores with the same dielectric permittivity in the pores and in the wall. The pores have a continuously distributed surface charge from 0 to 10 elementary charges and radii from 1 to 35 ionic diameters. When a pore is in equilibrium with an outside bulk solution, it acquires in the average a certain deviation from electroneutrality (spontaneous electrification). For any given pore surface charge this electrification is a given function of the radius of the accessible part of the pore scaled by the Debye length without regard to the Debye length without regard to the Bjerrum parameter or the bulk concentration of the electrolyte and without regard to the pore size relative to the ion diameter. If an additional uniform electric potential is applied in the pore, the electrification changes. At a certain potential the pore is electroneutral. This potential is a...