title: Green's function for a spherical dielectric discontinuity and its application to simulation.
abstract: We present rapidly convergent expressions for the Green's function of the Poisson equation for spherically symmetric systems where the dielectric constant varies discontinuously in the radial direction. These expressions are used in Monte Carlo simulations of various electrolyte systems, and their efficiency is assessed. With only the leading term of the expansion included, a precision of the polarization energy of 0.01 kJ mol(-1) or better was achieved, which is smaller than the statistical uncertainty of a typical simulation. The inclusion of the dielectric inhomogeneity leads to a 2.5-fold increase of the computational effort, which is modest for this type of model. The simulations are performed on six types of systems having either (i) a uniform surface charge distribution, (ii) a uniform volume charge distribution, or (iii) mobile ions, which were neutralized by mobile counterions. The ion density distributions are investigated for different dielectric conditions. These spatial distributions are discussed in terms of the importance of (i) the direct mean-field Coulomb interaction, (ii) the surface charge polarization at the dielectric discontinuity, and/or (iii) the change in the attractive Coulomb correlations.
authors: Physical Chemistry, Department of Chemistry, Lund University, P.O. Box 124, S-221 00 Lund, Sweden.
authors: Per
authors: P
authors: Linse
authors: Department of Chemical and Process Engineering, University of Strathclyde, James Weir Building, 75 Montrose Street, Glasgow G1 1XJ, United Kingdom.
authors: Leo
authors: L
authors: Lue
mesh_terms: D003198:Computer Simulation; D004573:Electrolytes / Q000737:chemistry; D008962:Models, Theoretical; D009010:Monte Carlo Method
chemical_list: D004573:Electrolytes