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 2.5fold 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 meanfield Coulomb interaction, (ii) the surface charge polarization at the dielectric discontinuity, and/or (iii) the change in the attractive Coulomb correlations.
Original language  English 

Article number  044903 
Number of pages  12 
Journal  Journal of Chemical Physics 
Volume  140 
Issue number  4 
DOIs  
Publication status  Published  28 Jan 2014 
Keywords
 dielectrics
 dielectric constant
 surface charge
 Green's function methods
Fingerprint
Dive into the research topics of 'Green's function for a spherical dielectric discontinuity and its application to simulation'. Together they form a unique fingerprint.Profiles

Leo Lue
Person: Academic