Green's function for a spherical dielectric discontinuity and its application to simulation

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Green's function for a spherical dielectric discontinuity and its application to simulation. / Linse, Per; Lue, Leo.

In: Journal of Chemical Physics, Vol. 140, No. 4, 044903, 2014.

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TY - JOUR

T1 - Green's function for a spherical dielectric discontinuity and its application to simulation

AU - Linse, Per

AU - Lue, Leo

PY - 2014

Y1 - 2014

N2 - 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. (C) 2014 AIP Publishing LLC.

AB - 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. (C) 2014 AIP Publishing LLC.

U2 - 10.1063/1.4862148

DO - 10.1063/1.4862148

M3 - Article

VL - 140

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 4

M1 - 044903

ER -