Simulation of electric double layers around charged colloids in aqueous solution of variable permittivity

• Published in: The Journal of chemical physics Vol. 141; no. 6; p. 064902
• Main Authors: Fahrenberger, Florian, Xu, Zhenli, Holm, Christian
• Format: Journal Article
• Language: English
• Published: United States 14-08-2014
• Subjects: Algorithms; Colloids - chemistry; Electrons; Molecular Dynamics Simulation; Solutions; Static Electricity; Water - chemistry
• ISSN: 1089-7690
• DOI: 10.1063/1.4892413

The ion distribution around charged colloids in solution has been investigated intensely during the last decade. However, few theoretical approaches have included the influence of variation in the dielectric permittivity within the system, let alone in the surrounding solvent. In this article, we introduce two relatively new methods that can solve the Poisson equation for systems with varying permittivity. The harmonic interpolation method approximately solves the Green's function in terms of a spherical harmonics series, and thus provides analytical ion-ion potentials for the Hamiltonian of charged systems. The Maxwell equations molecular dynamics algorithm features a local approach to electrostatics, allowing for arbitrary local changes of the dielectric constant. We show that the results of both methods are in very good agreement. We also found that the renormalized charge of the colloid, and with it the effective far field interaction, significantly changes if the dielectric properties within the vicinity of the colloid are changed.