Self-consistent field model for strong electrostatic correlations and inhomogeneous dielectric media

Abstract

Electrostatic correlations and variable permittivity of electrolytes are essential for exploring many chemical and physical properties of interfaces in aqueous solutions. We propose a continuum electrostatic model for the treatment of these effects in the framework of the self-consistent field theory. The model incorporates a space-or field-dependent dielectric permittivity and an excluded ion-size effect for the correlation energy. This results in a self-energy modified Poisson-Nernst-Planck or Poisson-Boltzmann equation together with state equations for the self energy and the dielectric function. We show that the ionic size is of significant importance in predicting a finite self energy for an ion in an inhomogeneous medium. Asymptotic approximation is proposed for the solution of a generalized Debye-Huckel equation, which has been shown to capture the ionic correlation and dielectric self energy. Through simulating ionic distribution surrounding a macroion, the modified self-consistent field model is shown to agree with particle-based Monte Carlo simulations. Numerical results for symmetric and asymmetric electrolytes demonstrate that the model is able to predict the charge inversion at high correlation regime in the presence of multivalent interfacial ions which is beyond the mean-field theory, and also show strong effect to double layer structure due to the space- or field-dependent dielectric permittivity.

12 pages; 6 figures; version to be published in J. Chem. Phys

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• Importance of Varying Permittivity on the Conductivity of Polyelectrolyte Solutions
• The influence of charged-induced variations in the local permittivity on the static and dynamic properties of polyelectrolyte solutions
• Electric-field-induced oscillations in ionic fluids: a unified formulation of modified Poisson-Nernst-Planck models and its relevance to correlation function analysis
• A Maxwell-Ampère Nernst-Planck Framework for Modeling Charge Dynamics
• Electrostatic contribution to colloidal solvation in terms of the self-energy modified Boltzmann distribution
• Hysteresis and Linear Stability Analysis on Multiple Steady-State Solutions to the Poisson--Nernst--Planck equations with Steric Interactions
• Linear-Scaling Selected Inversion based on Hierarchical Interpolative Factorization for Self Green's Function for Modified Poisson-Boltzmann Equation in Two Dimensions
• Competition between Born solvation, dielectric exclusion, and Coulomb attraction in spherical nanopores