Electrostatic contribution to colloidal solvation in terms of the self-energy modified Boltzmann distribution

Abstract

Electrostatic interactions make a large contribution to solvation free energy in ionic fluids such as electrolytes and colloidal dispersions. The electrostatic contribution to solvation free energy has been ascribed to the self-energy of a charged particle. Here we apply a variational field theory based on lower bound inequality to the inhomogeneous fluids of one-component charged hard-spheres, thereby verifying that the self-energy is given by the difference between the total correlation function and direct correlation function. Based on the knowledge of the liquid state theory, the self-energy specified in this study not only relates a direct correlation function to the Gaussian smearing of each charged sphere, but also provides the electrostatic contribution to solvation free energy that shows good agreement with simulation results. Furthermore, the Ornstein-Zernike equation leads to a new set of generalized Debye-Hückel equations reflecting the Gaussian distributed charges.

to be published in Phys. Rev. E

References in corpus (5)

• Local molecular field theory for effective attractions between like charged objects in systems with strong Coulomb interactions
• Local molecular field theory for the treatment of electrostatics
• Self-consistent field model for strong electrostatic correlations and inhomogeneous dielectric media
• Inhomogeneous fluid of penetrable-spheres: application of the random phase approximation
• Functional-integral approach to Coulomb fluids in the strong coupling limit

Cited by in corpus (3)

• Electric-field-induced oscillations in ionic fluids: a unified formulation of modified Poisson-Nernst-Planck models and its relevance to correlation function analysis
• Non-hyperuniform metastable states around a disordered hyperuniform state of densely packed spheres: stochastic density functional theory at strong coupling
• Competition between Born solvation, dielectric exclusion, and Coulomb attraction in spherical nanopores