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

TL;DR

This paper develops a variational field theory to accurately compute the electrostatic self-energy in ionic fluids, linking it to correlation functions and providing improved solvation energy estimates that align with simulations.

Contribution

It introduces a novel variational approach based on lower bound inequality to connect self-energy with correlation functions in charged fluids, enhancing solvation energy calculations.

Findings

Self-energy expressed as difference between total and direct correlation functions.

Derived generalized Debye-Hückel equations with Gaussian distributed charges.

Good agreement of theoretical solvation energies with simulation data.

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-H\"uckel equations reflecting the Gaussian distributed charges.