Towards an analytical theory for charged hard spheres

TL;DR

This paper develops an analytical theory for charged hard sphere ion mixtures, extending Debye-Hückel and MSA models to higher densities with a single screening parameter, and demonstrates good agreement with Monte Carlo simulations.

Contribution

It introduces the BIMSA model, a one-parameter representation valid for complex ionic systems, satisfying the infinite dilution limit of Debye-Hückel theory.

Findings

BIMSA accurately models ionic mixtures at higher densities.

The theory aligns well with Monte Carlo simulation results.

It provides a unified framework for complex and associating systems.

Abstract

Ion mixtures require an exclusion core to avoid collapse. The Debye Hueckel theory, where ions are point charges, is accurate only in the limit of infinite dilution. The MSA is the embedding of hard cores into DH, is valid for higher densities. In the MSA the properties of any ionic mixture can be represented by a single screening parameter $\Gamma$. For equal ionic size restricted model is obtained from the Debye parameter $\kappa$. This one parameter representation (BIMSA) is valid for complex and associating systems, such as the general n-polyelectrolytes. The BIMSA is the only theory that satisfies the infinite dilution limit of the DH theory for any chain length. The contact pair distribution function of hard ions mixture is a functional of $\Gamma$ and a small mean field parameter. This yields good agreement with the Monte Carlo (Bresme et al. Phys. Rev. E {\textbf 51} 289 (1995)) .