Toward making the mean spherical approximation of primitive model electrolytes analytic: An analytic approximation of the MSA screening parameter

Abstract

The mean spherical approximation (MSA) for the primitive model of electrolytes provides reasonable estimates of thermodynamic quantities such as the excess chemical potential and screening length. It is especially widely used because of its explicit formulas so that numerically solving equations is minimized. As originally formulated, the MSA screening parameter Γ (akin to the reciprocal of the Debye screening length) does not have an explicit analytic formula; an equation for Γ must be solved numerically. Here, an analytic approximation for Γ is presented whose relative error is generally ≲10(-5). If more accuracy is desired, one step of an iterative procedure (which also produces an explicit formula for Γ) is shown to give relative errors within machine precision in many cases. Even when ion diameter ratios are ∼10 and ion valences are ∼10, the relative error for the analytic approximation is still ≲10(-3) and for the single iterative substitution it is ≲10(-9).