Ion pairing in model electrolytes: A study via three particle correlation functions

Abstract

A novel integral equations approach is applied for studying ion pairing in the restricted primitive model (RPM) electrolyte, i. e., the three point extension (TPE) to the Ornstein-Zernike integral equations. In the TPE approach, the three-particle correlation functions $g^{[3]}({\bf r}_{1},{\bf r}_{2},{\bf r}_{3})$ are obtained. The TPE results are compared to molecular dynamics (MD) simulations and other theories. Good agreement between TPE and MD is observed for a wide range of parameters, particularly where standard integral equations theories fail, i. e., low salt concentration and high ionic valence. Our results support the formation of ion pairs and aligned ion complexes.