Ion association in aqueous LiCl solutions at high concentration: Predicted results via molecular simulation

Abstract

We perform molecular dynamics simulations to study the ionic solvation and association behavior in concentrated aqueous LiCl solutions at ambient conditions, including consideration of expected signatures of ion pairing that might be found in neutron diffraction experiments with isotopic substitution. The ten possible pair radial distribution functions that define the microstructure of the systems are determined and used to assess the first-order difference of the neutron-weighted correlation functions for these solutions in heavy and null water. Then, both sets of correlation functions are applied to the interpretation of the ion's local environment in terms of the location of the relevant peaks and the penetration of ions into the counterion solvation shells as a signature of ion-pair formation. Finally, we illustrate how first-order difference experiments involving null and heavy water might be used to assess the magnitude of the M(v+) - X(v-) ion-pair formation for a salt M(v+)X(n) v- in an aqueous solution, provided the significant experimental challenges in these studies could be overcome.