Effect of many-body interactions on the solid-liquid phase behavior of charge-stabilized colloidal suspensions

The solid-liquid phase diagram of charge-stabilized colloidal suspensions has been calculated using a technique that combines a continuous Poisson-Boltzmann description for the microscopic electrolyte ions with a molecular-dynamics simulation for the macroionic colloidal spheres. While correlations between the microions are neglected in this approach, many-body interactions between the colloids, mediated by the screening ionic fluid between them, are fully included. The Lindemann criterion has been used to determine the solid-to-liquid transition temperature in a colloidal system at a relatively high colloid volume fraction where many-body interactions are expected to be strong. With a view to the Derjaguin-Landau-Verwey-Overbeek theory predicting that colloids interact via Yukawa pair potentials, we compare our results with the phase diagram of a simple Yukawa liquid. We find an agreement under high-salt conditions, but considerable differences at low ionic strength. Using effective force calculations and data from molecular-dynamics simulations with simple model potentials, we further demonstrate that these differences are due to many-body interactions.