Layering in sedimentation of suspensions of charged colloids: simulation and theory

We study the equilibrium sediment of a multicomponent system of charged colloids using primitive model Monte Carlo simulations, which include counterions explicitly. We find separation of the different colloidal components into almost pure layers, where colloids with large charge-to-mass ratio sediment higher in the sample. This effect appears due to a competition between ionic entropy, gravitational energy, and electrostatic energy. Our simulations provide a direct confirmation of recent theoretical predictions on the sedimentation of multicomponent mixtures of charged colloids in regimes with relatively low total densities and low colloidal charges. To explore the limitations of the theory we perform simulations at higher total densities for monodisperse and multicomponent systems and at stronger electrostatic couplings by increasing the colloidal charge for monodisperse suspensions. We find good agreement between theory and simulation when the colloidal charge is increased in the monodisperse case. However, we find deviations between simulations and theory upon increasing the total densities in the monodisperse and multicomponent systems. The density profiles obtained from simulations are more homogeneous than those predicted by theory. The spontaneous formation of layered structures predicted by the theory and found by simulation can serve as a useful tool to separate different components from a mixture of charged colloids.