Breakdown of the Yukawa model in de-ionized colloidal suspensions

We study effective colloidal interactions in de-ionized colloidal mixtures through sedimentation-diffusion equilibrium. We derive a coarse-grained effective model (EM) and compare its density profiles with those of the computationally much more expensive primitive model (PM) of colloids and counterions in gravity. The EM, which contains not only standard pairwise screened-Coulomb interactions, but also explicit many-body effects by means of a so-called volume term, can quantitatively account for all observed sedimentation phenomena such as lifting of colloids to high altitudes, segregation into layers in mixtures, and floating of heavy colloids on top of lighter ones. Without the volume term there is no quantitative agreement between the PM and EM, even in the present high-temperature limit of interest, showing that de-ionized colloidal suspensions cannot be described by a pairwise Yukawa model.