Surface and extrapolated point charge renormalizations for charge-stabilized colloidal spheres

Abstract

Abstract.: The Derjaguin-Landau-Verwey-Overbeek (DLVO) theory is widely used to model interactions between weakly charged spheres in dilute suspensions. For particles bearing a higher charge, the linearized electrostatics underlying the DLVO theory is no longer valid but it is possible to map the real colloidal system to an auxiliary one that still obeys linear electrostatics but which involves a different, effective pair potential. This procedure, termed renormalization, can be performed in various ways, the most widely used being surface charge renormalization (SCR) based on the cell model. SCR is still limited to dilute suspensions since the auxiliary system is made of spheres interacting through a DLVO-like pair potential. The recent extrapolated point charge (EPC) renormalization overcomes this limitation by using point charges in the auxiliary system and has indeed been shown to produce better results than the SCR in dense suspensions. Here, we recall that the DLVO-like potential used in the SCR can be modified to account for many-body ion-colloid core exclusion effects (a model termed SCRX here); we show that the accuracy of the EPC and SCRX renormalizations is virtually identical, and conclude by explaining why the EPC method is still the most attractive option of the two in many cases.