The role of image charges in the interactions between colloidal particles

The dielectric interiors of colloidal particles are responsible for dispersion (van der Waals) interactions. However, these dielectric regions also alter the manner in which charges, such as on ions or other colloidal particles, interact with each other, due to the induction of charges at the dielectric interfaces. The impact of these induced charges can be represented in terms of "image charges". These image charges result in an ion depletion layer in the vicinity of low dielectric bodies. This depletion layer is responsible for the increase in the surface tension of water upon the addition of electrolytes. In the case of colloidal particles, this depletion layer also leads to an "electrostatic depletion force" with a range of the order of a Bjerrum length. The relevance of this force to the salting out of proteins is discussed. This electrostatic depletion force is directly analogous to the entropically driven depletion force (due to excluded volume). Although image charge effects have been known, their influence on the behavior of colloidal systems, especially in the presence of mobile ions, has generally not been accounted for (e.g., DLVO theory). We review the previous theoretical and simulation studies of how image charges influence the properties of electrolyte and colloidal systems and discuss the relevance of these effects on experimental systems.