Screening of a charged particle by multivalent counterions in salty water: Giant charge inversion

Abstract

Screening of a macroion such as a charged solid particle, a charged membrane, double helix DNA or actin by multivalent counterions is considered. Small colloidal particles, charged micelles, short or long polyelectrolytes can play the role of multivalent counterions. Due to strong lateral repulsion at the surface of macroion such multivalent counterions form a strongly correlated liquid, with the short range order resembling that of a Wigner crystal. These correlations create additional binding of multivalent counterions to the macroion surface with binding energy larger than $k_BT$. As a result even for a moderate concentration of multivalent counterions in the solution, their total charge at the surface of macroion exceeds the bare macroion charge in absolute value. Therefore, the net charge of the macroion inverts its sign. In the presence of a high concentration of monovalent salt the absolute value of inverted charge can be larger than the bare one. This giant inversion of charge can be observed by electrophoresis or by direct counting of multivalent counterions.