A cell-model study on counterion fluctuations in macroionic systems: effect of non-extensiveness in entropy

Abstract

Rigorously speaking, entropy is slightly non-extensive, and this non-extensiveness, which characterizes the degree of fluctuations, can contribute to effective interactions between mesoscopic objects. In this paper, we consider a pair of macroions, each accompanied by 1000 counterions, and with a cell-model description we demonstrate that the slow variation of non-extensiveness in counterion entropy over macroionic distance leads to an effective long-range attraction between the macroions. With the aid of Monte Carlo simulation and a Bragg–Williams theory including counterion number fluctuations, we find the depth of attraction in free energy to be approximately 0.2k_BT. The observation in our cell-model study provides an insight for further understanding of effective interactions in real macroionic systems.