Rodlike Counterions near Charged Cylinders: Counterion Condensation and Intercylinder Interaction.

We study a system composed of like-charged cylinders and dumbbell-like counterions, with the focus laid on the role of the internal structure of counterions, using Monte Carlo simulations. The dumbbell ions are found to exhibit novel counterion condensation behavior governed by their length. Effective electrostatic interactions mediated between charged parallel cylinders also turn out significantly different from the case of pointlike ions, as a result of the complex interplay between the spatially separated charge distribution in the dumbbell counterions, their orientation, and the curvature of the charged cylinder.

Hidden Criticality of Counterion Condensation Near a Charged Cylinder.

Counterion condensation onto a charged cylinder, known as the Manning transition, has received a great deal of attention since it is essential to understand the properties of polyelectrolytes in ionic solutions. However, the current understanding is still far from complete and poses a puzzling question: While the strong-coupling theory valid at large ionic correlations suggests a discontinuous nature of the counterion condensation, the mean-field theory always predicts a continuous transition at the same critical point. This naturally leads to a question how one can reconcile the mean-field theory with the strong-coupling prediction.

Scaling and criticality of the Manning transition.

We consider a system consisting of a charged cylinder in the presence of neutralizing counterions. This system is well known to exhibit the Manning transition of counterion condensation onto the charged cylinder. We study the criticality and the scaling properties of the Manning transition, analyzing involved thermodynamic quantities such as condensed fraction, its fluctuation, and heat capacity.