Scaling and Universality in the Counterion-Condensation Transition at Charged Cylinders

TL;DR

This paper investigates the universal and critical behavior of counterion condensation around charged cylinders in two and three dimensions using novel numerical and analytical methods, revealing universal exponents and phase transition characteristics.

Contribution

It introduces a new Monte-Carlo sampling method in logarithmic scale and provides comprehensive analysis of critical exponents and universality in counterion condensation in 2D and 3D.

Findings

Critical exponents match mean-field predictions in 3D.

Universal heat capacity jump at the critical point.

In 2D, mean-field theory becomes exact as particle number increases.

Abstract

We address the critical and universal aspects of counterion-condensation transition at a single charged cylinder in both two and three spatial dimensions using numerical and analytical methods. By introducing a novel Monte-Carlo sampling method in logarithmic radial scale, we are able to numerically simulate the critical limit of infinite system size (corresponding to infinite-dilution limit) within tractable equilibration times. The critical exponents are determined for the inverse moments of the counterionic density profile (which play the role of the order parameters and represent the inverse localization length of counterions) both within mean-field theory and within Monte-Carlo simulations. In three dimensions (3D), correlation effects (neglected within mean-field theory) lead to an excessive accumulation of counterions near the charged cylinder below the critical temperature (condensation phase), while surprisingly, the critical region exhibits universal critical exponents in accord with the mean-field theory. In two dimensions (2D), we demonstrate, using both numerical and analytical approaches, that the mean-field theory becomes exact at all temperatures (Manning parameters), when number of counterions tends to infinity. For finite particle number, however, the 2D problem displays a series of peculiar singular points (with diverging heat capacity), which reflect successive de-localization events of individual counterions from the central cylinder. In both 2D and 3D, the heat capacity shows a universal jump at the critical point, and the energy develops a pronounced peak. The asymptotic behavior of the energy peak location is used to locate the critical temperature, which is also found to be universal and in accordance with the mean-field prediction.