Scaling and universality in the counterion-condensation transition at charged cylinders.
Counterions at charged rodlike polymers exhibit a condensation transition at a critical temperature (or, equivalently, at a critical linear charge density for polymers), which dramatically influences various static and dynamic properties of charged polymer solutions. We address the critical and universal aspects of this transition for counterions at a single charged cylinder in two and three spatial dimensions using numerical and analytical methods. By introducing a Monte Carlo sampling method in logarithmic radial scale, we are able to numerically simulate the critical limit of infinite system size (corresponding to the 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 mean inverse localization length of counterions) both within mean-field theory and within Monte Carlo simulations. In three dimensions (3D), we demonstrate that correlation effects (neglected within mean-field theory) lead to an excessive accumulation of counterions near the charged cylinder below the critical temperature (i.e., in the condensation phase), while surprisingly, the critical region exhibits universal critical exponents in accordance with mean-field theory. Also in contrast with the typical trend in bulk critical phenomena, where fluctuations become more enhanced in lower dimensions, we demonstrate, using both numerical and analytical approaches, that mean-field theory becomes exact for the two-dimensional (2D) counterion-cylinder system at all temperatures (Manning parameters), when the number of counterions tends to infinity. For a finite number of particles, however, the 2D problem displays a series of peculiar singular points (with diverging heat capacity), which reflect successive delocalization 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 internal energy develops a pronounced peak. The asymptotic behavior of the energy peak location is used to determine the critical temperature, which is also found to be in agreement with the mean-field prediction.
Naji
Ali
A
Physics Department, Technical University of Munich, Garching, Germany. anaji@chem.ucsb.edu
Netz
Roland R
RR