The Osmotic Coefficient of Rod-like Polyelectrolytes: Computer Simulation, Analytical Theory, and Experiment

Abstract

The osmotic coefficient of solutions of rod-like polyelectrolytes is considered by comparing current theoretical treatments and simulations to recent experimental data. The discussion is restricted to the case of monovalent counterions and dilute, salt-free solutions. The classical Poisson-Boltzmann solution of the cell model correctly predicts a strong decrease in the osmotic coefficient, but upon closer look systematically overestimates its value. The contribution of ion-ion-correlations are quantitatively studied by MD simulations and the recently proposed DHHC theory. However, our comparison with experimental data obtained on synthetic, stiff-chain polyelectrolytes shows that correlation effects can only partly explain the discrepancy. A quantitative understanding thus requires theoretical efforts beyond the restricted primitive model of electrolytes.

16 pages, 2 figures

Cited by in corpus (5)

• Effective charge saturation in colloidal suspensions
• Scaling and Universality in the Counterion-Condensation Transition at Charged Cylinders
• Theory and simulations of rigid polyelectrolytes
• Soft effective interactions between weakly charged polyelectrolyte chains
• Counter-ion density profile around charged cylinders: the strong-coupling needle limit