Optimal cell approach to osmotic properties of finite stiff-chain polyelectrolytes.
We propose a self-consistent geometry optimized cell model approach to study osmotic properties of stiff-chain polyelectrolyte solutions. In contrast with the usual monotonic Poisson-Boltzmann prediction, the cell model predicts the correct nonmonotonic dependence of the osmotic coefficient on concentration. A lower degree of polymerization is found to reduce significantly the counterion condensation in a typical dilute strong polyelectrolyte. The results agree quantitatively with simulations of a corresponding many-body bulk system up to a dense semidilute regime.
Antypov
Dmytro
D
Max-Planck-Institut für Polymerforschung, Ackermannweg 10, 55128, Mainz, Germany. da275@cam.ac.uk
Holm
Christian
C
D004573:Electrolytes / Q000737:chemistry*; D008956:Models, Chemical; D009995:Osmosis; D009997:Osmotic Pressure; D012996:Solutions
D004573:Electrolytes; D012996:Solutions