Theory and simulations of rigid polyelectrolytes

Abstract

We present theoretical and numerical studies on stiff, linear polyelectrolytes within the framework of the cell model. We first review analytical results obtained on a mean-field Poisson-Boltzmann level, and then use molecular dynamics simulations to show, under which circumstances these fail quantitatively and qualitatively. For the hexagonally packed nematic phase of the polyelectrolytes we compute the osmotic coefficient as a function of density. In the presence of multivalent counterions it can become negative, leading to effective attractions. We show that this results from a reduced contribution of the virial part to the pressure. We compute the osmotic coefficient and ionic distribution functions from Poisson-Boltzmann theory with and without a recently proposed correlation correction, and also simulation results for the case of poly(para-phenylene) and compare it to recently obtained experimental data on this stiff polyelectrolyte. We also investigate ion-ion correlations in the strong coupling regime, and compare them to predictions of the recently advocated Wigner crystal theories.

32 pages, 15 figures, proceedings of the ASTATPHYS-MEX-2001, to be published in Mol. Phys

References in corpus (1)

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

Cited by in corpus (5)

• Salt-induced collapse and reexpansion of highly charged flexible polyelectrolytes
• Attraction and ionic correlations between charged stiff polyelectrolytes
• Chain morphology, swelling exponent, persistence length, like-charge attraction, and charge distribution around a chain in polyelectrolyte solutions: effects of salt concentration and ion size studied by molecular dynamics simulations
• Mechanism of chain collapse of strongly charged polyelectrolytes
• Dynamical clustering of counterions on flexible polyelectrolytes