Mesoscale Modeling of Polyelectrolyte Brushes with Salt

• Published in: The journal of physical chemistry. B Vol. 114; no. 21; pp. 7274 - 7285
• Main Authors: Ibergay, Cyrille, Malfreyt, Patrice, Tildesley, Dominic J
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 03.06.2010
• Subjects: B: Statistical Mechanics, Thermodynamics, Medium Effects; Electrolytes - chemistry; Models, Molecular; Polymers - chemistry; Salts - chemistry; Static Electricity
• ISSN: 1520-6106; 1520-5207
• DOI: 10.1021/jp9115832

We report dissipative particle dynamics (DPD) simulations of a polyelectrolyte brush under athermal solvent conditions. The electrostatic interactions are calculated using the particle−particle particle-mesh (PPPM) method with charges distributed over the particles. The polymer beads, counterions, co-ions, and solvent particles are modeled explicitly. The DPD simulations show a dependence of the brush height on the grafting density and the charge fraction that is typical of the nonlinear osmotic brush regime. We report the effect of the addition of salt on the structural properties of the brush. In the case of a polyelectrolyte brush with a high surface coverage, the simulations reproduce the transition between the nonlinear osmotic brush regime where the thickness of the brush is independent of the salt concentration and the salted regime where the brush height decreases weakly with the salt concentration.