Non-linear osmotic brush regime: Simulations and mean-field theory

We investigate polyelectrolyte brushes in the osmotic regime using both theoretical analysis and molecular dynamics simulation techniques. In the simulations at moderate Bjerrum length, we observe that the brush height varies weakly with grafting density, in contrast to the accepted scaling law, which predicts a brush thickness independent of the grafting density. We show that such behavior can be explained by considering lateral electrostatic effects (within the non-linear Poisson-Boltzmann theory) combined with the coupling between lateral and longitudinal degrees of freedom due to the conserved polymer volume (which are neglected in scaling arguments). We also take the non-linear elasticity of polyelectrolyte chains into consideration, which makes significant effects as chains are almost fully stretched in the osmotic regime. It is shown that all these factors lead to a non-monotonic behavior for the brush height as a function of the grafting density. At large grafting densities, the brush height increases with increasing the grafting density due to the volume constraint. At small grafting densities, we obtain a re-stretching of the chains for decreasing grafting density, which is caused by lateral electrostatic contributions and is controlled by the counterion-condensation process around polyelectrolyte chains. These results are obtained assuming all counterions to be trapped within the brush, which is valid for sufficiently long chains of large charge fraction.