Yu-Fan Ho, Tyler N. Shendruk, Gary W. Slater, Pai-Yi Hsiao

Molecular dynamic simulations of salt-free polyelectrolyte brushes subject to external fields applied normal to the grafting substrate reveal the three-dimensional monomer and counterion distributions. It is found that below a critical electric field, local electroneutrality holds for densely grafted brushes and the brush height remains independent of field intensity. Above this critical field (which scales as 1/3 with grafting density) brush height increases smoothly, and the fraction of condensed counterions decreases. The brush bifurcates into two subpopulations of stretched and collapsed chains when the grafting density is not low. At intermediate grafting densities, the majority of chains are stretched and the minority are nonstretched. At high grafting densities bifurcation and brush height growth occur consecutively. The majority of the chains are nonstretched at high grafting densities. Although not observed prior to overstretching of the chain model, it is predicted that the two subpopulations will re-merge to a single highly stretched phase when field intensity reaches a third critical value. The ability to control subpopulations of chains suggests that utilizing electric fields normal to polyelectrolyte brushes holds potential as controllable gates in microfluidic devices.