Simulations of 3-arm polyelectrolyte star brushes under external electric fields.

Langevin dynamics (LD) simulations have been performed to study the conformations and stratification of grafted three-arm polyelectrolyte (PE) stars in response to external electric fields. The grafted chains with neutral stems and fully charged branches were immersed in a salt-free solution sandwiched between the grafting electrode and a second oppositely charged electrode. The branching points of neutral-stem PE brushes at low grafting densities exhibit a bimodal distribution normal to the grafting electrode. With increasing grafting density, the molecular conformations in the brush layer become more complex with the emergence of multi-mode distributions of the branching point monomers. Under strong electric fields, the fraction of grafted chains with either nearly completely stretched stems or collapsed branches onto the grafting electrode gradually decreases with increasing grafting density due to the stronger electrostatic screening from counterions and monomer charges at higher grafting densities. Simulation results revealed that a collapsing electric field promotes the stratification within the brush layer, leading to high degrees of charge overcompensation from charged monomers collapsed onto the oppositely charged grafting electrode. An approximate analytical self-consistent field model was developed to examine the stratification within the brush layer. Regarding the fraction of grafted chains with the free branches in the upper layer, the prediction of the analytical model qualitatively agrees with the simulation results.