Polyelectrolyte brushes in external fields: molecular dynamics simulations and mean-field theory

Soft Matter. 2015 Jul 28;11(28):5688-96. doi: 10.1039/c5sm01275a.

Abstract

A mean-field model is developed to predict the layer-thickness of sparse and salt-free polyelectrolyte brushes, exposed to an external electric field, which attracts the polyelectrolytes to the substrate. In molecular dynamics simulations, it is shown that a fraction of polymers collapses entirely to screen the charge of the substrate. The remaining brushes are then treated as field-free brushes at reduced grafting density. The mean-field model may thus be applied to field-free brushes, both in their osmotic and their weak charge regimes. It yields simple, closed equations for the brush height and for the partition of counterions in- and outside the brushes, and accurately reproduces simulation data of the collapse of the brushes during the crossover between both charge regimes.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Electrolytes / chemistry*
  • Molecular Dynamics Simulation*
  • Osmosis
  • Polymers / chemistry*

Substances

  • Electrolytes
  • Polymers