The Influence of Polymer and Ion Solvation on the Conformational Properties of Flexible Polyelectrolytes

The study of the coupling between the conformational properties of a polyelectrolyte chain and the distribution of counter-ions surrounding the chain is important in developing predictive theories for more complex polymer materials, such as polyelectrolyte gels. We investigated the influence of solvent affinity to counter-ions and the polyelectrolyte backbone on the conformational properties of highly charged flexible polymer chains using molecular dynamics simulations that include both ions and an explicit solvent. We find that the solvation of the polyelectrolyte backbone can be achieved by either increasing the solvent affinity for the polyelectrolyte segments or by increasing the solvent affinity for the counter-ions. However, these two mechanisms influence the conformational properties of the polyelectrolyte chain in rather different ways, suggesting the inadequacy of polyelectrolyte solution models that treat the solvent as a continuum medium.