Polyelectrolyte association and solvation

Published: July 10, 2018


Alexandros Chremos, Jack F. Douglas


There has been significant interest in the tendency of highly charged particles having the same charge to form dynamic clusters in solution, but an accepted theoretical framework that can account for this ubiquitous phenomenon has been slow to develop. The theoretical difficulties are especially great for flexible polyelectrolytes due to the additional complex coupling between the polyelectrolyte chain configurations and the spatial distribution of the ionic species in solution. For highly charged polyelectrolytes, this leads to the formation of a diffuse “polarizable” cloud of counter-ions around these polymers, an effect having significant implications for the function of proteins and other natural occurring polyelectrolytes, as emphasized long ago by Kirkwood and coworkers. To address this phenomenon, we perform molecular dynamics simulations of a minimal model of polyelectrolyte solutions that includes an explicit solvent and counter-ions, where the relative affinity of the counter-ions and the polymer for the solvent is tunable through the variation of the relative strength of the dispersion interactions of the polymer and ions. In particular, we find that these dispersion interactions can greatly influence the nature of the association between the polyelectrolyte chains under salt-free conditions. We calculate static and dynamic correlation functions to quantify the equilibrium structure and dynamics of these complex liquids. Based on our coarse-grained model of polyelectrolyte solutions, we identify conditions in which three distinct types polyelectrolyte association arise. We rationalize these types of polyelectrolyte association based on the impact of the selective solvent affinity for the charged species on the structure and dynamics of these charged particles. Our findings demonstrate the essential role of the solvent in the description of the polyelectrolyte solutions, as well as providing a guideline for the development of novel and accurate polyelectro
Citation: Journal of Chemical Physics
Volume: 149
Pub Type: Journals


polyelectrolytes, polymers, solvation
Created July 10, 2018, Updated July 10, 2018