Structural Properties of Ions and Polyelectrolytes in Aqueous Solutions under External Electric Fields: The Sign Effect

Abstract

We utilize molecular dynamics simulations to investigate the microstructures of ions and polyelectrolytes in aqueous solutions under external electric fields. By focusing on the multi-body interactions between ionic components and H₂O molecules, as well as their responses to the external electric fields, we clarify several nontrivial molecular features of the ionic and polyelectrolyte solutions, such as the solvations of cations and anions, clustering of the ions, and dispersions/aggregations of polyelectrolyte chains, as well as the corresponding responses of H₂O molecules in these contexts. Our simulations illustrate the variations in structures of ionic solutions caused by reversing the charge sign of the ions, and elucidate the disparity in structures between anionic and cationic polyelectrolyte solutions in the presence of the external electric fields. This work clarifies the mechanism for the alternations in complex multi-body interactions in aqueous solutions caused by the application electric field, which can contribute to the fundamental understanding of the physical and chemical natures of ion-containing and charged polymeric systems.