Theoretical and Computational Insight into Solvent and Specific Ion Effects for Polyelectrolytes: The Importance of Local Molecular Interactions

Abstract

Polyelectrolytes in solution show a broad plethora of interesting effects. In this short review article, we focus on recent theoretical and computational findings regarding specific ion and solvent effects and their impact on the polyelectrolyte behavior. In contrast to standard mean field descriptions, the properties of polyelectrolytes are significantly influenced by crucial interactions with the solvent, co-solvent and ion species. The corresponding experimental and simulation results reveal a significant deviation from theoretical predictions, which also highlights the importance of charge transfer, dispersion and polarization interactions in combination with solvation mechanisms. We discuss recent theoretical and computational findings in addition to novel approaches which help broaden the applicability of simple mean field theories.