Explicit-water molecular dynamics study of a short-chain 3,3 ionene in solutions with sodium halides

Abstract

Ionenes are alkyl polymer chains in which hydrophobic groups are separated by ionic charges. They are useful for studying the properties of water as a solvent because they demonstrate a sufficiently complex combination of hydrophobicity, charge interactions, and specific-ion effects that some properties cannot be predicted by implicit-solvation theories. On the other hand, they are simple enough that their molecular structures can be varied and controlled in systematic experiments. In particular, implicit-solvent models predict that all such solutes will have negative enthalpies of dilution, whereas experiments show that enthalpies of dilution are positive for the chaotropic counterions. Here, we study ionenes that are short chains (six monomer units) in solutions of different counterions, with sodium as the coion by molecular dynamics simulations in explicit water. We explore the pair distributions of various atoms within the system at three different temperatures: T=278, 298, and 318 K. We find (i) that the molecular dynamics simulations are consistent with the experimental trends for the osmotic coefficients and enthalpies of dilution, (ii) that the fluorine-nitrogen and fluorine-carbon correlations decrease with decreasing temperature, (iii) while the opposite behavior is found for iodine ions, and (iv) that in the counterion-Na(+) pair distributions, too, fluorine ions behave oppositely to iodine ions upon temperature increase.