Influence of Charge Scaling on the Solvation Properties of Ionic Liquid Solutions.

Scaled-charge force fields (FFs) are widely employed in the simulation of neat ionic liquids (ILs), where the charges on the ions are empirically scaled to approximately account for electronic polarization and/or charge transfer. Such charge scaling has been found to yield significant improvement in liquid-state thermodynamic and dynamic properties (when compared to experiment). However, the mean field approximation inherent in charge scaling becomes suspect when applied to IL mixtures or solutions. In this work, we simulate solutions of IL with various nonpolar and polar gas solutes and compare results of charge-scaled and polarizable FFs to experiment. Our results demonstrate that scaling of the Coulomb interaction inherent in scaled-charge FFs leads to an underestimation of the solute-solvent electrostatic interaction and thus also the enthalpy and free energy of solvation; this effect is particularly pronounced for polar solutes. In some cases, we find that this artificial reduction in the solute-solvent interaction can also alter the apparent phase behavior of the resulting solution. Overall, the totality of our results suggests that explicit polarization (rather than charge scaling) is likely necessary to provide high transferability to both neat IL and IL mixtures and solutions.