Deep Eutectic Solvents: Molecular Simulations with a First-Principles Polarizable Force Field

Abstract

The unique properties of deep eutectic solvents make them useful in a variety of applications. In this work we develop a first-principles force field for reline, which is composed of choline chloride and urea in the molar ratio 1:2. We start with the symmetry adapted perturbation theory (SAPT) protocol and then make adjustments to better reproduce the structure and dynamics of the liquid when compared to first-principles molecular dynamics (FPMD) simulations. The resulting force field is in good agreement with experiments in addition to being consistent with the FPMD simulations. The simulations show that primitive molecular clusters are preferentially formed with choline-chloride ionic pairs bound with a hydrogen bond in the hydroxyl group and that urea molecules coordinate the chloride mainly via the trans-H chelating hydrogen bonds. Incorporating polarizability qualitatively influences the radial distributions and lifetimes of hydrogen bonds and affects long-range structural order and dynamics. The polarizable force field predicts a diffusion constant about an order of magnitude larger than the nonpolarizable force field and is therefore less computationally intensive. We hope this study paves the way for studying complex hydrogen-bonding liquids from a first-principles approach.