Influence of Hydration on the Structure of Reline Deep Eutectic Solvent: A Molecular Dynamics Study

[Image: see text] In this article, we have performed an all-atom molecular dynamics simulation study to investigate the influence of water on the molecular level arrangement of reline deep eutectic solvent for different hydration levels ranging from 3.4 to 58.1 wt % of water and complemented the observations of recently measured neutron scattering experimental data. This study is particularly important because water is being introduced as a second hydrogen bond donor/acceptor in reline, wherein the structure is primarily governed by hydrogen bonding and electrostatic interactions. We have analyzed the simulated X-ray scattering structure functions, their partial components, and hydrogen bonding interactions to understand the effects of water on various intermolecular interactions in reline–water mixtures. It is observed that at lower hydration level, reline structure is qualitatively retained. At higher hydration level, most water molecules preferentially solvate chloride anions and ammonium group of choline cations mostly impacting choline–choline, choline–chloride, and chloride–chloride interactions. The present study reveals that at and above 41 wt % of water, the molecular arrangement of reline drastically changes and set to transition from reline to an aqueous solution of reline components with further increase in the hydration level. Hydrogen bond analysis reveals the presence of strong chloride–water H-bonding interaction, which gradually replaces choline–chloride and urea–chloride hydrogen bondings as the hydration level in the mixture increases.