Molecular dynamics insights into the dynamical behavior of structurally modified water in aqueous deep eutectic...

Recent studies have demonstrated that the presence of water in deep eutectic solvents (DESs) significantly affects their dynamics, structure, and physical properties. Although the structural changes due to the addition of water are well understood, the microscopic dynamics of these changes have been rarely studied. Here, we performed molecular dynamics simulation of 30% (v/v) (∼0.57 molar fraction) water mixture of DES containing CH3CONH2 and NaSCN/KSCN at various salt fractions to understand the microscopic structure and dynamics of water. The simulated results reveal a heterogeneous environment for water molecules in aqueous DES (ADES), which is influenced by the nature of the cation. The diffusion coefficients of water in ADESs are significantly lower than that in neat water and concentrated aqueous NaSCN/KSCN solution. When Na+ ions are replaced by K+ ions in the ADES system, the diffusion coefficient increases, which is consistent with the measured nuclear magnetic resonance data. Self-dynamic structure factor for water and other simulated dynamic quantities, such as reorientation, hydrogen-bond, and residence time correlation functions, show markedly slower dynamics inside ADES than in the neat water and aqueous salt solution. Moreover, these dynamics become faster when Na+ ions in ADES are replaced by K+ ions. The results suggest that the structural environment of water in Na+-rich ADES is rigid due to the presence of cation-bound water and geometrically constrained water. The medium becomes less rigid as the KSCN fraction increases due to the relatively weaker interaction of K+ ions with water than Na+ ions, which accelerates the dynamical processes.