Difference in "Supercooling" Affinity between (Acetamide + Na/KSCN) Deep Eutectics: Reflections in the Simulated...

Deep depression of freezing points of ionic amide deep eutectic solvents (DESs) is known to exhibit a significant dependence on the identity of ions present in those systems and the nature of the functional group attached to the host amide. This deep depression of the freezing point is sometimes termed as "supercooling". For (acetamide + electrolyte) DESs, experiments have revealed signatures of ion-dependent spatiotemporal heterogeneity features. The focus of this work is to provide microscopic explanations of these experimentally observed macroscopic system properties in terms of particle jumps and insights about the origin of the cation dependence. For this purpose, extensive molecular dynamics simulations have been performed employing (acetamide + Na/KSCN) deep eutectics as representative ionic systems at 303, 318, 333, and 348 K. The individual translational motions of acetamide and the ions are followed, and their connections to solution heterogeneity are explored. The center-of-mass motion for Na⁺ has been found to be more anomalous than that for K⁺. This difference corroborates well with experimental reports on heterogeneous relaxations in these systems. Simulated viscosity coefficients and dynamic heterogeneity features also reflect this difference. Moreover, simulated reorientational relaxations of acetamide molecules in these ionic DESs suggest that a Na⁺-containing DES is more heterogeneous than the corresponding K⁺-containing system. Estimated void and neck distributions for acetamide molecules differ as the alkali metal ions differ. In brief, this study provides a detailed microscopic view of the cation dependence of the microheterogeneous relaxation dynamics of these DESs reported repeatedly by different experiments.