Heterogeneous relaxation dynamics often characterizes deep eutectic solvents. Extensive and molecular dynamics simulations have been carried out in the temperature range, 303 ≤ T/K ≤ 370, for studying the anion and temperature dependencies of heterogeneous dynamics of three different ionic acetamide deep eutectics: acetamide + LiX, X being bromide (Br−), nitrate (NO3−), and perchlorate (ClO4−). These systems are chosen because the fractional viscosity dependence of average relaxation rates reported by various measurements has been attributed to the heterogeneous dynamics of these systems. Simulations performed here attempt to characterize the heterogeneous relaxation dynamics in terms of correlated time and length scales and understand the solution inhomogeneity in microscopic terms. Additionally, simulation studies for pure molten acetamide have been performed to understand the impact of ions on motional features of acetamide in these ionic deep eutectic systems. The computed radial distribution functions suggest microheterogeneous solution structure and dependence upon anion identity and temperature. A significant plateau in the simulated time dependent mean squared displacements indicates pronounced cage-rattling and inhomogeneity in relaxation dynamics. Simulated diffusion coefficients for acetamide and ions show decoupling from the simulated viscosities of these deep eutectics. Calculated two- and four-point correlation functions reveal the presence of dynamic heterogeneity even at ∼180 K above the measured thermodynamic glass transition temperature (Tg). Further analyses reveal the existence of multiple timescales that respond strongly to the rise in solution temperature. The simulated dynamic structure factor and overlap function relaxations show strong stretched exponential relaxations. The simulation results support the experimental observation that the bromide system is the most dynamically heterogeneous among these three systems. Correlated length scales show much weaker anion and temperature dependencies with an estimated length of ∼1 nm, suggesting formation of clusters at the local level as the origin for the micro-heterogeneous nature of these ionic deep eutectics.

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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.

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