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.

Molecular dynamics simulations and dielectric relaxation (DR) measurements in the frequency window, 0.2 ≤ ν/GHz ≤ 50, have been performed to explore the heterogeneous reorientation dynamics in [f choline chloride + (1 – f) urea] deep eutectic solvents (DESs) at f = 0.33 and 0.40 in the temperature range 293 ≤ T/K ≤ 333. The solution viscosity varies by more than an order of magnitude. DR measurements in these DESs reveal multiple relaxation timescalesτ1 ∼ 500 ps, τ2 ∼ 100 ps, τ3 ∼ 30 ps, and τ4 ∼ 5 ps. Simulated rank-dependent collective single-particle reorientational (C l (t), l being the rank) and structural H-bond [C HB(t)] relaxations can explain the microscopic origin of all these DR timescales. The average DR times, ⟨τDR⟩, exhibit a pronounced fractional viscosity dependence, ⟨τDR⟩ ∝ (η/T) p , with p = 0.1. This experimental evidence of pronounced heterogeneous reorientation dynamics in these DESs is supported by a strong translation–rotation decoupling and a significant deviation of the average reorientational correlation times (⟨τ l ⟩) from Debye’s l(l + 1) law. The simulated ratios between the average rotation and translation timescales for both urea and choline correctly reduce to the appropriate hydrodynamic limit at high temperatures. The stretched exponential relaxations of the simulated self-dynamic structure factors and the non-Gaussian single-particle displacement distributions further support strong temporal heterogeneity in these DESs. Dynamic susceptibilities from the simulated four-point correlations exhibit long correlated timescales. Moreover, simulated activation energies estimated from the temperature-dependent C 1(t) decays and the translational diffusion coefficients from the velocity autocorrelation functions agree favorably with those from the corresponding DR and the pulsed field gradient nuclear magnetic resonance measurements.

We report here temperature-dependent (293 ≤ T (K) ≤ 336) dielectric relaxation (DR) measurements of (acetamide + LiBr/NO 3 −

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Molecular dynamics simulations have been performed on a highly viscous (η~255 cP) naturally abundant deep eutectic solvent (NADES) composed of glucose, urea and water at a weight ratio of 6:4:1...