Temperature-Dependent Dielectric Relaxation in Ionic Acetamide Deep Eutectics: Partial Viscosity Decoupling and Explanations from the Simulated Single-Particle Reorientation Dynamics and Hydrogen-Bond Fluctuations.

Abstract

We report here temperature-dependent (293 ≤ T (K) ≤ 336) dielectric relaxation (DR) measurements of (acetamide + LiBr/NO3-/ClO4-) deep eutectic solvents (DESs) in the frequency window of 0.2 ≤ ν (GHz) ≤ 50 and explore, via molecular dynamics simulations, the relative roles for the collective single-particle reorientational relaxations and the H-bond dynamics of acetamide in the measured DR response. In addition, DR measurements of neat molten acetamide were performed. Recorded DR spectra of these DESs require multi-Debye fits and produce well-separated DR time scales that are spread over several picoseconds to ∼1 ns. Simulations suggest DR time scales derive contributions from both the collective reorientational () relaxation and structural H-bond (CHB(t)) dynamics of acetamide. A good correlation between the measured and simulated activation energies further reveals a strong connection between the measured DR and the simulated and CHB(t). Average DR times exhibit a strong fractional viscosity dependence, suggesting substantial microheterogeneity in these media. Simulations of and CHB(t) reveal strong stretched exponential relaxations with a stretching exponent, 0.4 ≤ β ≤ 0.7. The ratio between the average reorientational correlation times of first and second ranks, , deviates appreciably from Debye's law for homogeneous media. Importantly, a pronounced translation-rotation decoupling between the simulated reorientation and center-of-mass diffusion times was observed.