Transport Mechanism of Acetamide in Deep Eutectic Solvents.

Over the last couple of decades, deep eutectic solvents (DESs) have emerged as novel alternatives to ionic liquids that are extensively used in the synthesis of innovative materials, metal processing, catalysis, etc. However, their usage is limited, primarily because of their large viscosity and poor conductivity. Therefore, an understanding of the molecular origin of these transport properties is essential to improve their industrial applicability. Here, we present the report of the nanoscopic diffusion mechanism of acetamide in a DES synthesized with lithium perchlorate as studied using neutron scattering and molecular dynamics (MD) simulation techniques. A diffusion model is constructed with the help of MD simulation data comprising two distinct processes, corresponding to long-range jump diffusion and localized diffusion within a restricted volume. This diffusion model is validated through the analysis of neutron scattering data in the acetamide based DES (ADES) and molten acetamide. Although ADES has a remarkably lower freezing point compared to pure acetamide, the molecular mobility is found to be enormously restricted in the former. Particularly, the long-range jump diffusion process of acetamide is slower by a factor of 3 in ADES in comparison with molten acetamide. Further, the geometry of localized diffusion is found to be unaltered, but the dynamics is observed to be slightly slower in ADES. The diffusion model is found to be consistent over a wide temperature range for the ADES. Both long-range and localized diffusion show Arrhenius dependence with temperature in ADES. MD simulation analysis reveals that the long-range diffusion in ADES is restricted mainly due to the formation of hydrogen bond mediated complexes between the ionic species of the salt and acetamide molecules. Hence, the origin of higher viscosity observed in ADES can be attributed to the complexation in the ADES. The complex formation also explains the inhibition of the crystallization process while cooling and thereby results in depression of the freezing point of ADES.