Modulation of Diffusion Mechanism and Its Correlation with Complexation in Aqueous Deep Eutectic Solvents.

Aqueous mixtures of deep eutectic solvents (DESs) have gained traction recently as an effective template to tailor their physicochemical properties. But detailed microscopic insights into the effects of water on the molecular relaxation phenomenon in DESs are not entirely understood. DESs are strong network-forming liquids due to the extensive hydrogen bonding and complex formation between their species, and therefore, water can behave as a controlled disruptor altering the microscopic structure and dynamics in DESs. In this study, the role of water in the diffusion mechanism of acetamide in the aqueous mixtures of DESs synthesized using acetamide and lithium perchlorate is investigated using molecular dynamics (MD) simulation and quasielastic neutron scattering (QENS). The acetamide dynamics comprises localized diffusion within transient cages and a jump diffusion process across cages. The jump diffusion process is observed to be strongly enhanced by about a factor of 10 as the water content in the system is increased. Meanwhile, the geometry of the localized dynamics is unaltered by addition of water, but the localized diffusion becomes significantly faster and more heterogeneous with increasing water concentration. The accelerating effects of water on localized diffusion are also substantiated by QENS experiments. The water concentration in the DES is observed to control the solvation structure of lithium ions, with the ions becoming significantly hydrated at 20 wt % water. The formation of interwater and water-acetamide hydrogen bonds is observed. The increase in water concentration is found to increase the number of H-bonds; however, their lifetimes are found to decrease substantially. Similarly, the lifetimes of acetamide-lithium complexes are also found to be diminished by increasing water concentration. A power-law scaling relationship between lifetimes and diffusion constants is established, elucidating the extent of coupling between diffusive processes and hydrogen bonding and microscopic complexation. This study demonstrates the ability to use water as an agent to probe the role of structural relaxation and complex lifetimes of diffusive processes at different time and length scales.