Intermolecular Vibrational and Orientational Dynamics of Deep Eutectic Solvents Composed of Lithium Bis(trifluoromethylsulfonyl)amide and Organic Amides Revealed by Dynamic Kerr Effect Spectroscopy

In this study, we investigated the intermolecular dynamics, including intermolecular vibration and orientational dynamics, of five deep eutectic solvents (DESs) consisting of lithium bis(trifluoromethylsulfonyl)amide and organic amides, such as acetamide, propanamide, <i>N</i>-methylacetamide, butyramide, and urea, at a mole ratio of 1:3 using femtosecond Raman-induced Kerr effect spectroscopy (fs-RIKES) and subpicosecond optical Kerr effect spectroscopy (ps-OKES). The fs-RIKES results showed that the line shape of the low-frequency band of the <i>N</i>-methylacetamide was trapezoidal, while that of the other organic amide-based DESs was bimodal. The peak and first moment of the intermolecular vibrational band appearing in the frequency range less than 250 cm^-1 for the acetamide- and urea-based DESs were in a higher-frequency region compared to the other three DESs, indicating stronger intermolecular interactions. Furthermore, analysis of the intramolecular vibrational bands of the bis(trifluoromethylsulfonyl)amide anion showed that the population of the transoid conformer of the anion was slightly higher in the urea-based DES than in the other organic amide-based DESs, suggesting that urea solvate lithium cations more than the other organic amides. The slow relaxation dynamics of all five DESs were captured for up to 1 ns using ps-OKES. The slow relaxation dynamics also depended on the organic amide species. However, the slow relaxation time constant did not show a clear correlation with the viscosity; therefore, the relaxation dynamics of the DESs did not follow the Stokes-Einstein-Debye hydrodynamic model. The densities, viscosities, surface tensions, and electrical conductivities of the DESs were also measured for comparison with spectroscopic results.