Dynamics of Formamide–Water Mixtures Investigated by Linear and Nonlinear Infrared Spectroscopy

Abstract

Formamide (FA) exhibits complete miscibility with water, offering a simplified model for exploring the solvation dynamics of peptide linkages in biophysical processes. Its liquid state demonstrates a three-dimensional hydrogen bonding network akin to water, reflecting solvent-like behavior. Analyzing the microscopic structure and dynamics of FA−water mixtures is expected to provide crucial insights into hydrogen bonding dynamics�a key aspect of various biophysical phenomena. This study is focused on the dynamics of FA−water mixtures using linear and femtosecond infrared spectroscopies. By using the intrinsic OD stretch and extrinsic probe SCN − , the local vibrational behaviors across various FA−water compositions were systematically investigated. The vibrational relaxation of OD stretch revealed a negligible impact of FA addition on the vibrational lifetime of water molecules, underscoring the mixture's water-like behavior. However, the reorientational dynamics of OD stretch slowed with increasing FA mole fraction (X FA ), plateauing beyond X FA > 0.5. This suggests a correlation between OD's reorientational time and the strength of the hydrogen bond network, likely tied to the solution's changing dielectric constant. Conversely, the vibrational relaxation dynamics of SCN − was strongly correlated with X FA , highlighting a competition between water and FA molecules in solvating SCN − . Moreover, a linear relationship between rising viscosity and the prolonged correlation time of SCN − 's slow dynamics indicates that the solution's macroscopic viscosity is dictated by the extended structures formed between FA and water molecules. The relation between the reorientation dynamics of the SCN − and the macroscopic viscosity in aqueous FA−water mixture solutions was analyzed by using the Stokes−Einstein−Debye equations. The direct viscosity-diffusion coupling is observed, which can be attributed to the homogeneous dynamics feature in FA−water mixture solutions. The inclusion of these intrinsic and extrinsic probes not only enhances the comprehensiveness of our analysis but also provides valuable insights into various aspects of the dynamics within the FA−water system. This investigation sheds light on the fundamental dynamics of FA−water mixtures, emphasizing their molecular-level homogeneity in this binary mixture solution.