Temperature- and solvation-dependent dynamics of liquid sulfur dioxide studied through the ultrafast optical Kerr...

The ultrafast dynamics of liquid sulphur dioxide have been studied over a wide temperature range and in solution. The optically heterodyne-detected and spatially masked optical Kerr effect (OKE) has been used to record the anisotropic and isotropic third-order responses, respectively. Analysis of the anisotropic response reveals two components, an ultrafast nonexponential relaxation and a slower exponential relaxation. The slower component is well described by the Stokes-Einstein-Debye equation for diffusive orientational relaxation. The simple form of the temperature dependence and the agreement between collective (OKE) and single molecule (e.g., NMR) measurements of the orientational relaxation time suggests that orientational pair correlation is not significant in this liquid. The relative contributions of intermolecular interaction-induced and single-molecule orientational dynamics to the ultrafast part of the spectral density are discussed. Single-molecule librational-orientational dynamics appear to dominate the ultrafast OKE response of liquid SO2. The temperature-dependent OKE data are transformed to the frequency domain to yield the Raman spectral density for the low-frequency intermolecular modes. These are bimodal with the lowest-frequency component arising from diffusive orientational relaxation and a higher-frequency component connected with the ultrafast time-domain response. This component is characterized by a shift to higher frequency at lower temperature. This result is analyzed in terms of a harmonic librational oscillator model, which describes the data accurately. The observed spectral shifts with temperature are ascribed to increasing intermolecular interactions with increasing liquid density. Overall, the dynamics of liquid SO2 are found to be well described in terms of molecular orientational relaxation which is controlled over every relevant time range by intermolecular interactions.