Temperature-Dependent Dynamics of CS2: An OHD-RIKES Study
The intermolecular modes of liquids play a crucial role in chemical dynamics in solution, as has been demonstrated by numerous experimental  and theoretical  studies. A microscopic understanding of these modes is essential to the development of a coherent picture of solution-phase chemistry. For a given chemical process, one would like to know the physical nature of the relevant modes (e.g., whether they are predominantly rotational or translational) as well as their dynamic nature (i.e., whether they are homogeneously or inhomogeneously broadened). These issues have proven difficult to resolve even for bulk liquids, for which the intermolecular modes have traditionally been studied with variants of far-IR or depolarized Raman spectroscopy. These techniques are formally linear in the modes being studied, and therefore give no direct information about the nature or the broadening mechanisms of the modes.