The Raman spectra below 300 wavenumbers of six different aromatic molecular liquids have been measured with a time and polarization resolved optical Kerr effect technique. The isotropic and anisotropic contributions were determined to yield the complete third order response, and thus a more detailed description of the microscopic liquid dynamics. The anisotropic contributions accurately reproduced previously published results. Both the isotropic and anisotropic Raman spectral densities shift toward lower frequencies with decreasing molecular weights. The first moment of the isotropic spectral densities scales linearly with the inverse square root of the molecular weight, which is consistent with interaction-induced dynamics in these liquids being driven mainly by motions with a translational character. Also, the isotropic spectral densities could be fit to a single Bucaro–Litovitz function. The exponent d of this function increases monotonically with the inverse square root of the molecular weight. A possible physical origin of this behavior is discussed.
|Journal||The Journal of Chemical Physics|
|Publication status||Published - 7 May 2010|