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Temperature dependent Raman study of molecular motions and interactions of CH3I in the liquid phase

机译:Temperature dependent Raman study of molecular motions and interactions of CH3I in the liquid phase

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The polarized and depolarized components of the 524 cmminus;1Raman band in liquid methyl iodide were measured between 196 and 300deg;K. A technique, utilizing the isotropic scattering intensity, allowed the separation of reorientational line broadening of the anisotropic spectrum from the broadening due to other processes. The reorientational correlation times derived from the anisotropic Raman spectrum were found to agree well with those obtained by other techniques throughout the temperature range studied. The temperature dependence of the isotropic correlation times was opposite to that predicted by current theories of vibrational relaxation and collisional broadening. The depolarization ratio was also measured as a function of temperature and is seen to vary quite markedly. The depolarized low frequency spectra of methyl iodide were also studied and the results were fit to a theoretical expression for collision induced scattering to obtain values for the linewidth parameter Dgr;. The temperature dependence of Dgr; proved to be opposite from that predicted by theory and is qualitatively similar to the temperature dependence of the isotropic linewidths, indicating that the same broadening mechanism is probably present in both spectra.

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