Raman studies of rotational and vibrational relaxation in liquid fluoroform

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Abstract
The rotational correlation functions and correlation times have been determined for liquid fluoroform from 135 to 296 °K by using depolarized Raman light scattering. Both the ν1(A1) hydrogen stretching mode and the ν3(A1) deformation mode were analyzed and found to give comparable results for the reorientational motion. The temperature dependence of the reorientational correlation times obtained can be described by an activation energy of 0.97 kcal/mole, and a comparison of these times with previously reported values of the deuterium spin–lattice relaxation times in CDF3 establishes a deuterium quadrupole coupling constant of ± (159±5) kHz. The isotropic linewidths of the ν1(A1) mode, which were found to be unusually large and completely insensitive to temperature, are reported and compared with the isotropic linewidths of the same vibrational mode in CDF3.