Abstract
Abstract The polarized Raman spectra of the υ 1 (CH 3 str.) mode in 1,1,1-trichloroethylsilane (TMSi), 1,1,1-trichloromethylgermane (TMGe) and 1,1,1-trichloromethylstannane (TMSn) were recorded in a number of solvents. The vibrational peak frequency displacements in TMSi were approximately linearly dependent on solvent polarizability. However, the correlation was substantially lower for TMGe and TMSn, indicating that forces other than dispersion interactions contribute significantly to the net frequency shifts in the heavier members of the series. Isotropic linewidths in TMSi and TMGe were observed to remain approximately constant in non-polar solvents, but increased markedly in polar media, In contrast to the results of an earlier investigation of 1,1,1-trichloroethane in solution, the isolated Binary Collision model of homogeneous dephasing does not correctly predict the experimental variations in linewidth. Therefore, it is concluded that vibrational linebroadening in these compounds is probably caused by inhomogeneous dipolar interactions.
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