Raman and Rayleigh spectroscopy and molecular motions

Raman and Rayleigh scattering experiments on HCl, DCl, HBr and DBr molecules (pure liquid or isotopically diluted) have been carried out at room temperature. Results are discussed in the light of the existing theories on molecular motions in the liquid phase. The comparison of Rayleigh and Raman scattering results shows that reorientational processes are not sufficient to explain completely the profile of anisotropic Raman scattering. According to a recent theory due to Bratos, the rotational correlation function can be obtained only after elimination of the vibrational correlation function determined from the isotropic Raman scattering. In this last case broadening may arise from three causes: translational motion, resonance broadening and vibration-rotation coupling. A comparative study of the band profile of anisotropic Rayleigh and Raman scattering shows that the wings in both cases come from essentially the same origin while a band moment analysis is consistent with Gordon's theory according to which they are of reorientational origin.