High order polarizabilities from optical interaction-induced Spectroscopy

Multipolar polarizability contributions to the collision-induced light scattering spectra of optically isotropic molecules may be put in evidence in the Rayleigh wings and in the vicinities of the v1 Raman vibrational lines. Experiments on CH4 or CF4 (tetrahedral symmetry) and SF6 (octahedral symmetry) make possible evaluations of the multipolar polarizabilities provided that isotropic Rayleigh spectra and anisotropic Raman bands are obtained in some relatively large frequency ranges. These evaluations — in particular those based on set inversion analysis — constitute experimental references for quantum chemistry computations of the multipolar polarizabilities. In the case of CH4, CF4 and SF6, the agreement between experimental and ab initio values is quite good