Double vibrational collision-induced Raman scattering by SF 6 -N 2 : Beyond the point-polarizable molecule model

摘要: Collision-induced Raman bandshapes and zeroth-order spectral moments are calculated both for the depolarized spectrum extremely weak isotropic of SF{sub 6}({nu}{sub 1}) +N{sub 2}({nu}{sub double-Raman-scattering band. A critical comparison is made with experiments conducted recently by authors [Phys. Rev. 81, 012702 (2010); 042705 (2010)]. The study this transition, hitherto restricted to model framework two point-polarizable molecules, now completed incorporate effects beyond point-molecule approximation. Whereas extended offers a few percent improvement in spectrum, it reveals huge 80% increase its moment, owing essentially polarizability anisotropy N{sub 2}. For spectra, agreement between quantum-mechanical calculations our found, provided that best ab initio data (hyper)polarizability parameters used. This refined shows clearly need include all mechanisms high level accuracy allows one decide alternatives about difficult controversial issues such as intermolecular potential or sensitive Hamaker force constants.