Collision-induced Raman spectra and diatom polarizabilities of the rare gases – an update

Abstract

Calibrated Raman spectra of the rare gas homonuclear diatoms are obtained over a wide range of intensities, with polarizations of the incident beam parallel and perpendicular to the direction of observation. From the resulting spectra [Formula: see text], [Formula: see text], the polarized (P) and depolarized[Formula: see text] components are separated for the first time for the diatoms of 3 He, Ar, Kr, and Xe. For direct comparison with the measurements, wave mechanical lineshapes are computed using models of the diatom polarizability tensor invariants as input. New empirical trace and anisotropy functions, consistent with the spectroscopic measurements, are thus obtained for the rare gases. We compare these where possible with existing measurements and ab initio computations.