Rare gas diatom polarizabilities

Publisher Website
Google Scholar
Abstract
Large scale self-consistent field (SCF) computations of the polarizabilities of the rare gas symmetric diatoms were recently reported, the effect of electron correlation was evaluated for the He2 and Ne2 systems, and a new procedure proposed of scaling SCF results to approximate diatom polarizabilities. In this work, these new results are used to compute from an exact wave mechanical theory binary collision-induced Raman spectra of the rare gases for comparison with recent measurements. Depolarized spectra show agreement typically within the small experimental uncertainties and over a range of intensities that may exceed 100 000:1. Computed and measured polarized spectra similarly agree, but with lesser precision. The scaling of SCF polarizabilities appears to be remarkably successful. Uncertainties arising from the use of semiempirical potentials are not always negligible.