On the isotropic Raman spectrum of Ar-2 and how to benchmark ab initio calculations of small atomic clusters: Paradox lost

摘要

This is the long-overdue answer to the discrepancies observed between theory and experiment in Ar-2 regarding both the isotropic Raman spectrum and the second refractivity virial coefficient, B-R [Gaye et al., Phys. Rev. A 55, 3484 (1997)]. At the origin of this progress is the advent (posterior to 1997) of advanced computational methods for weakly interconnected neutral species at close separations. Here, we report agreement between the previously taken Raman measurements and quantum lineshapes now computed with the employ of large-scale CCSD or smartly constructed MP2 induced-polarizability data. By using these measurements as a benchmark tool, we assess the degree of performance of various other ab initio computed data for the mean polarizability a, and we show that an excellent agreement with the most recently measured value of B-R is reached. We propose an even more refined model for a, which is solution of the inverse-scattering problem and whose lineshape matches exactly the measured spectrum over the entire frequency-shift range probed. (C) 2015 AIP Publishing LLC.