On the isotropic Raman spectrum of Ar2 and how to benchmark ab initio calculations of small atomic clusters: Paradox lost - Archive ouverte HAL
Article Dans Une Revue The Journal of Chemical Physics Année : 2015

On the isotropic Raman spectrum of Ar2 and how to benchmark ab initio calculations of small atomic clusters: Paradox lost

Michel Chrysos
  • Fonction : Auteur
  • PersonId : 991927
Florent Rachet

Résumé

This is the long-overdue answer to the discrepancies observed between theory and experiment in Ar2 regarding both the isotropic Raman spectrum and the second refractivity virial coefficient, BR [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 α, and we show that an excellent agreement with the most recently measured value of BR is reached. We propose an even more refined model for α, which is solution of the inverse-scattering problem and whose lineshape matches exactly the measured spectrum over the entire frequency-shift range probed.

Domaines

Chimie
Fichier non déposé

Dates et versions

hal-01390925 , version 1 (02-11-2016)

Identifiants

Citer

Michel Chrysos, Sophie Dixneuf, Florent Rachet. On the isotropic Raman spectrum of Ar2 and how to benchmark ab initio calculations of small atomic clusters: Paradox lost. The Journal of Chemical Physics, 2015, 143 (2), pp.024304. ⟨10.1063/1.4923370⟩. ⟨hal-01390925⟩
37 Consultations
0 Téléchargements

Altmetric

Partager

More