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

Journal Article · Mon Nov 15 04:00:00 EST 2010 · Physical Review. A

DOI:https://doi.org/10.1103/PHYSREVA.82.052701· OSTI ID:21528645

Verzhbitskiy, I A; Chrysos, M ^[1]; Kouzov, A P ^[2]

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1. Institut des Sciences et Technologies Moleculaires d'Angers, MolTech Anjou, UMR CNRS 6200, Universite d'Angers, 2 boulevard Lavoisier, F-49045 Angers (France)
2. Institute of Physics, Saint Petersburg State University, Ulyanovskaya str. 1, Peterhof, Saint Petersburg RU-198504 (Russian Federation)

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

• OSTI ID: 21528645
• Journal Information: Physical Review. A, Journal Name: Physical Review. A Journal Issue: 5 Vol. 82; ISSN 1050-2947; ISSN PLRAAN
• Country of Publication: United States
• Language: English

Related Subjects

71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
74 ATOMIC AND MOLECULAR PHYSICS
ACCURACY
ANISOTROPY
APPROXIMATIONS
CALCULATION METHODS
COLLISIONS
ELECTRICAL PROPERTIES
ELEMENTS
ENERGY LEVELS
EXCITED STATES
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
MECHANICS
MOLECULES
NITROGEN
NONMETALS
PHYSICAL PROPERTIES
POLARIZABILITY
POTENTIALS
QUANTUM MECHANICS
RAMAN EFFECT
SPECTRA
SULFUR COMPOUNDS
SULFUR FLUORIDES
VIBRATIONAL STATES