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Rovibrational laser jet-cooled spectroscopy of SF6-rare gas complexes in the ν3 region of SF6

Abstract

High resolution infrared spectroscopy combining an external cavity quantum cascade laser with a pulsed pin hole supersonic jet is used to investigate small van der Waals (vdW) hetero clusters containing SF6 and rare gas (Rg) atoms in the ν3 region of SF6. In a first analysis, the rovibrational band contours of parallel and perpendicular transitions of 1:1 SF6-Rg hetero dimers (Rg = Ar, Kr, Xe) are simulated to derive ground and excited state parameters and hence S-Rg distances with a precision better than 0.005 Å. These values are used to assess quantum chemistry calculations (DFT-D method) as well as semi-empirical predictions (combination rules). In a second step, the spectral signatures of these 1:1 and of larger heteroclusters containing up to three Rg atoms have been identified by considering reduced red shifts, i.e., shifts normalized to the average 1:1 red shift. The number of bands observed with their reduced red shift are shown to be nearly independent upon the Rg atom, which suggests similar structures with an increased lifting of degeneracy when going from monomer to 1:2 complexes. Finally, the vibrational shifts of the 1:1 SF6-Rg hetero dimers are found to fit an intermolecular interaction model in which long–range attractive and short-range repulsive contributions are found to partially compensate, the former being dominant. From the same model, well depths are obtained and are found to compare well with quantum chemistry calculations and semi-empirical combination rules.

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Publication details

The article was received on 11 Jul 2018, accepted on 09 Oct 2018 and first published on 12 Oct 2018


Article type: Paper
DOI: 10.1039/C8CP04387F
Citation: Phys. Chem. Chem. Phys., 2018, Accepted Manuscript
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    Rovibrational laser jet-cooled spectroscopy of SF6-rare gas complexes in the ν3 region of SF6

    P. Asselin, A. C. Turner, L. Bruel, V. brenner, M. GAVEAU and M. MONS, Phys. Chem. Chem. Phys., 2018, Accepted Manuscript , DOI: 10.1039/C8CP04387F

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