PRESSURE BROADENING AND SHIFTING COEFFICIENTS AS TESTS OF H2(D2)-He POTENTIAL ENERGY SURFACES - Université de Rennes Accéder directement au contenu
Poster De Conférence Année : 2015

PRESSURE BROADENING AND SHIFTING COEFFICIENTS AS TESTS OF H2(D2)-He POTENTIAL ENERGY SURFACES

Résumé

We have calculated the helium-pressure broadening and shifting coefficients of the isotropic Raman Q(1) lines of the fundamental of H 2 and D 2. The quantum dynamical close coupling calculations were performed on five 3-dimensional PESs, namely: the pot3d potential of Bakr et al, 1 the so-called BMP PES, 2 the modified Muchnik and Russek PES, 3 the modified BMP PES, 1 and the Schaefer and Köhler PES. 4 The last one being the oldest one and obtained at the lowest-level of quantum chemical accuracy but has the advantage of covering interactions over a larger intramolecular interval. Moreover, the theoretical values it leads to 5,6,7 are in quite good agreement with experimental pressure broadening and shifting coeffients. 7,8,9,10 By decomposing the kinetic energy dependent pressure broadening cross-sections in an inelastic part and a dephasing one and by also looking at the isotropic contribution of the pressure shifting cross-sections allow us to bring to the fore the main differences that exist between the five PESs we have considered. The modBMP PES has been readily rejected because it is only a slight modification of the original BMP PES. The BMP and modMR PESs lead to thermally averaged values far from the experimental ones. The quantum chemical " state of the art " PES of Bakr et al provides shifting parameters in better agreement than the SK PES with experimental shifts but, the broadening parameters seem to be slightly more accurate with the SK PES. This last point should be confirmed by an accu-1
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Dates et versions

hal-01263187 , version 1 (01-02-2016)

Identifiants

  • HAL Id : hal-01263187 , version 1

Citer

Franck Thibault, P Wcislo, R Ciurylo. PRESSURE BROADENING AND SHIFTING COEFFICIENTS AS TESTS OF H2(D2)-He POTENTIAL ENERGY SURFACES. The 24th Colloquium on High Resolution Molecular Spectroscopy HRMS 2015, Aug 2015, Dijon, France. 2013. ⟨hal-01263187⟩
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