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High-resolution, near-infrared CW-CRDS, and ab initio investigations of N2O–HDO

par Foldes, Tomas ;Lauzin, Clément ;Vanfleteren, Thomas ;Herman, Michel ;Liévin, Jacques ;Didriche, Keevin
Référence Molecular Physics, 113, page (473-482)
Publication Publié, 2015

Article révisé par les pairs

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Résumé :

We have investigated the N2O–HDO molecular complex using ab initio calculations at the CCSD(T)-F12a/aug-cc-pVTZ level of theory and using cavity ring-down spectroscopy to probe an HDO/N2O/Ar supersonic jet around 1.58 μm. A single a-type vibrational band was observed, 13 cm−1 redshifted compared to the OH+OD excited band in HDO, and 173 vibration-rotation lines were assigned (Trot ≈ 20 K). A weighted fit of existing microwave and present near infrared (NIR) data was achieved using a standard Watson's Hamiltonian (σ = 1.26), producing ground and excited states rotational constants. The comparison of the former with those calculated ab initio suggests a planar geometry in which the OD rather than the OH bond in water is almost parallel to NNO. The equilibrium geometry and dissociation energy (De = –11.7 kJ/mol) of the water–nitrous oxide complex were calculated. The calculations further demonstrate and allow characterising another minimum, 404 cm−1 (ΔE0) higher in energy. Harmonic vibrational frequencies and dissociation energies, D0, were calculated for various conformers and isotopic forms of the complex, in both minima. The absence of N2O–D2O from dedicated NIR experiments is reported and discussed.