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Nitrogen-broadened lineshapes in the oxygen A-band: Experimental results and theoretical calculations

par Predoi-Cross, Adriana;Holladay, Christopher;Heung, Henry;Bouanich, Jean Pierre;Mellau, Georg Ch.Georg;Keller, Reimund;Hurtmans, Daniel
Référence Journal of Molecular Spectroscopy, 251, 1-2, page (159-175)
Publication Publié, 2008-09

Article révisé par les pairs

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Résumé :

We report measurements for N2-broadening, pressure-shift and line mixing coefficients for 55 oxygen transitions in the A-band retrieved using a multispectrum fitting technique. Nineteen laboratory absorption spectra were recorded at 0.02 cm-1 resolution using a multi-pass absorption cell with path length of 1636.9 cm and the IFS 120 Fourier transform spectrometer located at Justus-Liebig-University in Giessen, Germany. The total sample pressures ranged from 8.8 to 3004.5 Torr with oxygen volume mixing ratios in nitrogen ranging between 0.057 and 0.62. An Exponential Power Gap (EPG) scaling law was used to calculate the N2-broadening and N2-line mixing coefficients. The line broadening and shift coefficients for the A-band of oxygen self-perturbed and perturbed by N2 are modeled using semiclassical calculations based on the Robert-Bonamy formalism and two intermolecular potentials. These potentials involve electrostatic contributions including the hexadecapole moment of the molecules and (a) a simple dispersion contribution with one adjustable parameter to fit the broadening coefficients or (b) the atom-atom Lennard-Jones model without such adjustable parameters. The first potential leads to very weak broadening coefficients for high J transitions whereas the second potential gives much more improved results at medium and large J values, in reasonable agreement with the experimental data. For the line shifts which mainly arise in our calculation from the electronic state dependence of the isotropic potential, their general trends with increasing J values can be well predicted, especially from the first potential. From the theoretical results, we have derived air-broadening and air-induced shift coefficients with an agreement comparable to that obtained for O2-O2 and O2-N2. © 2008 Elsevier Inc. All rights reserved.