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Spectroscopic lineshape study of the self-perturbed oxygen A-band

par Predoi-Cross, Adriana;Hambrook, Kyle;Keller, Reimund;Povey, Chad;Schofield, Ian;Hurtmans, Daniel ;Over, Herbert;Mellau, Georg Ch.Georg
Référence Journal of Molecular Spectroscopy, 248, 2, page (85-110)
Publication Publié, 2008-04

Article révisé par les pairs

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Résumé :

This paper reports accurate line positions, intensities, self-broadening, -shift and -line mixing coefficients for 56 rotational transitions from multispectrum fits of low noise, high-resolution Fourier-transform spectra. The measured line intensities are within the statistical spread of the previous measurements available in the literature-thus contributing to the efforts to measure the oxygen A-band intensities with an accuracy better than 1%. We determined the integrated band strength and Einstein A coefficient. Using our spectrum calibration method we could clearly show for the first time that there is a meaningful statistical discrepancy in the frequency standards used in spectroscopic studies for the oxygen A-band. We were able to explain how this discrepancy leads to two different sets of shifts reported in the literature and demonstrate the need for precise frequency-type transition wavenumber measurements of the oxygen A-band transitions. We observed deviations from the conventional Voigt profile due to speed-dependent broadening and line mixing effects. Dicke narrowing was observed on a selected group of spectra recorded at pressures between 98 and 337 Torr. The Dicke narrowed lineshapes were best modeled using a Galatry profile implemented using a fixed value for the velocity-changing collision rate. The weak line mixing coefficients were determined from fits using the speed-dependent models. Exponential Power Gap (EPG) and Energy Corrected Sudden (ECS) scaling laws were used to calculate the self-broadening and self-line mixing coefficients. © 2007 Elsevier Inc. All rights reserved.