Recommended isolated-line profile for representing high-resolution spectroscopic transitions (IUPAC Technical Report)

• Published in: Pure and applied chemistry Vol. 86; no. 12; pp. 1931 - 1943
• Main Authors: Tennyson, Jonathan, Bernath, Peter F., Campargue, Alain, Császár, Attila G., Daumont, Ludovic, Gamache, Robert R., Hodges, Joseph T., Lisak, Daniel, Naumenko, Olga V., Rothman, Laurence S., Tran, Ha, Zobov, Nikolai F., Buldyreva, Jeanna, Boone, Chris D., De Vizia, Maria Domenica, Gianfrani, Livio, Hartmann, Jean-Michel, McPheat, Robert, Weidmann, Damien, Murray, Jonathan, Ngo, Ngoc Hoa, Polyansky, Oleg L.
• Format: Journal Article
• Language: English
• Published: Berlin De Gruyter 01.12.2014; Walter de Gruyter GmbH
• Subjects: Correlation; Doppler; Doppler effect; High resolution; high-resolution spectroscopy; IUPAC Physical and Biophysical Chemistry Division; line profiles; Line shape; line shifts; Line spectra; Neutral gases; Optics; Physics; Pressure effects; Spectroscopy; Spectrum analysis; Tasks; Water chemistry; water vapor
• ISSN: 0033-4545; 1365-3075
• DOI: 10.1515/pac-2014-0208

The report of an IUPAC Task Group, formed in 2011 on “Intensities and line shapes in high-resolution spectra of water isotopologues from experiment and theory” (Project No. 2011-022-2-100), on line profiles of isolated high-resolution rotational-vibrational transitions perturbed by neutral gas-phase molecules is presented. The well-documented inadequacies of the Voigt profile (VP), used almost universally by databases and radiative-transfer codes, to represent pressure effects and Doppler broadening in isolated vibrational-rotational and pure rotational transitions of the water molecule have resulted in the development of a variety of alternative line-profile models. These models capture more of the physics of the influence of pressure on line shapes but, in general, at the price of greater complexity. The Task Group recommends that the partially Correlated quadratic-Speed-Dependent Hard-Collision profile (pCqSD-HCP) should be adopted as the appropriate model for high-resolution spectroscopy. For simplicity this should be called the Hartmann–Tran profile (HTP). The HTP is sophisticated enough to capture the various collisional contributions to the isolated line shape, can be computed in a straightforward and rapid manner, and reduces to simpler profiles, including the Voigt profile, under certain simplifying assumptions.