The implementation of non-Voigt line profiles in the HITRAN database: H sub(2) case study

• Published in: Journal of quantitative spectroscopy & radiative transfer 2016-07, Vol.177, p.75-91
• Main Authors: Wcisloa, P, Gordona, I E, Tranc, H, Tana, Y, Hud, S-M, Camparguee, A, Kassie, S, Romaninie, D, Hilla, C, Kochanova, R V, Rothmana, L S
• Format: Article
• Language: English
• Subjects: Collisions; Mathematical models; Radiative transfer; Representations; Spectra; Spectral lines; Stores
• ISSN: 0022-4073
• DOI: 10.1016/j.jqsrt.2016.01.024

Experimental capabilities of molecular spectroscopy and its applications nowadays require a sub-percent or even sub-per mille accuracy of the representation of the shapes of molecular transitions. This implies the necessity of using more advanced line-shape models which are characterized by many more parameters than a simple Voigt profile. It is a great challenge for modern molecular spectral databases to store and maintain the extended set of line-shape parameters as well as their temperature dependences. It is even more challenging to reliably retrieve these parameters from experimental spectra over a large range of pressures and temperatures. In this paper we address this problem starting from the case of the H sub(2) molecule for which the non-Voigt line-shape effects are exceptionally pronounced. For this purpose we reanalyzed the experimental data reported in the literature. In particular, we performed detailed line-shape analysis of high-quality spectra obtained with cavity-enhanced techniques. We also report the first high-quality cavity-enhanced measurement of the H sub(2) fundamental vibrational mode. We develop a correction to the Hartmann-Tran profile (HTP) which adjusts the HTP to the particular model of the velocity-changing collisions. This allows the measured spectra to be better represented over a wide range of pressures. The problem of storing the HTP parameters in the HITRAN database together with their temperature dependences is also discussed.