New analysis of the ν5 and 2 ν9 bands of HNO 3 by infrared and millimeter wave techniques: line positions and intensities

Abstract

Nitric acid (HNO 3) plays an important role in the Earth’s atmosphere as a reservoir molecule of NO x species. It has a strong infrared signature at 11 μm which is one of the most commonly used for the infrared retrieval of this species in the atmosphere since this spectral region coincides with an atmospheric window. It is therefore essential to have high quality spectral parameters in this spectral region. The main goal of this work is then to generate as reliable as possible line positions and intensities for the ν 5 and 2 ν 9 cold bands centered at 879.1075 and 896.4467 cm −1, respectively. In particular the existing line parameters need improvement in the wings of the 11 μm window in order to retrieve more accurately the CFC-11 (CCl 3F) and CFC-12 (CCl 2F 2) atmospheric species at ∼850 and ∼920 cm −1, respectively. This work is also motivated by theoretical considerations. Very strong resonances couple indeed the 5 1 and 9 2 rotational levels. In addition the ν 9 mode (OH torsion) is a “large amplitude” motion, and torsional splittings affect both the v 9=2 and the v 5=1 rotational transitions. In the present study, these effects are accounted for simultaneously both for the line position and line intensity calculations. To calculate the line positions the Hamiltonian matrix accounts for the very strong Fermi and the weaker Coriolis interactions linking the 5 1⇔9 2 rotational levels, and the torsional effects are accounted for within the frame of the IAM (Internal Axis Method) approach. In addition, the v-diagonal blocks involve non-orthorhombic operators together with Watson’s type rotational operators. This means that the z-quantization axis deviates from the a inertial axis for both the 5 1 and 9 2 vibrational states. The line intensity calculations were performed accounting also for the axis switching effects. As far as the experimental line positions are concerned we have used the millimeter wave data available in the literature [J. Mol. Spectrosc., 175 (1996) 395; J. Mol. Spectrosc., 208 (2001) 121; and references therein], as well as new centimeter wave measurements performed in Kiel and new Fourier transform infrared spectra recorded in Giessen. For the line intensities we have used an extensive set of individual line intensities measured recently [J. Mol. Spectrosc., 218 (2003) 151]. All these experimental data were very satisfactorily reproduced using the theoretical model described above and an improved set of line positions and intensities was generated for the ν 5 and 2 ν 9 bands allowing one to better model the HNO 3 absorption in the 11 μm spectral domain.