Comment on the paper ;NDSD-1000: High-resolution, high-temperature nitrogen dioxide spectroscopic Databank; by A.A. Lukashevskaya, N.N. Lavrentieva, A.C. Dudaryonok, V.I. Perevalov, J Quant Spectrosc Radiat Transfer 2016;184:205-17

Abstract A recent paper [1] presents a high-resolution, high-temperature version of the Nitrogen Dioxide Spectroscopic Databank called NDSD-1000. The NDSD-1000 database contains line parameters (positions, intensities, self- and air-broadening coefficients, exponents of the temperature dependence of self- and air-broadening coefficients) for numerous cold and hot bands of the 14 N 16 O 2 isotopomer of nitrogen dioxide. The parameters used for the line positions and intensities calculation were generated through a global modeling of experimental data collected in the literature within the framework of the method of effective operators. However, the form of the effective dipole moment operator used to compute the NO 2 line intensities in the NDSD-1000 database differs from the classical one used for line intensities calculation in the NO 2 infrared literature [12]. Using Fourier transform spectra recorded at high resolution in the 6.3 µm region, it is shown here, that the NDSD-1000 formulation is incorrect since the computed intensities do not account properly for the (Int(+)/Int(−)) intensity ratio between the (+) (J = N+ 1/2) and (−) (J = N−1/2) electron – spin rotation subcomponents of the computed vibration rotation transitions. On the other hand, in the HITRAN or GEISA spectroscopic databases, the NO 2 line intensities were computed using the classical theoretical approach, and it is shown here that these data lead to a significant better agreement between the observed and calculated spectra.

[1]  Walter Gordy,et al.  Microwave Molecular Spectra , 1970 .

[2]  Jean-Marie Flaud,et al.  NO2 AND SO2 LINE PARAMETERS: 1996 HITRAN UPDATE AND NEW RESULTS , 1998 .

[3]  A. R. Edmonds Angular Momentum in Quantum Mechanics , 1957 .

[4]  Detection of atmospheric 15NO2 in the ν3 spectral region (6.3μm) , 2015 .

[5]  V. Malathy Devi,et al.  Diode laser measurements of intensities, N2-broadening, and self-broadening coefficients of lines of the ν2 band of 14N16O2 , 1981 .

[6]  P. Roy,et al.  Improved mid infrared detector for high spectral or spatial resolution and synchrotron radiation use. , 2016, The Review of scientific instruments.

[7]  V. I. Perevalov,et al.  Parameterization of the effective dipole moment matrix elements in the case of the asymmetric top molecules. Application to NO2 molecule , 2015 .

[8]  Bruno Carli,et al.  The far infrared spectrum of 14N16O2 , 1988 .

[9]  Jonathan Tennyson,et al.  The 2015 edition of the GEISA spectroscopic database , 2016 .

[10]  Frank J. Murcray,et al.  The ν1, 2ν2, and ν3 interacting bands of 14N16O2: Line positions and intensities , 1992 .

[11]  Jean-Marie Flaud,et al.  Infrared nitrogen dioxide: Line parameters in the HITRAN database , 1992 .

[12]  Frank J. Murcray,et al.  The ν2 and 2ν2 - ν2 bands of 14N 16O2: Electron Spin-Rotation and Hyperfine Contact Resonances in the (010) Vibrational State , 1993 .

[13]  J.-Y. Mandin,et al.  The {ν1+ 2ν2, ν1+ ν3} Bands of14N16O2: Line Positions and Intensities; Line Intensities in the ν1+ ν2+ ν3− ν2Hot Band , 1997 .

[14]  Nina N. Lavrentieva,et al.  NDSD-1000: High-resolution, high-temperature Nitrogen Dioxide Spectroscopic Databank , 2016 .

[15]  A. Perrin,et al.  Global modeling of NO2 line positions , 2015 .

[16]  J. Brown,et al.  Microwave spectroscopy of nonlinear free radicals - I. General theory and application to the Zeeman effect in HCO , 1973, Proceedings of the Royal Society of London. A. Mathematical and Physical Sciences.