The new nitrogen dioxide (NO2) linelist in the GEISA database and first identification of the ν1+2ν3-ν3 band of 14N16O2

doi:10.1016/j.jms.2020.111394

Journal of Molecular Spectroscopy

Volume 376, February 2021, 111394

https://doi.org/10.1016/j.jms.2020.111394 Get rights and content

Highlights

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Line positions and intensities for NO₂ in GEISA-19 (https://geisa.aeris-data.fr/) and line shape (GEISA-19) for GEISA (https://geisa.aeris-data.fr/) dioxide.
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¹⁴N¹⁶O₂ and ¹⁵N¹⁶O₂. 1153–4775 cm⁻¹ spectral range.
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Validation with high resolution Fourier transform spectra.
Comparisons with HITEMP and HITRAN2016-updated.
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First determination of the (1,0,2) energy level parameters and improvements for the (0,1,1) state.

Abstract

We have generated new lists of line position, line intensity and line shape parameters of nitrogen dioxide (¹⁴N¹⁶O₂ and ¹⁵N¹⁶O₂), here labeled as “GEISA-19”, which have been included in the (Gestion et Etude des Informations Spectroscopiques Atmosphériques) GEISA database (https://geisa.aeris-data.fr/). Except for the far infrared and the 13.3 µm regions, all spectral regions of the 1153–4775 cm⁻¹ spectral domain are significantly modified by this major update of the GEISA linelist. For the 6.2 µm and 3.4 µm spectral regions, which correspond to the strongest absorption of NO₂, we proceed to a complete replacement of the lists for the first hot bands, ν₂ + ν₃-ν₂ and ν₁ +ν₂ + ν₃-ν₂, respectively, and to the inclusion, whenever possible, of higher order hot bands involving the (1,0,0), (0,2,0) and (0,0,1), (1,1,0), (2,0,0) or (0,0,2) states as lower states. Also, the ν₁ + ν₃ linelist was improved for high rotational quantum numbers and the ν₃ and ν₁+ν₃ bands for ¹⁵N¹⁶O₂, which is the second most abundant isotopologue of NO₂, are now included in the database. Finally several weak cold bands in the 2.2–4.9 µm region were added for the first time to the GEISA linelist. These new vibration rotation transitions were generated using existing literature data or making use of experimental data extracted from high resolution Fourier transform spectra recorded at SOLEIL for the purpose of this study. One outcome of this study was the first identification of the ν₁+2ν₃-ν₃ hot band, leading to the first determination of the (1,0,2) energy level parameters. Also, an improved set of parameters was derived for the (0,1,1) state. The validation of the GEISA-19 linelist was performed through a detailed comparison at 296 K between computed and observed Fourier transform laboratory spectra. Also, the consistency, from one band to another, of the energy levels values was carefully checked. Finally inter-comparisons and verifications were performed using the recent versions of the HITRAN (https://hitran.org/) and HITEMP databases [R.J. Hargreaves, I. E. Gordon, L. S. Rothman, S. A. Tashkun, V. I. Perevalov, A. A. Lukashevskaya, S. N. Yurchenko, J. Tennyson, and H. S.P. Müller. J. Quant. Spectrosc. Radiat. Transf. 232 35 (2019)]. Our conclusions are that, at 296 K, GEISA-19 is of better quality than HITRAN2016-updated or HITEMP in the overall 1153–4775 cm⁻¹ spectral region. As compared to its previous version, this new linelist will lead to an improved quality of the NO₂ retrievals that will be performed for the future IASI-NG (Infrared Atmospheric Sounding Interferometer New Generation) satellite instrument (https://iasi-ng.cnes.fr/fr). However, contrary to HITEMP, GEISA-19 which does not include transitions involving high rotational quantum numbers or belonging to very high order hot bands cannot be used for hot temperature conditions.

Graphical abstract

Introduction

Because of its important role in the photochemistry of the atmosphere, nitrogen dioxide has been the subject of numerous spectroscopic studies. These led to the generation of linelists which are now included in the GEISA [1], HITRAN [2], and HITEMP [3] databases.

Until very recently (2016), the linelists present in the 2016 version of HITRAN [2] and in the 2015 version of GEISA [1] for nitrogen dioxide did not differ significantly. This 2015 version of the NO₂ linelist, which concerns only the ¹⁴N¹⁶O₂ isotopomer, will be noted as “HITRAN-GEISA-15” in the rest of the text. For the ¹⁴N¹⁶O₂ species, four spectral regions are considered in HITRAN-GEISA-15 which correspond to the microwave to far infrared region (pure rotation within the (0,0,0) state), the 13.3 µm (ν₂ band), the 6.2 µm (the strong ν₃ band and the weaker ν₁ and 2ν₂ dark resonating bands) and 3.4 µm (the rather strong ν₁+ν₃ band and the weaker ν₁+2ν₂ dark resonating band) regions, respectively. Together with these cold bands, the HITRAN-GEISA-15 list includes in all four regions lines from the first hot bands which involve the (0,1,0) state as lower vibrational state. These linelists were generated at different time, and with different accuracy, and as it will be discussed in this paper, HITRAN-GEISA-15 presents clear deficiencies.

The most recent version of the HITEMP (“HIgh-TEMPerature molecular spectroscopic database“) linelist includes NO₂ for the first time [3]. The aim of HITEMP is to model gas phase spectra for high-temperature applications. For NO₂, a composite HITEMP linelist was generated in the 0–4775 cm⁻¹ by extending the current HITRAN linelist [2] (here labelled as HITRAN2016-updated”)¹ using inputs from the recent “Nitrogen Dioxide Spectroscopic Databank” (NDSD-1000) [4], [5] line list. These additional inputs concern all spectral regions except the pure rotations bands (microwave to far infrared). For the vibrational transitions already considered in HITRAN, the NDSD-1000 has provided extension of the current list up to the higher N (N ≤ 100) and K_a values. HITEMP also includes linelists for several cold and hot bands² which, up to now, were missing in HITRAN-GEISA-15. Up to now, HITEMP does not include linelists for the ¹⁵N¹⁶O₂ (second) isotope species of nitrogen dioxide.

Subsequently, the “HITRAN2016-updated”, the 2020 version of HITRAN, was created [6]. The 1153–4775 cm⁻¹ spectral range now include lines from several weaker vibration–rotation bands present in HITEMP which were not considered previously in HITRAN-GEISA-15 [1], [2]. More recently, the spectral range for NO₂ has been extended to include transitions between 5720 and 8000 cm⁻¹, with the addition of several combination and overtone bands [7], [8], [9], [10], [11], [12], [13], [14], [15]. Finally, HITRAN2016-updated now includes line parameters for the ν₃ band of ¹⁵N¹⁶O₂ [16] which is the most abundant daughter isotopologue of NO₂.

Therefore, as compared to the previous version of HITRAN [2], both HITRAN2016-updated and HITEMP [3] databases were significantly extended. However, the existing deficiencies in HITRAN-GEISA-15 were not corrected.

The purpose of the present work was to generate a new version of GEISA linelist for NO₂, here identified as ‘GEISA-19″, which now includes NO₂ lines parameters for the 0–4775.3 cm⁻¹ region.³ As far as the line positions and intensities are concerned, this update does not concern the microwave to far infrared region, while all other spectral regions (1153- 4777.3 cm⁻¹) took benefit of new parameters generated during this work.

For the 6.2 µm and 3.4 µm regions which correspond to the strongest NO₂ infrared absorption, we process to the replacement of the cold and of «first» hot bands, and GEISA-19 now includes, when possible, line parameters from higher order hot bands. We also implement in GEISA-19 linelists for several weak cold bands that absorb in the 2000–4775 cm⁻¹ spectral range. In addition, GEISA-19 includes linelists for the ν₃ and ν₁+ν₃ bands for the ¹⁵N¹⁶O₂ isotopic species.

Therefore, it is clear that the GEISA-19 linelist differs from HITRAN-GEISA-15, HITRAN2016-updated [6], and HITEMP [3].

The present work was performed using, as input to our calculations, not only the spectroscopic data available in the literature but also additional data issued from two recent spectroscopic studies (Refs. [17], [18]), or obtained from the analysis of two new FTS spectra recorded during this work.

Before going into detail description of the work, we will define the vibrational and rotational quantum numbers and the energy levels used in this paper. Then we will describe the theoretical models used for the computations.

Section snippets

The NO₂ vibrational and rotational quantum numbers

Nitrogen dioxide (¹⁴N¹⁶O₂) is an asymmetric rotor, with three vibrational modes, ω₁, ω₂, which are symmetric and ω₃ which is antisymmetric, and the vibrational modes are noted as (v₁,v₂,v₃). As a matter of consequence, the vibrational states are grouped in polyads of interacting states. When necessary, the rovibrational interactions were accounted for in order to reproduce the measured line positions and intensities, and the present computations were performed polyad by polyad.

This molecule

Line position, line intensity and line shape parameters

During this work the linelists for numerous vibration – rotation bands were generated in the 1153–4775.4 cm⁻¹ spectral region, and the theoretical models used to compute the line positions and intensities account both for the spin- rotation resonances and for various vibration – rotational resonances.

Experimental details

Three high-resolution absorption spectra (FTS12, FTS3 and FTS3bis) of nitrogen dioxide were recorded on the Bruker IFS125HR Fourier transform spectrometer of the AILES Beamline at Synchrotron SOLEIL, coupled to the newly developed corrosive gas multipass cell [30]. For the spectrum in the ν₁+ν₂ region, (FTS12) the cell path length was set to 10.88 m, the interferometer was equipped with a Si/CaF₂ beam splitter and an InSb detector. The spectral resolution was chosen to give an apparatus

The microwave to far infrared region and the 13.3 µm regions

In HITRAN-GEISA-15 the microwave and far infrared region, involves rotational transitions within the (0,0,0) and (0,1,0) vibrational state [19], [20], [37]. The 13.3 µm region considers the lines belonging to the ν₂ band [20] and its associated 2ν₂-ν₂ «first» hot band [33], [20]. The details on the line intensities calculations, models and parameters, are given in Refs. [19], [20], [33]. As far as the line positions and intensities, these microwave to far-infrared and 13.3 µm linelists were not

The GEISA-19 database in the 1153–4775 cm⁻¹ spectral region

For wavenumbers greater than 1153 cm⁻¹, GEISA-19 was largely modified as compared to its previous version. First, we updated the lists for the main cold bands and the first hot bands which were the only originally present in HITRAN-GEISA-15 at 6.2 and 3.4 µm. Also, we add new linelists which concern (i) higher order hot bands in the 6.2 µm and 3.4 µm regions (ii) several weaker bands in the 2.3 to 4.9 µm region, and (iii) the ν₃ and ν₁+ν₃ bands for the ¹⁵N¹⁶O₂ isotopic species of nitrogen

Validations of the new GEISA-19 database

Two different types of validations for the GEISA-19, HITEMP and HITRAN2016-updated linelists were performed. First the existing laboratory FTS spectra (see Table 2) were used to check these linelists through inter-comparison between observed and calculated spectra. In a second step, we checked, within these databases, the internal consistency of the computed energy levels in term of the Rydberg–Ritz combination principle.

Conclusion

During this work, a new version of the line by energy level parameters (line positions, intensities and shape) for nitrogen dioxide was generated for the 0–4700 cm⁻¹ spectral range and implemented in the (Gestion et Etude des Informations Spectroscopiques Atmosphériques) GEISA database (https://geisa.aeris-data.fr/). Except for the far infrared and 13.3 µm regions all spectral regions are significantly affected by this major update.

For the main (¹⁴N¹⁶O₂) isotope species, the updated lists

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgments

The authors acknowledge support from synchrotron SOLEIL (project 99200018). This work was supported by the French National program LEFE « Les Enveloppes Fluides et l’Environnement » through the « MEANSPECFORUM » project. It is also funded by the French National program ANR (ANR-19-CE29-0013) through the « QUASARS » project. Also, we thank the reviewer for his very valuable comments.

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Citation Excerpt :
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The new nitrogen dioxide (NO2) linelist in the GEISA database and first identification of the ν1+2ν3-ν3 band of 14N16O2

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

The NO2 vibrational and rotational quantum numbers

Line position, line intensity and line shape parameters

Experimental details

The microwave to far infrared region and the 13.3 µm regions

The GEISA-19 database in the 1153–4775 cm−1 spectral region

Validations of the new GEISA-19 database

Conclusion

Declaration of Competing Interest

Acknowledgments

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J. Mol. Spectrosc.

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J. Quant. Spectrosc. Radiat. Transf.

J. Mol. Spectrosc.

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J. Mol. Spectrosc.

J. Mol. Spectrosc.

The new nitrogen dioxide (NO₂) linelist in the GEISA database and first identification of the ν₁+2ν₃-ν₃ band of ¹⁴N¹⁶O₂

The NO₂ vibrational and rotational quantum numbers

The GEISA-19 database in the 1153–4775 cm⁻¹ spectral region