High sensitivity Cavity Ring Down spectroscopy of 18O enriched carbon dioxide between 5850 and 7000 cm-1: Part III-Analysis and theoretical modeling of the 12C17O2, 16O12C17O, 17O12C18O, 16O13C17O and 17O13C18O spectra

More than 19,700 transitions belonging to 11 isotopologues of carbon dioxide have been assigned in the room temperature absorption spectrum of highly 18O enriched carbon dioxide recorded by very high sensitivity CW-Cavity Ring Down spectroscopy between 5851 and 6990 cm-1 (1.71-1.43 \mum). This third and last report is devoted to the analysis of the bands of five 17O containing isotopologues present at very low concentration in the studied spectra: 16O12C17O, 17O12C18O, 16O13C17O, 17O13C18O and 12C17O2 (627, 728, 637, 738 and 727 in short hand notation). On the basis of the predictions of effective Hamiltonian models, a total of 1759, 1786, 335, 273 and 551 transitions belonging to 24, 24, 5, 4 and 7 bands were rovibrationally assigned for 627, 728, 637, 738 and 727, respectively. For comparison, only five bands were previously measured in the region for the 728 species. All the identified bands belong to the \deltaP=8 and 9 series of transitions, where P=2V1+V2+3V3 is the polyad number (Vi are vibrational quantum numbers). The band-by-band analysis has allowed deriving accurate spectroscopic parameters of 61 bands from a fit of the measured line positions. Two interpolyad resonance perturbations were identified

Electric-quadrupole and magnetic-dipole contributions to the ν₂+ν₃ band of carbon dioxide near 3.3 µm

The recent detections of electric-quadrupole (E2) transitions in water vapor and magnetic-dipole (M1) transitions in carbon dioxide have opened a new field in molecular spectroscopy. While in their present status, the spectroscopic databases provide only electric-dipole (E1) transitions for polyatomic molecules (H_{2}O, CO_{2}, N_{2}O, CH_{4}, O_{3}…), the possible impact of weak E2 and M1 bands to the modeling of the Earth and planetary atmospheres has to be addressed. This is especially important in the case of carbon dioxide for which E2 and M1 bands may be located in spectral windows of weak E1 absorption. In the present work, a high sensitivity absorption spectrum of CO_{2} is recorded by Optical-Feedback-Cavity Enhanced Absorption Spectroscopy (OFCEAS) in the 3.3 µm transparency window of carbon dioxide. The studied spectral interval corresponds to the region where M1 transitions of the ν_{2}+ν_{3} band of carbon dioxide were recently identified in the spectrum of the Martian atmosphere. Here, both M1 and E2 transitions of the ν_{2}+ν_{3} band are detected by OFCEAS. Using recent ab initio calculations of the E2 spectrum of {12}^C^{16}O_{2}, intensity measurements of five M1 lines and three E2 lines allow us to disentangle the M1 and E2 contributions. Indeed, E2 intensity values (on the order of a few 10^{–29} cm/molecule) are found in reasonable agreement with ab initio calculations while the intensity of the M1 lines (including an E2 contribution) agree very well with recent very long path measurements by Fourier Transform spectroscopy. We thus conclude that both E2 and M1 transitions should be systematically incorporated in the CO_{2} line list provided by spectroscopic databases

Study of ozone smog episodes by Lidar 3D measurements in Lyon and Paris during summer 1999

Every summer, ozone smog episodes systematically take place in large agglomerations. In order to prevent them, a better understanding of formation dynamics is needed using numerical models. These models must, however, be validated. Lidar is a unique tool for this task since it provides 3D measurements, for example combining 2D spatial measurements with time in an "animation movie". We present here two recent examples of such ozone Lidar measurement campaigns: the first over Lyon, was mainly used to evaluate a UAM-V type photochemical model and obtain ozone inter comparison data between ground level monitors and Lidar results. The other was performed in Paris and dedicated to validating the Lidar measurements themselves

New transitions and energy levels of water vapor by high sensitivity CRDS near 1.73 and 1.54 µm

This contribution is part of a long term project aiming at improving the water absorption spectroscopy by high sensitivity cavity ring down spectroscopy (CRDS) in the near infrared. Two new sources of CRDS spectra are considered: (i) The room temperature absorption spectrum of water vapor in natural isotopic abundance is recorded near 1.73 µm. A series of recordings was performed from 5693 to 5991 cm−1 with a pressure value of about 6 Torr. The noise equivalent absorption (αmin) of the spectra is better than 10− 10 cm−1. A total of 1453 lines were assigned to 1573 transitions of four water isotopologues (H2 16O, H2 17O, H2 18O and HD16O). Their intensities span more than five orders of magnitude from 3.0 × 10−30 to 4.7 × 10−25 cm/molecule at 296 K. The assignments were performed using known experimental energy levels as well as calculated line lists based on the results of Schwenke and Partridge. Two hundred fifty-one lines (assigned to 280 transitions) are observed for the first time and twelve energy levels are newly determined. The comparison of the obtained line parameters with those of the HITRAN database is discussed. Forty-six line positions are observed to significantly differ from their HITRAN values (δν = │νHITRAN – νCRDS│ > 0.02 cm−1). The derived set of energy levels is compared to those recommended by an IUPAC task group. (ii) The room temperature CRDS spectrum of water vapor highly enriched in 17O was recorded near 1.54 µm (6223–6672 cm−1) at a pressure of 12 Torr. Compared to a previous study, the higher pressure of the recordings allowed for extending the observations. Overall, twenty-six new levels were determined for both H2 17O and HD17O. All these observations together with other recent measurements will allow for an extension and an update of our empirical database in the 5693– 8340 cm−1 region. © 2019 Elsevier Lt

The HITRAN2020 Molecular Spectroscopic Database

The HITRAN database is a compilation of molecular spectroscopic parameters. It was established in the early 1970s and is used by various computer codes to predict and simulate the transmission and emission of light in gaseous media (with an emphasis on terrestrial and planetary atmospheres). The HITRAN compilation is composed of five major components: the line-by-line spectroscopic parameters required for high-resolution radiative-transfer codes, experimental infrared absorption cross-sections (for molecules where it is not yet feasible for representation in a line-by-line form), collision-induced absorption data, aerosol indices of refraction, and general tables (including partition sums) that apply globally to the data. This paper describes the contents of the 2020 quadrennial edition of HITRAN. The HITRAN2020 edition takes advantage of recent experimental and theoretical data that were meticulously validated, in particular, against laboratory and atmospheric spectra. The new edition replaces the previous HITRAN edition of 2016 (including its updates during the intervening years). All five components of HITRAN have undergone major updates. In particular, the extent of the updates in the HITRAN2020 edition range from updating a few lines of specific molecules to complete replacements of the lists, and also the introduction of additional isotopologues and new (to HITRAN) molecules: SO, CH3F, GeH4, CS2, CH3I and NF3. Many new vibrational bands were added, extending the spectral coverage and completeness of the line lists. Also, the accuracy of the parameters for major atmospheric absorbers has been increased substantially, often featuring sub-percent uncertainties. Broadening parameters associated with the ambient pressure of water vapor were introduced to HITRAN for the first time and are now available for several molecules. The HITRAN2020 edition continues to take advantage of the relational structure and efficient interface available at www.hitran.org and the HITRAN Application Programming Interface (HAPI). The functionality of both tools has been extended for the new edition

The HITRAN2020 molecular spectroscopic database

The HITRAN database is a compilation of molecular spectroscopic parameters. It was established in the early 1970s and is used by various computer codes to predict and simulate the transmission and emission of light in gaseous media (with an emphasis on terrestrial and planetary atmospheres). The HITRAN compilation is composed of five major components: the line-by-line spectroscopic parameters required for high-resolution radiative-transfer codes, experimental infrared absorption cross-sections (for molecules where it is not yet feasible for representation in a line-by-line form), collision-induced absorption data, aerosol indices of refraction, and general tables (including partition sums) that apply globally to the data. This paper describes the contents of the 2020 quadrennial edition of HITRAN. The HITRAN2020 edition takes advantage of recent experimental and theoretical data that were meticulously validated, in particular, against laboratory and atmospheric spectra. The new edition replaces the previous HITRAN edition of 2016 (including its updates during the intervening years). All five components of HITRAN have undergone major updates. In particular, the extent of the updates in the HITRAN2020 edition range from updating a few lines of specific molecules to complete replacements of the lists, and also the introduction of additional isotopologues and new (to HITRAN) molecules: SO, CH3F, GeH4, CS2, CH3I and NF3. Many new vibrational bands were added, extending the spectral coverage and completeness of the line lists. Also, the accuracy of the parameters for major atmospheric absorbers has been increased substantially, often featuring sub-percent uncertainties. Broadening parameters associated with the ambient pressure of water vapor were introduced to HITRAN for the first time and are now available for several molecules. The HITRAN2020 edition continues to take advantage of the relational structure and efficient interface available at www.hitran.org and the HITRAN Application Programming Interface (HAPI). The functionality of both tools has been extended for the new edition

ULTRA SENSITIVE CAVITY RING DOWN SPECTROSCOPY OF MAJOR ATMOSPHERIC SPECIES BETWEEN 1.20 AND 1.71 μ \mum

Author Institution: Universite Grenoble 1/CNRS, UMR5588 \mbox{LIPhy}, Grenoble, F-38041, FranceDuring recent years, we have developed a fibered DFB laser CW-CRDS spectrometer providing routine noise equivalent absorption of $\alpha_{min}\approx5\times10^{-11}$cm$^{-1}$, over the 5850-8350 cm$^{-1}$ range. A detection limit of $\alpha_{min}\approx5\times10^{-13}$cm$^{-1}$ has been recently achieved by averaging spectra over a small spectral interval. The performances of this set up have allowed extending significantly the knowledge of the absorption spectra of molecules of major importance: methane, oxygen, water, ozone, carbon dioxide, hydrogen, nitrogen. The most striking results will be presented

Performance of a 12.49 meter folded path copper Herriott cell designed for temperatures between 296 and 20 K

International audienceUsing a set of gold-coated copper mirrors identical to those reported previously we were able to increase the useful absorption path from 5.9 meters to 12.49 meters. The low temperature performance of the new cell is similar to that of the previously described cell. The testing procedure and results are described here

Accurate measurements and temperature dependence of the water vapor self-continuum absorption in the 2.1 μm atmospheric window

International audienc

The water vapour self-continuum by CRDS at room temperature in the 1.6 µm transparency window

International audienceThe water vapour self-continuum has been investigated by high sensitivity Cavity Ring Down Spectroscopy at room temperature in the 1.6 µm window. The real time pressure dependence of the continuum was investigated during pressure cycles up to 12 Torr for fifteen selected wavenumber values. The continuum absorption coefficient measured between 5875 and 6450 cm-1 shows a minimum value around 6300 cm-1 and ranges between 1×10-9 and 8×10-9 cm-1 for 8 Torr of water vapour. The continuum level is observed to deviate significantly from the expected quadratic dependence versus the pressure. This deviation is interpreted as due to a significant contribution of water adsorbed on the super mirrors to the cavity loss rate. The pressure dependence is well reproduced by a second order polynomial. We interpret the linear and quadratic terms as the adsorbed water and vapour water contribution, respectively