High-resolution infrared spectra of OOO ozone isotopomer in the range 900-5000 cm: line positions

Continuing the systematic study of ozone high-resolution infrared spectra, we present in this paper the measurements and analyses of line positions for the ¹⁸O¹⁶O¹⁸O isotopomer. In the range 900-5000 cm⁻¹, corresponding to the observed spectra, 15 bands are analysed: ν₁, ν₃, ν₂+ν₃, ν₁+ν₂, 2ν₃, ν₁+ν₃, 2ν₁, ν₂+2ν₃, ν₁+ν₂+ν₃, 3ν₃, 2ν₁+ν₃, ν₂+3ν₃, ν₁+3ν₃, ν₁+ν₂+3ν₃, and 5ν₃. As in the case of ¹⁶O₃, ¹⁸O₃, and ¹⁶O¹⁸O¹⁶O, the analysis of these bands is performed using effective rovibrational Hamiltonians for nine polyads of interacting upper vibrational states. To correctly reproduce all observed transitions, we have to account for resonance perturbations due to 13 “Dark” states: (0 3 0), (0 4 0), (2 1 0), (0 3 1), (1 0 2), (0 4 1), (1 1 2), (3 1 0), (0 3 2), (0 0 4), (3 2 0), (0 1 4), and (0 4 2). We present the range of observed transitions, the results for spectroscopic parameters (vibrational energy levels, rotational and centrifugal distortion constants, and resonance coupling parameters), as well as the statistics for rovibrational energy levels, calculations and measurements. A comparison of observed band centres with those predicted from an isotopically invariant potential function is discussed. The RMS deviation between predicted and directly observed band centres is ≈0.03 cm⁻¹ up to 3000 and ≈0.25 cm⁻¹ for all 16 bands up to 5000 cm⁻¹.     

Detection and analysis of new bands of O3 by CRDS between 6500 and 7300 cm

The absorption spectrum of the ¹⁶O₃ isotopologue of ozone has been recorded in the 7000-7920 cm⁻¹ region by high sensitivity CW-Cavity Ring Down Spectroscopy. This report is devoted to the analyses of the 7065-7300 cm⁻¹ region dominated by the ν₁ + 2ν₂ + 5ν₃ and ν₁ + 5ν₂ + 3ν₃ A-type bands at 7130.8 and 7286.8 cm⁻¹ respectively. 289 transitions were assigned to the ν₁ + 2ν₂ + 5ν₃ band. The corresponding line positions were modeled with an effective Hamiltonian involving Coriolis resonance interactions between the (1 2 5) upper state and the (4 4 0), (0 2 6) and (6 1 0) dark states, and an anharmonic resonance interaction with the (2 0 5) state. The very strong interaction (up to 50% mixing of the wavefunctions) between the (1 2 5) and (6 1 0) states leads to the observation of two extra lines of the 6ν₁ + ν₂ band due to a resonance intensity transfer. 213 transitions of the ν₁ + 5ν₂ + 3ν₃ band were assigned and modeled taking into account a Coriolis resonance interaction with the (3 6 0) state.We take the opportunity of the present work to report the analysis of the very weak 4ν₂ + 4ν₃ B-type band at 6506.1 cm⁻¹ which was assigned from previously recorded CRDS spectra. 286 transitions were modeled using the effective Hamiltonian approach.The dipole transition moment parameters of the three analyzed bands were determined by a least-squares fit to the measured line intensities. For the three studied band systems, the effective Hamiltonian and transition moment operator parameters were used to generate line lists provided as Supplementary Materials.     

A (nearly) complete experimental linelist for CO2, OCO, OCO, CO2 and OCO by high-sensitivity CW-CRDS spectroscopy between 5851 and 7045 cm

An experimental database for the ¹³C¹⁶O₂, ¹⁶O¹³C¹⁸O, ¹⁶O¹³C¹⁷O, ¹³C¹⁸O₂ and ¹⁷O¹³C¹⁸O isotopologues of carbon dioxide has been constructed on the basis of the high-sensitivity absorption spectrum of carbon dioxide with 99% enrichment in ¹³C recorded by CW-cavity ring down spectroscopy (CW-CRDS) between 5851 and 7045 cm⁻¹. As a result of the achieved sensitivity (typical noise equivalent absorption α_min∼2-5×10⁻¹⁰ cm⁻¹) combined with the high linearity and dynamics (more than four decades) of the CW-CRDS technique, the amount of spectroscopic information contained in these spectra was considerable. A total of 8639 transitions of the ¹³C¹⁶O₂, ¹⁶O¹³C¹⁸O, ¹⁶O¹³C¹⁷O, ¹³C¹⁸O₂ and ¹⁷O¹³C¹⁸O isotopologues with line strength as low as 5×10⁻²⁹ cm/molecule were assigned. They belong to a total of 150 bands, while less than 20 bands were previously reported by Fourier transform spectroscopy. The excellent agreement between the predictions of the effective operators model and the observations has allowed using an automatic search program to assign the weaker lines observed in the congested spectrum. The spectroscopic parameters of the vibrational upper levels were obtained from a fit of the measured line positions. A number of resonance interactions were observed; in particular, several occurrences of interpolyad anharmonic couplings not included in the polyad model of effective Hamiltonian, were found to affect a few bands of the ¹⁶O¹³C¹⁸O and ¹⁶O¹³C¹⁷O isotopologues. In the list of 8639 transitions, which are provided as Supplementary material, line positions are experimental values (typical uncertainty in the order of 1×10⁻³ cm⁻¹), while line strengths were calculated at 296 K by using the effective operators approach (typical uncertainty in the order of 5%). In the case of the ¹³C¹⁶O₂ isotopologue, the reported transitions represent 99.65% of the total absorbance in the region considered.     

Line positions and energy levels of the O substitutions from the HDO/D2O spectra between 5600 and 8800 cm

Absorption spectra of HDO/D₂O mixtures recorded in the 5600-8800 cm⁻¹ region with a total pressure of water from 13 up to 18 hPa and an absorption path length of 600 m have been analyzed in order to obtain new spectroscopic data for HD¹⁸O and D₂¹⁸O. In spite of the low natural ¹⁸O concentration (about 2×10⁻³ with respect to the ¹⁶O one), about 1100 transitions belonging to HD¹⁸O and more than 280 transitions belonging to D₂¹⁸O have been assigned. Most of the D₂¹⁸O transitions belong to the ν₁+ν₂+ν₃ and 2ν₁+ν₃ bands. Sets of energy levels for seven vibrational states of D₂¹⁸O and four states of HD¹⁸O are reported for the first time. The comparison of the experimental data with the calculated values based on Partridge-Schwenke global variational calculations is discussed.     

High sensitivity ICLAS of H2O in the region of the second decade (11 520-12 810 cm)

The high resolution absorption spectrum of the H₂¹⁸O isotopologue of water has been recorded by Intracavity Laser Absorption Spectroscopy (ICLAS) with a sensitivity on the order of α_min ∼ 10⁻⁹ cm⁻¹. The 11 520-12 810 cm⁻¹ spectral region corresponding to the 3ν + δ decade of vibrational states, was explored with an ICLAS spectrometer based on a Ti:Sapphire laser. It allowed detecting transitions with an intensity down to 10⁻²⁷ cm/molecule which is about 100 times lower than the weaker line intensities available in the literature, in particular in the HITRAN database.The rovibrational assignment was performed on the basis of the results of variational calculations and allowed for assigning 3659 lines to the H₂¹⁶O, H₂¹⁸O, H₂¹⁷O, HD¹⁶O and HD¹⁸O species, leaving only 1.7% unassigned transitions. A line list including 1712 transitions of H₂¹⁸O has been generated and assigned leading to the determination of 692 rovibrational energy levels belonging to a total of 16 vibrational states, 386 being newly observed. A deviation on the order of 25% has been evidenced for the average intensity values given by HITRAN and the results of variational calculations. Ninety two transitions of the HD¹⁸O isotopologue could also be assigned and the corresponding upper rovibrational levels are given.     

CW-Cavity Ring Down spectroscopy of O3. Part 1: Experiment and analysis of the 6200-6400 cm spectral region

The absorption spectrum of the ¹⁸O₃ isotopologue of ozone has been recorded in the 6200-6400 cm⁻¹ region by high sensitivity CW-Cavity Ring Down Spectroscopy. The spectrum is dominated by the 2ν₁ + 5ν₃ and 2ν₁ + 3ν₂ + 3ν₃ bands at 6270.6 and 6392.2 cm⁻¹, respectively which were treated independently. The rovibrational analysis of the 2ν₁ + 5ν₃ band has evidenced that the (2 0 5) upper state is perturbed by Coriolis resonance interactions with the (0 1 6), (3 0 4) and (3 5 0) states. A total of 659, 89, 131 and 5 transitions were assigned to the 2ν₁ + 5ν₃, ν₂ + 6ν₃, 3ν₁ + 4ν₃ and 3ν₁ + 5ν₂ bands, respectively. In the case of the 2ν₁ + 3ν₂ + 3ν₃ band, 344 transitions were assigned. Some of them were found perturbed by a Coriolis interaction of the (2 3 3) state with the (5 2 0) state.Overall, 681 energy levels were derived from the analysis of the 2ν₁ + 5ν₃ and 2ν₁ + 3ν₂ + 3ν₃ band systems. In both cases, a suitable effective Hamiltonian was elaborated, allowing accounting satisfactorily for the retrieved rovibrational energy levels. In addition, dipole transition moment parameters were determined by a least-squares fit to the measured line intensities. The effective Hamiltonian and transition moment operator parameters were used to generate a list of 1619 transitions given as Supplementary material.     

The ν1 + 3ν2 + 3ν3 and 4ν1 + ν2 + ν3 bands of ozone by CW-cavity ring down spectroscopy between 5900 and 5960 cm

The absorption spectrum of ozone, ¹⁶O₃, has been recorded in the 5903-5960 cm⁻¹ region by high sensitivity CW-cavity ring down spectroscopy (α_min ∼ 5 × 10⁻¹⁰ cm⁻¹). The ν₁ + 3ν₂ + 3ν₃ and 4ν₁ + ν₂ + ν₃ A-type bands centred at 5919.15 and 5947.07 cm⁻¹ were newly observed. A set of 173 and 168 energy levels could be experimentally determined for the (1 3 3) and (4 1 1) states, respectively. Except for a few K_a = 5 levels of the (4 1 1) state, the rotational structure of the two states was found mostly unperturbed. The spectroscopic parameters were determined from a fit of the corresponding line positions by considering the (1 3 3) and (4 1 1) states as isolated. The determined effective Hamiltonian and transition moment operators were used to generate a list of 785 transitions given as Supplementary Material.     

CRDS spectroscopy of O3. Part 2: Analysis of six interacting bands between 5930 and 6080 cm

The absorption spectrum of ¹⁸O₃ has been recorded in the 5930-6080 cm⁻¹ region using CW-Cavity Ring Down Spectroscopy. 1888 transitions belonging to five bands have been assigned. Three of them are A-type bands: 2ν₂ + 5ν₃, ν₁ + ν₂ + 5ν₃ and 5ν₁ + ν₃, and two bands are of B-type: 2ν₁ + ν₂ + 4ν₃ and 4ν₁ + 3ν₂. Despite a complex spectral pattern perturbed by many rovibrational resonances, it has been possible to find a suitable effective Hamiltonian model reproducing all the transition wavenumbers (corresponding to 1016 energy levels) with an rms deviation of 9.5 × 10⁻³ cm⁻¹. A set of 721 line intensities was determined and fitted to derive the effective transition moment parameters. This set of parameters and the experimental energy levels were used to generate a complete line list of 2795 transitions allowing to generate synthetic spectrum in good agreement with the experimental spectrum.     

CW-Cavity Ring Down Spectroscopy of the ozone molecule in the 5980-6220 cm region

The absorption spectrum of ozone, ¹⁶O₃, has been recorded in the 5980-6220 cm⁻¹ region by high sensitivity CW-Cavity Ring Down Spectroscopy (α_min ∼ 3 × 10⁻¹⁰ cm⁻¹). This study extends a first investigation with the same experimental set-up limited to the 6030-6090 cm⁻¹ spectral region [M.-R. De Backer-Barilly, A. Barbe, Vl.G. Tyuterev, D. Romanini, B. Moeskops, A. Campargue, J. Mol. Struct. 780-781 (2006) 225-233] where the analysis of two A-type bands was reported, using FTS spectra for complementary information. The spectral extension of the recordings allows not only to enlarge considerably the observed transitions of these two bands, but more importantly, to assign four new bands: the 3ν₂ + 4ν₃,5ν₁ + ν₂ and ν₁ + 2ν₂ + 4ν₃ B-type bands which were considered as dark in our previous report and the 3ν₁ + 3ν₂ + ν₃ A-type band. The high mixing of the observed states approaching the dissociation limit, leads to the breakdown of the polyad structure and ambiguities in the vibrational labelling which are discussed. Finally, 1789 transitions were assigned, and a suitable Hamiltonian model allows reproducing correctly the observations for five of the six observed bands. The list of 1004 experimentally determined energy levels is provided. The determined effective Hamiltonian and transition moment operators were used to generate a list of 5338 transitions given as Supplementary Material. It is interesting to note that the d₅ parameter of the effective transition moment is of great importance to account for the observed intensities of the B-type bands.     

CW-cavity ring down spectroscopy of the ozone molecule in the 6220-6400 cm region

The absorption spectrum of ozone,¹⁶O₃, has been recorded in the 6220-6400 cm⁻¹ region by high sensitivity CW-cavity ring down spectroscopy (α_min ∼ 3 × 10⁻¹⁰ cm⁻¹). 1836 rovibrational transitions have been assigned to the 2ν₂ + 5ν₃, 5ν₁ + ν₃ and 2ν₁ +  2ν₂ + 3ν₃ A-type bands centred at 6305, 6355 and 6387 cm⁻¹, respectively. In addition, 99 lines of the very weak ν₁ + 2ν₂ +  4ν₃ and 4ν₁ + 3ν₂ B-type bands are identified. The modeling of the observed spectrum in the effective Hamiltonian approach was particularly laborious and complex as several rovibrational interactions of both Coriolis and anaharmonic type were found to be of importance, in particular for the (124) vibrational state. Nevertheless, it has finally been possible to fit the 990 experimentally determined energy levels with an rms deviation of 8.29 × 10⁻³ cm⁻¹ and to derive the transition moment parameters allowing a satisfactory reproduction of the observed intensities. As the differences in positions between the final calculations and observations are still larger than the experimental accuracy, we provide the list of all energy levels derived from the observation, in addition to their differences with the calculated ones. These experimental energy levels, with the transition moment parameters were used to generate a line-list of 2451 transitions, reproducing the observed spectrum. This list is given as Supplementary Material.     

High sensitivity CW-CRDS spectroscopy of CO2, OCO and OCO between 5851 and 7045 cm: Line positions analysis and critical review of the current databases

The exhaustive line positions analysis of the absorption spectrum of carbon dioxide in natural abundance has been performed on the basis of high sensitivity CW-Cavity Ring Down spectroscopy between 5851 and 7045 cm⁻¹ (1.71-1.42 μm). The achieved sensitivity (noise equivalent absorption α_min ∼ 2-5 × 10⁻¹⁰ cm⁻¹) have allowed the detection of 8293 transitions of the ¹²C¹⁶O₂, ¹⁶O¹²C¹⁷O and ¹⁶O¹²C¹⁸O isotopologues. They belong to a total of 130 bands. Line intensities of the weakest transitions are on the order of 2 × 10⁻²⁹ cm/molecule. The rovibrational assignments were performed on the basis of accurate predictions of the effective Hamiltonian model of the respective isotopologues. The band-by-band analysis has allowed deriving accurate spectroscopic parameters of 121 bands from a fit of the measured line positions. A number of resonance interactions were identified. In particular, the first observation of an interpolyad coupling is reported for the ¹⁶O¹²C¹⁸O isotopologue. The results of the complete line positions analysis are provided as Supplementary material.The obtained experimental dataset which is the most complete in the considered region, has been used for a critical review of the most currently used spectroscopic databases of carbon dioxide: HITRAN, GEISA, HITEMP, and the recent JPL and CDSD databases.     

High sensitivity CW-CRDS of O enriched water near 1.6 μm

The absorption spectrum of ¹⁸O enriched water has been recorded by continuous wave cavity ring down spectroscopy between 5905.7 and 6725.7 cm⁻¹ using a series of fibred DFB lasers. The investigated spectral region corresponds to the important 1.55 μm transparency window of the atmosphere where water absorption is very weak. The typical CRDS sensitivity (noise equivalent absorption of 5×10⁻¹⁰ cm⁻¹) allowed for the detection of lines with intensity as low as 10⁻²⁸ cm/molecule while the minimum intensity value provided by HITRAN in the considered spectral region is 1.7×10⁻²⁴ cm/molecule. The line parameters were retrieved with the help of an interactive least squares multi-lines fitting program assuming a Voigt function as line profile. Overall, 4510 absorption lines belonging to the H₂¹⁸O, H₂¹⁶O, HD¹⁸O, HD¹⁶O and H₂¹⁷O water isotopologues were measured. Their intensities range between 3×10⁻²⁹ and 5×10⁻²³ cm/molecule at 296 K and the typical accuracy on the line positions is 1×10⁻³ cm⁻¹. 2074 of the observed lines attributed to H₂¹⁸O, HD¹⁸O and H₂¹⁷O are reported for the first time. The transitions were assigned on the basis of variational calculations resulting in 288, 135 and 38 newly determined rovibrational energy levels for the H₂¹⁸O, HD¹⁸O and H₂¹⁷O isotopologues, respectively. The new data set includes the band origin of the 4ν₂ bending overtone of H₂¹⁸O at 6110.4239 cm⁻¹ and rovibrational levels corresponding to J and K_a values up to 18 and 12, respectively, for the strongest bands of H₂¹⁸O: 4ν₂, ν₁+2ν₂, 2ν₂+ν₃, 2ν₁, ν₁+ν₃, and ν₂+ν₃. The obtained experimental results have been compared to the spectroscopic parameters provided by the HITRAN database and to the recent IUPAC critical review of the rovibrational spectrum of H₂¹⁸O and H₂¹⁷O as well as to variational calculations. Large discrepancies between the 4ν₂ variationally predicted and experimental intensities have been evidenced for the H₂¹⁸O and H₂¹⁶O molecules.     

New high-resolution analysis of the {ν1 + ν3} band of the NO2 isotopomer of nitrogen dioxide: Line positions and intensities

The high-resolution Fourier transform absorption spectrum of an isotopic sample of nitrogen dioxide, ¹⁵N¹⁶O₂, was recorded in the 3.4 μm region. Starting from the results of a previous study [Y. Hamada, J. Mol. Struct. 242 (1991) 367-377] a new analysis of the ν₁ + ν₃ band located at 2858.7077 cm⁻¹ has been performed. This new assignment concerns (1 0 1) energy levels involving rotational quantum numbers up to K_a = 10 and N = 54. Using a theoretical model which accounts for both the electron spin-rotation resonances within each vibrational state and the Coriolis interactions between the (1 2 0) and (1 0 1) vibrational states, the spin-rotation energy levels of the (1 0 1) vibrational state could be reproduced within their experimental uncertainty. In this way, the precise vibrational energy, rotational, spin-rotation, and coupling constants were achieved for the {(1 2 0), (1 0 1)} interacting states of ¹⁵N¹⁶O₂. Using these parameters and the transition moment operator which was obtained for the main isotopic species, ¹⁴N¹⁶O₂, a comprehensive list of the line positions and intensities was generated for the ν₁ + ν₃ band of ¹⁵N¹⁶O₂.     

CW-cavity ring down spectroscopy of the ozone molecule in the 6625-6830 cm region

The absorption spectrum of ozone, ¹⁶O₃, has been recorded by CW-cavity ring down spectroscopy in the 6625-6830 cm⁻¹ region. The typical sensitivity of these recordings (α_min ∼ 3 × 10⁻¹⁰ cm⁻¹) allows observing very weak transitions with intensity down to 2 × 10⁻²⁸ cm/molecule. 483 and 299 transitions have been assigned to the 2ν₁ + 3ν₂ + 3ν₃A-type band and to the 2ν₁ + 4ν₂ + 2ν₃B-type band, respectively, which are the highest frequency bands of ozone recorded so far under high resolution. Rovibrational transitions with J and K_a values up to 46 and 12, respectively, could be assigned. Despite well-known difficulties to correctly reproduce the energy levels not far from the dissociation limit, it was possible to determine the parameters of an effective Hamiltonian which includes six vibrational states, four of them being dark states. The line positions analysis led to an rms deviation of 8.5 × 10⁻³ cm⁻¹ while the experimental line intensities could be satisfactorily reproduced. Additional experiments in the 5970-6021 cm⁻¹ region allows detecting the (233) ← (010) hot band reaching the same upper state as the preceding cold band. From the effective parameters of the (233) state just determined and those of the (010) level available in the literature, 329 transitions could be assigned and used for a further refinement of the rovibrational parameters of the effective Hamiltonian leading to a value of 7.6 × 10⁻³ cm⁻¹ for the global rms deviation. The complete list of the experimentally determined rovibrational energy levels of the (233), (242), and (520) states is given. The determined effective Hamiltonian and transition moment operators allowed calculating a line list (intensity cut off of 10⁻²⁸ cm/molecule at 296 K), available as Supplementary material for the 6590-6860 and 5916-6021 cm⁻¹ regions. The integrated band strength values are 1.75 × 10⁻²⁴ and 4.78 × 10⁻²⁵ cm/molecule at 296 K for the 2ν₁ + 3ν₂ + 3ν₃A-type band and to the 2ν₁ + 4ν₂ + 2ν₃B-type band, respectively, while the band intensity value of the (233) ← (010) is estimated to be 1.03 × 10⁻²⁴ cm/molecule.     

High sensitivity CW-Cavity Ring Down Spectroscopy of five CO2 isotopologues of carbon dioxide in the 1.26-1.44 μm region (I): Line positions

The absorption spectrum of highly enriched ¹³C carbon dioxide has been investigated by CW-Cavity Ring Down Spectroscopy with a setup based on fibered distributed feedback (DFB) laser diodes. By using a series of 30 DFB lasers, the CO₂ spectrum was recorded in the 7029-7917 cm⁻¹ region with a typical sensitivity of 3×10⁻¹⁰ cm⁻¹. The uncertainty on the determined line positions is on the order of 8×10⁻⁴ cm⁻¹. More than 3800 transitions with intensities as low as 1×10⁻²⁹ cm/molecule were detected and assigned to the ¹³C¹⁶O₂, ¹⁶O¹³C¹⁷O, ¹⁶O¹³C¹⁸O, ¹⁷O¹³C¹⁸O and ¹³C¹⁸O₂ isotopologues. For comparison, only 104 line positions of ¹³C¹⁶O₂ were previously reported in the literature in the considered region. The band-by-band analysis has led to the determination of the rovibrational parameters of a total of 83 bands including 56 bands of the ¹³C¹⁶O₂ species. The measured line positions of ¹³C¹⁶O₂ and ¹⁶O¹³C¹⁸O were found in good agreement with the predictions of the respective effective Hamiltonian (EH) models but the agreement degrades for the minor isotopologues. Several cases of resonance interactions were found and discussed. In the 20033-10002 band of ¹³C¹⁶O₂, an anharmonic resonance interaction leads to deviations on the order of 0.05 cm⁻¹ compared to the EH predictions. The existence of interpolyad interactions affecting the non-symmetric isotopologues of carbon dioxide is confirmed by the observation of two occurrences in ¹⁶O¹³C¹⁷O and ¹⁶O¹³C¹⁸O. The obtained results improve significantly the knowledge of the spectroscopy of the ¹³C isotopologues of carbon dioxide. They will be valuable to refine the sets of effective Hamiltonian parameters used to generate the CDSD database.     

High sensitivity CW-cavity ring down spectroscopy of CO2 near 1.35 μm (II): New observations and line intensities modeling

In a previous contribution [Kassi S, Song KF, Campargue A. High sensitivity CW-cavity ring down spectroscopy of ¹²CO₂ near 1.35 μm (I): line positions. JQSRT 110 (2009) 1801-1814], the line positions analysis of the high sensitivity absorption spectrum of carbon dioxide has been reported in the 7123-7793 cm⁻¹ region. In this second contribution, the spectral region investigated by CW-cavity ring down spectroscopy has been extended up to 7917 cm⁻¹. It added about 400 lines to our previous list of about 2500 transitions. These additional lines include transitions belonging to six newly observed ¹²C¹⁶O₂ bands for which we provide the spectroscopic parameters. Over the whole 7123-7917 cm⁻¹ region, the accurate intensities of about 2900 lines belonging to four isotopologues (¹²C¹⁶O₂, ¹³C¹⁶O₂, ¹⁶O¹²C¹⁸O and ¹⁶O¹²C¹⁷O) were retrieved with an average accuracy of 3%. Intensity values range between 1.2×10⁻²⁹ and 4.1×10⁻²⁵ cm/mol. Compared to the present version of the carbon dioxide spectroscopic databank recently adopted for the HITRAN database, important deviations were evidenced for some weak bands of the main isotopologue. The CW-CRDS intensity data relative to a total of 46 ¹²C¹⁶O₂ bands together with selected intensity information available in the literature for nine bands have been fitted simultaneously using the effective operators approach. The ΔP=11 set of the ¹²C¹⁶O₂ effective dipole moment parameters has been refined leading to a much better agreement with the measured intensity values. In addition, the ΔP=10 effective dipole moment parameters of the ¹⁶O¹²C¹⁸O minor isotopologue were determined for the first time. The obtained results will help to improve the carbon dioxide spectroscopic databank (CDSD).     

Near infrared spectroscopy of carbon dioxide. II: OCO and OCO line positions

High-resolution near-infrared (4000-8500 cm⁻¹) spectra of ¹³C-enriched carbon dioxide have been recorded using the McMath-Pierce Fourier transform spectrometer at the Kitt Peak National Solar Observatory. We observed over 1000 line positions for the ¹⁶O¹³C¹⁶O isotopologue, the majority of which have previously been observed only in spectra of the Venusian atmosphere [J. Mol. Spectrosc. 67 (1977) 304]. These have been analyzed to determine spectroscopic constants for 28 different vibrational states. The analysis yielded RMS fitting residuals <1.5 × 10⁻⁴ cm⁻¹ for the strongest bands and RMS residuals <5 × 10⁻⁴ cm⁻¹ for most other fitted bands. A 5% ¹⁸O-enrichment in the sample enabled us to observe 410 line positions from 5 near-infrared vibrational bands of the ¹⁶O¹³C¹⁸O isotopologue. Analysis of the ¹⁶O¹³C¹⁸O bands yielded RMS fitting residuals <2 × 10⁻⁴ cm⁻¹. Additionally, the first fits for the ¹⁶O¹³C¹⁸O 11101 ← 01101 and 11102 ← 01101 hot bands yielded RMS residuals of 2.3 × 10⁻⁴ and 2.2 × 10⁻⁴ cm⁻¹, respectively. Critical reevaluations of the spectroscopic constants for the low lying vibrational states for both isotopologues have been performed as part of the analysis.     

Diode laser absorption spectrum of cold bands of C2HD at 6500 cm

The absorption spectrum of acetylene-d has been observed at high resolution between 6470 and 6630 cm⁻¹ using an external cavity diode laser. Three cold bands have been observed: the strong 2ν₁ band, the weaker ν₁ + ν₂ + 2ν₅ band, and the (ν₁ + ν₃ + ν₅)¹ band, which gains its intensity through Coriolis resonance with 2ν₁. Centers of unblended lines are determined with an accuracy of approximately 10 MHz.     

CW-cavity ringdown spectroscopy of carbon dioxide isotopologues near 1.5 μm

The absorption spectra of carbon dioxide in natural isotopic abundance and with 99% enrichment in ¹³C have been recorded by CW-cavity ringdown spectroscopy in two specific spectral regions: 5957-6122 and 6745-6833 cm⁻¹. The spectra were obtained at Doppler limited resolution by using a CW-CRDS spectrometer based on fibered DFB lasers. The typical sensitivity of 5 × 10⁻¹⁰ cm⁻¹, allowed for the detection of lines with intensity as weak as 5 × 10⁻²⁹ cm/molecule. More than 2900 line positions of the six major isotopologues contributing to the spectra (¹²C¹⁶O₂, ¹⁶O¹²C¹⁷O, ¹⁶O¹²C¹⁸O, ¹³C¹⁶O₂, ¹⁶O¹³C¹⁷O and ¹⁶O¹³C¹⁸O), were measured and assigned on the basis of their respective global effective Hamiltonian models. For comparison, only 507 lines are provided by the HITRAN database in these spectral regions. The band by band analysis has led to the determination of the rovibrational parameters of a total of 52 bands, 30 of them being newly reported. Most of the observed line positions show an agreement close to the experimental uncertainty (1-2 × 10⁻³ cm⁻¹) with the predictions of their respective effective Hamiltonian models. However, the quality of the predictions degrades for the minor isotopologues reaching maximum deviations of 0.35 cm⁻¹ in one specific case. For several bands, rovibrational transitions with J values between 60 and 90 could be newly detected. While an excellent agreement is observed with the line positions predicted by the Hamiltonian models, the comparison of these observations with the line positions listed in the HITRAN database or extrapolated by using the best FTS rotational constants available in the literature has evidenced significant deviations.     

High sensitivity cw-cavity ringdown and Fourier transform absorption spectroscopies of CO2

The absorption spectrum of ¹³CO₂ has been recorded by cw-cavity ringdown spectroscopy with a new set up based on fibered DFB lasers. By using a series of 31 DFB lasers, the spectrum of carbon dioxide could be recorded in the 6130-6750 cm⁻¹ region with a typical sensitivity of 5 × 10⁻¹⁰ cm⁻¹. The spectrum has also been recorded between 4400 and 8500 cm⁻¹ with a Fourier transform spectrometer associated with a multi-pass cell (maximum path length of 105 m). The new observations obtained both by FTS and CRDS represent a significant extension of the available data. For instance, more than 4000 line positions were measured and assigned in the CRDS spectrum while only 232 line positions are listed in the HITRAN database. Altogether, the band by band analysis has led to the determination of the rovibrational parameters of 65, 7, and 24 bands for the ¹³C¹⁶O₂, ¹⁶O¹³C¹⁷O, and ¹⁶O¹³C¹⁸O isotopomers, respectively. As some observed line positions show significant deviations from the predictions of the effective Hamiltonian model, the new observed line positions were gathered with the data available in the literature to refine the set of effective Hamiltonian parameters of the ¹³C¹⁶O₂ isotopic species. The refined set of 96 effective Hamiltonian parameters reproduces more than 14 650 line positions of ¹³C¹⁶O₂ with an RMS=0.002 cm⁻¹. A detailed comparison with the line positions retrieved from Venus spectra and the line list provided by HITRAN is also presented and discussed.