Complete Line List Research Articles

Corrigendum to “Line parameters measurements and modeling for the ν6 band of CH3F: Generation of a complete line list for atmospheric databases”

Corrigendum to “Line parameters measurements and modeling for the ν6 band of CH3F: Generation of a complete line list for atmospheric databases”

Structure, spectroscopic signatures, and formation of hydroxy-azirine: a potential interstellar prebiotic molecule

ABSTRACT Hydroxy-azirine (C2H3NO) is a -OH derivative of azirine (C2H3N), molecule that has been the subject of several unfruitful searches in space. Hydroxy-azirine is an isomer of the detected prebiotic species methyl isocyanate, CH3NCO, and glycolonitrile, HOCH2CN, as well as the yet undetected imine acetaldehyde, NHCHCHO. However, the lack of preliminary spectroscopic data on hydroxy-azirine has prevented its astronomical search. The aim of this study is to provide high-level theoretical spectroscopic signatures of the most stable hydroxy-azirine isomers to enable their eventual interstellar search. A total of 12 isomers have been characterized for hydroxy-azirine and their isomerization processes have been analysed at the CCSD(T)-F12/cc-pVTZ-F12 level. The most stable structures are 3-hydroxy-2H-azirine (I) and 2-hydroxy-2H-azirine (II) in their syn- and anti-configurations, which are suggested as the most relevant candidates for laboratory and interstellar detection. To ease their identification by means of rotational spectroscopy, we report a set of the required spectroscopic parameters using state-of-the-art composite and coupled-cluster approaches. For astronomical purposes, we provide a complete line list for I-syn and I-antihydroxy-azirine up to 50 GHz, which takes the hyperfine structure into account, and will be essential to hunt for these interstellar candidates experimentally. In addition, anharmonic vibrational frequencies and intensities are reported to predict a trustworthy vibrational spectra and to estimate the vibrational partition function. Finally, we analyse the possibility of formation of hydroxy-azirine from the reaction of azirine with the hydroxyl radical in the gas-phase and on the surface of ices, finding for the latter a feasible formation route under interstellar conditions.

Temperature dependence of the absorption of the R(6) manifold of the 2ν3 band of methane in air in support of the MERLIN mission

Fifty nine high sensitivity spectra of the R(6) manifold of the 2ν3 band of methane in air, near 1.64 µm, have been recorded in support of the MERLIN mission. For this purpose, a cavity ring down spectrometer (CRDS) with a spectrally narrowed and stable (sub-kHz) laser source was coupled to a temperature regulated high-finesse optical cavity. The frequency scale of each spectrum was accurately determined from measurements of the beat note between a part of the laser light and the closest tooth of a frequency comb referenced to a rubidium clock. Series of spectra were recorded between 243 and 313 K with a 10 K temperature step. For each series, total pressure values of 50, 100, 250, 500 and 750 Torr were adopted. A multi-spectrum fitting procedure with the Hartmann-Tran (HT) line profile, including the first-order line-mixing parameter, has been used to derive the spectroscopic parameters for each of the six R(6) components, along with the temperature dependence of the line-shape parameters. The results show that the fitted effective model is able to reproduce the experimental spectra with a relative precision better than 0.2% for the entire R(6) manifold spectral region and better than 0.05% at the ON-line position of the MERLIN mission for the 250, 500 and 750 Torr spectra. The relative precision increases to 0.3% and the residuals at the ON-line position to 0.1% when including the 50 and 100 Torr spectra. Comparisons with ground-based atmospheric measurements show that these data significantly improve the modeling of methane absorption in this spectral region. The complete line list of the methane spectrum in the region of the R(6) manifold allowing notable improvement of the modeling of the absorption cross-section at the ON-line position of the MERLIN mission is provided as Supplementary Material.

A quantitative assessment of the VO line list: Inaccuracies hamper high-resolution VO detections in exoplanet atmospheres

Context.Metal hydrides and oxides are important species in hot-Jupiters since they can affect their energy budgets and the thermal structure of their atmospheres. One such species is vanadium-oxide (VO), which is prominent in stellar M-dwarf spectra. Evidence for VO has been found in the low-resolution transmission spectrum of WASP-121b, but this has not been confirmed at high resolution. It has been suggested that this is due to inaccuracies in its line list.Aims.In this paper, we quantitatively evaluate the VO line list and assess whether inaccuracies are indeed the reason for the non-detections at high resolution in WASP-121b. Furthermore, we investigate whether the detectability can be improved by selecting only those lines associated with the most accurate quantum transitions.Methods.A cross-correlation analysis was applied to archival High Accuracy Radial velocity Planet Searcher and CARMENES spectra of several M-dwarfs. VO cross-correlation signals from the spectra were compared with those in which synthetic VO models were injected, providing an estimate of the ratio between the potential strength (in case of a perfect model) and the observed strength of the signal. This was repeated for the reduced model covering the most accurate quantum transitions. The findings were subsequently fed into injection and recovery tests of VO in a Ultraviolet and Visual Echelle Spectrograph transmission spectrum of WASP-121b.Results.We find that inaccuracies cause cross-correlation signals from VO in M-dwarf spectra to be suppressed by about a factor 2.1 and 1.1 for the complete and reduced line lists, respectively, corresponding to a reduced observing efficiency of a factor 4.3 and 1.2. The reduced line list outperforms the complete line list in recovering the actual VO signal in the M-dwarf spectra by about a factor of 1.8. Neither line list results in a VO detection in WASP-121b. Injection tests show that with the reduced efficiency of the line lists, the potential signal as seen at low resolution is not detectable in these data.

Line lists for the b1Σ+-X3Σ− and a1Δ-X3Σ− transitions of SO

SO is found in many astronomical sources such as the atmospheres of Io and Venus. In order to create more complete line lists, we fit spectroscopic data on SO from the literature using PGOPHER. The fits covered v = 0 to v = 6 for the X3Σ−state, v = 0–5 for the a1Δ state and v = 0–2 for b1Σ+ state. LeRoy's RKR program was used to produce pointwise potential energy curves. High level ab initio calculations, including spin-orbit coupling, were carried out to obtain the electric transition dipole moment functions for the nominally forbidden b1Σ+-X3Σ−and a1Δ-X3Σ−transitions. The RKR potentials and transition dipole moment points were input into LeRoy's LEVEL program to calculate the transition dipole matrix elements for all possible b-X and a-X bands. For the b1Σ+-X3Σ−transition, the electric and magnetic transition dipole matrix elements were scaled using the experimental values obtained by Setzer et al. [J Mol Spectrosc 1999;198:163–174] for the 0–0 band. The transition dipole moment matrix elements were used in PGOPHER to produce our line lists for all possible bands of the b1Σ+-X3Σ−and a1Δ-X3Σ−transitions.

An experimentally-accurate and complete room-temperature infrared HCN line-list for the HITRAN database

A hydrogen cyanide line list (MOMeNT-90) developed for the HITRAN spectroscopic database covering 0–7500 cm−1 range (λ>1330 nm) is presented. The line list is a combination of the variationally calculated line intensities with line centers obtained from experimentally derived energy levels. There are four features of this line list which distinguishes it from the previously calculated ones. First, the intensities are variationally calculated using a new, high-accuracy potential energy surface (PES) obtained via fitting the PES using experimental energy levels. Second, a new ab initio dipole moment surface was calculated at a high level of quantum chemical theory. Based on the wave functions calculated with the new PES and use of the new dipole moment surface, line intensities are reported which of similar accuracy to those obtained experimentally. Third, the calculated states are mapped to the existing complete set of experimental eigenenergies, resulting in an assigned and complete HCN line list down to the HITRAN intensity threshold of 10−34 cm/molecule. Fourth, extensive validation of the line list is provided through line-by-line comparisons of the results with measured HCN spectra which confirms the accuracy of the intensities used to construct the line list. The line list is augmented with parameters needed to calculate line widths for pressure-dependent simulations.

PLATON II: New Capabilities and a Comprehensive Retrieval on HD 189733b Transit and Eclipse Data

Abstract Recently, we introduced PLanetary Atmospheric Tool for Observer Noobs (PLATON), a Python package that calculates model transmission spectra for exoplanets and retrieves atmospheric characteristics based on observed spectra. We now expand its capabilities to include the ability to compute secondary eclipse depths. We have also added the option to calculate models using the correlated-k method for radiative transfer, which improves accuracy without sacrificing speed. Additionally, we update the opacities in PLATON—many of which were generated using old or proprietary line lists—using the most recent and complete public line lists. These opacities are made available at R = 1000 and R = 10,000 over the 0.3–30 μm range, and at R = 375,000 in select near-IR bands, making it possible to utilize PLATON for ground-based high-resolution cross-correlation studies. To demonstrate PLATON’s new capabilities, we perform a retrieval on published Hubble Space Telescope (HST) and Spitzer transmission and emission spectra of the archetypal hot Jupiter HD 189733b. This is the first joint transit and secondary eclipse retrieval for this planet in the literature, as well as the most comprehensive set of both transit and eclipse data assembled for a retrieval to date. We find that these high signal-to-noise data are well matched by atmosphere models with a C/O ratio of and a metallicity of times solar where the terminator is dominated by extended nanometer-sized haze particles at optical wavelengths. These are among the smallest uncertainties reported to date for an exoplanet, demonstrating both the power and the limitations of HST and Spitzer exoplanet observations.

ExoMol molecular line lists – XXXVII. Spectra of acetylene

ABSTRACT A new ro-vibrational line list for the ground electronic state of the main isotopologue of acetylene, 12C2H2, is computed as part of the ExoMol project. The aCeTY line list covers the transition wavenumbers up to 10 000 cm−1 (λ > 1 $\mu$m), with lower and upper energy levels up to 12 000 and 22 000 cm−1 considered, respectively. The calculations are performed up to a maximum value for the vibrational angular momentum, Kmax = Lmax = 16, and maximum rotational angular momentum, J = 99. Higher values of J were not within the specified wavenumber window. The aCeTY line list is considered to be complete up to 2200 K, making it suitable for use in characterizing high-temperature exoplanet or cool stellar atmospheres. Einstein-A coefficients, which can directly be used to calculate intensities at a particular temperature, are computed for 4.3 billion (4 347 381 911) transitions between 5 million (5 160 803) energy levels. We make comparisons against other available data for 12C2H2, and demonstrate this to be the most complete line list available. The line list is available in electronic form from the online CDS and ExoMol data bases.

Line parameters measurements and modeling for the ν6 band of CH3I: A complete line list for atmospheric databases

The present work is dedicated to the ν6 band of 12CH3I with the aim of generating a complete line list for databases. High resolution Fourier transform spectra have been recorded in MONARIS and a multispectrum fitting procedure using Voigt profile has been applied to retrieve line positions, intensities, and self-broadening coefficients for around 1200 transitions of the ν6 band between 854 and 963 cm−1. Rotational dependences of transition dipole moment squared and self-widths have been studied and empirically modeled. Line positions are retrieved with accuracy equal to 4.10−4 cm−1. The accuracy of line intensities and self-widths measurements is estimated between 5 and 10 %. Theoretical estimates of CH3I self-broadening coefficients for large ranges of rotational quantum numbers (0 ≤ J ≤ 70, 0 ≤ K ≤ 20) are also provided in the frame of a semi-classical approach with exact trajectories and of a semi-empirical method including a correction factor to the Anderson-type line-width expression. Comparisons of our results with the data previously published in the literature are presented and discussed. A complete line list of 5787 transitions is generated. Available as supplementary material, this line list can be used for spectroscopic databases and atmospheric or industrial detection of CH3I.

An Algorithm to Compress Line-transition Data for Radiative-transfer Calculations

Abstract Molecular line-transition lists are an essential ingredient for radiative-transfer calculations. With recent databases now surpassing the billion-line mark, handling them has become computationally prohibitive, due to both the required processing power and memory. Here I present a temperature-dependent algorithm to separate strong from weak line transitions, reformatting the large majority of the weaker lines into a cross-section data file, and retaining the detailed line-by-line information of the fewer strong lines. For any given molecule over the 0.3–30 μm range, this algorithm reduces the number of lines to a few million, enabling faster radiative-transfer computations without a significant loss of information. The final compression rate depends on how densely populated the spectrum is. I validate this algorithm by comparing Exomol’s HCN extinction-coefficient spectra between the complete (65 million line transitions) and compressed (7.7 million) line lists. Over the 0.6–33 μm range, the average difference between extinction-coefficient values is less than 1%. A Python/C implementation of this algorithm is open-source and available at https://github.com/pcubillos/repack. So far, this code handles the Exomol and HITRAN line-transition format.

Accurate Theoretical Methane Line Lists in the Infrared up to 3000 K and Quasi-continuum Absorption/Emission Modeling for Astrophysical Applications

Abstract Modeling atmospheres of hot exoplanets and brown dwarfs requires high-T databases that include methane as the major hydrocarbon. We report a complete theoretical line list of 12CH4 in the infrared range 0–13,400 cm−1 up to T max = 3000 K computed via a full quantum-mechanical method from ab initio potential energy and dipole moment surfaces. Over 150 billion transitions were generated with the lower rovibrational energy cutoff 33,000 cm−1 and intensity cutoff down to 10−33 cm/molecule to ensure convergent opacity predictions. Empirical corrections for 3.7 million of the strongest transitions permitted line position accuracies of 0.001–0.01 cm−1. Full data are partitioned into two sets. “Light lists” contain strong and medium transitions necessary for an accurate description of sharp features in absorption/emission spectra. For a fast and efficient modeling of quasi-continuum cross sections, billions of tiny lines are compressed in “super-line” libraries according to Rey et al. These combined data will be freely accessible via the TheoReTS information system (http://theorets.univ-reims.fr, http://theorets.tsu.ru), which provides a user-friendly interface for simulations of absorption coefficients, cross-sectional transmittance, and radiance. Comparisons with cold, room, and high-T experimental data show that the data reported here represent the first global theoretical methane lists suitable for high-resolution astrophysical applications.

Complete spectral energy distribution of the hot, helium-rich white dwarf RX J0503.9–2854

In the line-of-sight toward the DO-type white dwarf RX J0503.9-2854, the density of the interstellar medium (ISM) is very low, and thus the contamination of the stellar spectrum almost negligible. This allows us to identify many metal lines in a wide wavelength range from the extreme ultraviolet to the near infrared. In previous spectral analyses, many metal lines in the ultraviolet spectrum of RX J0503.9-2854 have been identified. A complete line list of observed and identified lines is presented here. We compared synthetic spectra that had been calculated from model atmospheres in non-local thermodynamical equilibrium, with observations. In total, we identified 1272 lines (279 of them were newly assigned) in the wavelength range from the extreme ultraviolet to the near infrared. 287 lines remain unidentified. A close inspection of the EUV shows that still no good fit to the observed shape of the stellar continuum flux can be achieved although He, C, N, O, Al, Si, P, S, Ca, Sc, Ti, V, Cr, Mn, Fe, Cr, Ni Zn, Ga, Ge, As, Kr, Zr, Mo, Sn, Xe, and Ba are included in the stellar atmosphere models. There are two possible reasons for the deviation between observed and synthetic flux in the EUV. Opacities from hitherto unconsidered elements in the model-atmosphere calculation may be missing and/or the effective temperature is slightly lower than previously determined.

Geospatial Techniques in Health Survey to Overcome the Lack of Sampling Frame

Sampling frame is a complete list of items or population from which a sample is drawn. More often researchers face difficulties in getting an up to date line list of sampling units, especially in the field where rapid changes are frequent. In household surveys it is difficult as newly constructed houses are seen as a continuous process in urban as well as rural areas. To overcome this issue, in this paper, we proposed a novel method by using Google-Earth with the GIS technologies. A study was done with the primary objective to identify the health impact of people living in and around quarries/crusher units at Thiruneermalai region nearer to Chennai. Since the boundary of the study area is found to be radial, it was difficult in getting the complete line list of the people living within the required radius. To overcome the issue the entire region was divided into small 30 x 30 meter grid cells. A total of 43652 sampling units (grid cells) formed the sampling frame. Among them, the required sample size was selected for the study. This method of GIS based grid sampling serve as an alternate tool for developing sampling frame with no or least cost.

Small Molecules-Big Data.

Quantum mechanics builds large-scale graphs (networks): the vertices are the discrete energy levels the quantum system possesses, and the edges are the (quantum-mechanically allowed) transitions. Parts of the complete quantum mechanical networks can be probed experimentally via high-resolution, energy-resolved spectroscopic techniques. The complete rovibronic line list information for a given molecule can only be obtained through sophisticated quantum-chemical computations. Experiments as well as computations yield what we call spectroscopic networks (SN). First-principles SNs of even small, three to five atomic molecules can be huge, qualifying for the big data description. Besides helping to interpret high-resolution spectra, the network-theoretical view offers several ideas for improving the accuracy and robustness of the increasingly important information systems containing line-by-line spectroscopic data. For example, the smallest number of measurements necessary to perform to obtain the complete list of energy levels is given by the minimum-weight spanning tree of the SN and network clustering studies may call attention to "weakest links" of a spectroscopic database. A present-day application of spectroscopic networks is within the MARVEL (Measured Active Rotational-Vibrational Energy Levels) approach, whereby the transitions information on a measured SN is turned into experimental energy levels via a weighted linear least-squares refinement. MARVEL has been used successfully for 15 molecules and allowed to validate most of the transitions measured and come up with energy levels with well-defined and realistic uncertainties. Accurate knowledge of the energy levels with computed transition intensities allows the realistic prediction of spectra under many different circumstances, e.g., for widely different temperatures. Detailed knowledge of the energy level structure of a molecule coming from a MARVEL analysis is important for a considerable number of modeling efforts in chemistry, physics, and engineering.

First theoretical global line lists of ethylene (12C2H4) spectra for the temperature range 50−700 K in the far-infrared for quantification of absorption and emission in planetary atmospheres

We present the construction of complete and comprehensive ethylene line lists for the temperatures 50−700 K based on accurate ab initio potential and dipole moment surfaces and extensive first-principle calculations. Three lists spanning the [0−6400] cm-1 infrared region were built at T = 80, 160, and 296 K, and two lists in the range [0−5200] cm-1 were built at 500 and 700 K. For each of these five temperatures, we considered possible convergence problems to ensure reliable opacity calculations. Our final list at 700 K was computed up to J = 71 and contains almost 60 million lines for intensities I > 5 × 10-27 cm/molecule. Comparisons with experimental spectra carried out in this study showed that for the most active infrared bands, the accuracy of band centers in our theoretical lists is better on average than 0.3 cm-1, and the integrated absorbance errors in the intervals relevant for spectral analyses are about 1−3%. These lists can be applied to simulations of absorption and emission spectra, radiative and non-LTE processes, and opacity calculations for planetary and astrophysical applications.

Line parameters measurements and modeling for the ν6 band of CH3F: Generation of a complete line list for atmospheric databases

The 8.5µm-spectral region of methyl fluoride was studied in terms of line positions, intensities and self-broadening coefficients at room temperature. A multispectrum fitting was used to retrieve from 7 high-resolution Fourier transform spectra line parameters for 787 transitions belonging to the ν6 band between 1078 and 1240cm−1. The accuracy of line intensities and widths measurements were estimated to be around 5% and 5–10% respectively. J- and K-rotational dependences of the transition dipole moment squared and the self-broadening coefficients were observed and modeled from the measurements. A complete line list of almost 1500 transitions was generated for atmospheric or industrial detection of CH3F. Comparisons with previous studies from the literature were also performed.

Accurate dipole moment curve and non-adiabatic effects on the high resolution spectroscopic properties of the LiH molecule

A very accurate dipole moment curve (DMC) for the ground X1Σ+ electronic state of the 7LiH molecule is reported. It is calculated with the use of all-particle explicitly correlated Gaussian functions with shifted centers. The DMC – the most accurate to our knowledge – and the corresponding highly accurate potential energy curve are used to calculate the transition energies, the transition dipole moments, and the Einstein coefficients for the rovibrational transitions with ΔJ=-1 and Δv⩽5. The importance of the non-adiabatic effects in determining these properties is evaluated using the model of a vibrational R-dependent effective reduced mass in the rovibrational calculations introduced earlier (Diniz et al., 2015). The results of the present calculations are used to assess the quality of the two complete linelists of 7LiH available in the literature.

THz extended spectrum of the monodeuterated methyl formate (DCOOCH3)

Context. Laboratory spectral recordings and an accurate molecular spectral analysis of any potential interstellar molecule are essential for generating a complete spectroscopic line list. This permits predicting the frequencies and intensities of any transition so that subsequently, it can be identified in the interstellar medium. Aims. Our analysis of DCOOCH3 aims to provide a comprehensive spectral catalog that encompasses as much as possible the frequency coverage of the new-generation far-IR and submillimeter wave observation facilities. Methods. We newly measured the rotational spectrum of DCOOCH3 in the laboratory of the Jet Propulsion Laboratory in the frequency range of 0.85 to 1.5 THz. We jointly analyzed the new data with literature data using the rho axis method, which is a tool developed for the spectral analysis of molecules with large-amplitude internal CH3 rotors. Results. We fit 27 spectroscopic constants of DCOOCH3 to 3763 transitions with highest values of J = 69 and Ka = 36 of the ground torsional state with a standard (unitless) deviation of 0.97. With respect to previous work, this is a significantly better result that was obtained with 2060 more transitions, and we also achieved a better accuracy for the new parameter values.

The methane mole fraction in Titan’s stratosphere from DISR measurements during the Huygens probe’s descent

We present a determination of the methane mole fraction in Titan’s stratosphere using spectral measurements by the Upward Looking Infrared Spectrometer (ULIS) of the Descent Imager/Spectral Radiometer (DISR) aboard the Huygens probe. We analyzed the 1.4-μm band of methane for which a complete linelist, down to very low intensities, was recently made available. The DISR/ULIS measurements were used to derive the methane transmittance along the path from the probe to the Sun during the descent from 135 to 29km. Fitting the transmittance ratios to remove residual instrumental effects, we derived a stratospheric methane mole fraction of 1.44 (+0.27/−0.11)%, taking into account random errors and uncertainties in the spectroscopic parameters. This value is fully consistent with the simultaneous measurement of the methane profile by the Huygens Gas Chromatograph/Mass Spectrometer (GCMS). It disagrees with the ∼1% mixing ratio recently inferred from Cassini/CIRS spectra at low latitudes near 85km. Possible reasons for the discrepancy and uncertainties in the methane spectroscopic parameters are discussed.

An accurate and complete empirical line list for water vapor between 5850 and 7920 cm−1

An empirical line list has been constructed for “natural” water vapor at 296K in the 5850–7920cm−1 region. It was obtained by gathering separate line lists recently published on the basis of spectra recorded by high sensitivity Continuous Wave Cavity Ring Down Spectroscopy (CW-CRDS) of natural water, complemented with literature data for the strongest lines. The list includes 38,318 transitions of four major water isotopologues (H216O, H218O, H217O and HD16O) with an intensity cut-off of 1×10−29cm/molecule at 296K. The list is made mostly complete over the whole spectral region by including a large number of weak lines with positions calculated using experimentally determined energy levels and intensities obtained from variational calculations. In addition, we provide HD18O and HD17O lists in the same region for transitions with intensities larger than 1×10−29cm/molecule. The HD18O and HD17O lists (1972 lines in total) were obtained using empirical energy levels available in the literature and variational intensities.The global list (40,290 transitions) for water including the contribution of the six major isotopologues will be adopted for the next edition of the GEISA database in the region.The advantages and drawbacks of our list are discussed in comparison with the list provided for the same region in the 2012 edition of the HITRAN database. The direct comparison of the CRDS spectra to simulations based on the HITRAN list has revealed some insufficiencies which could easily be corrected: missing HDO lines, duplicated lines, inaccurate line positions or line intensities from variational calculations.