The water vapor continuum absorption is studied in a spectral range covering most of the pure rotational spectrum of water molecule up to 500 cm⁻¹. The continuum absorption was derived from the broad band water vapor spectra recorded by Fourier transform spectrometer equipped with the 151-m multipass gas cell at the AILES beam line of the SOLEIL synchrotron. The coherent (10-35 cm⁻¹) and standard (40-500 cm⁻¹) radiation modes of the synchrotron were used. In order to refine the magnitude and clarify the physical origin of the continuum, spectra of the two major water isotopologues, H₂¹⁶O and H₂¹⁸O, were considered. Recordings at several water vapor pressures were used to check the expected quadratic pressure dependence of the continuum.

The new data extend and supplement previous measurements filling, in particular, the gap between 200 and 350 cm⁻¹, which was never studied before. The H₂¹⁶O and H₂¹⁸O absorption continua in the range of 50-650 cm⁻¹ show similar frequency dependence and magnitude. In particular, both continua exhibit a clear water dimer spectral signature near 15 cm⁻¹, in good agreement with previous ab initio calculations. The present data confirm that the MT-CKD empirical continuum model widely used in atmospheric applications, overestimates importantly the continuum magnitude in the whole range of the rotational band. The observed irregular frequency dependence of the retrieved C_S values is tentatively interpreted as due to uncertainties on the resonance lines of the water monomer spectrum which is subtracted from the recorded spectra. On the basis of spectra simulations, the inadequate description of the line shapes in the range of the intermediate wings (detuning of 5-10 cm⁻¹ from line center) and the uncertainties on the self-broadening coefficients of water monomer lines are identified as possible mechanisms responsible of the observed irregular fluctuations.

The absorption spectra of the mixture of SO₂ and CO₂ at different partial pressures of both gases have been recorded at room temperature in the 4 µm region using the Bruker IFS 125 HR FTIR spectrometer. The multispectrum fitting procedure has been applied to these spectra to recover the CO₂-broadening and shift parameters of the sulfur dioxide spectral lines. The CO₂ broadening and the pressure induced shift coefficients for 1422 and 116 lines of the ν₁ + ν₃ A-type band of ³²S¹⁶O₂ and ³⁴S¹⁶O₂, respectively, have been derived. Beside, these coefficients have been derived for 254 lines of the ν₁ + ν₂ + ν₃ − ν₂ hot band of ³²S¹⁶O₂. The rotational dependence of the values of these coefficients is discussed. The CO₂ pressure induced shift coefficients for this molecule are published for the first time. The comparison of the obtained broadening coefficients to those published by other authors for one pure rotational line and for the lines of the ν₁ B-type band is given.

The quality of Ames-296K SO₂ Infrared (IR) line list intensities is first validated by quantitative exploration of several dipole moment surfaces (DMSs) and partition sum convergence. The DMSs are computed with several of Dunning's correlation-consistent basis sets and their vibrational dependence are compared to the empirical model derived from Stark effect experiments reported by D. Patel, D. Margolese, and T.R. Dyke [J. Chem. Phys. 70, 2740 (1979)]. The effective dipole deviations from the DMS adopted in the Ames IR lists is 0.2–0.4% for vibrational states up to 3ν₃. The vibrational dependence of the dipole moment is also in good agreement, except for nν₁. Partition sum convergence at 296 K is confirmed by new calculations with rotational quantum number J up to 150 and upper state E’ up to 8000 cm⁻¹. The isotopologue consistency of the Ames IR line lists is superior relative to the regular Effective Hamiltonian (EH) models and Effective Dipole Moment (EDM) models. The ν₁+ ν₂ and ν₂+ ν₃ intensity consistency check reveals the recently reported experimental intensities need significant improvement or re-analysis. After the accuracy, convergence, and isotopologue consistency have been confirmed, the theoretical Ames-296K intensities are combined with the experimental line positions or EH models that experimental spectroscopists published after 2009. Three high-resolution IR line sets are reported for the ^32/33/34S¹⁶O₂, ³²S¹⁸O₂ and ¹⁶O³²S¹⁸O isotopologues: (1) the “New Lines Sets” include experimentally measured line positions; (2) the “Expanded Line Sets” include possible transitions among new rovibrational levels assigned in experiments and ground state (GS) levels predicted by reliable EH models; (3) the “Ames + MARVEL Sets” include possible transitions among all those levels reported in a recent MARVEL analysis. [Tóbiás et al, JQSRT 208, 152 (2018)]. Compared to the limited data in High-resolution TRANsmission molecular absorption database (HITRAN), these line sets have significantly improved the data coverage up to 4000 cm⁻¹. Some missing bands can be traced to the unpublished experimental data. The isotopologue consistency of these line sets will help identify the uncertainties and defects in the experimental EH and EDM models. These line sets are good candidates for the next HITRAN update, if line shape parameters are available. The line sets can be downloaded from supplementary files or from the Ames Molecular Spectroscopic Database at http://huang.seti.org.

Рассмотрено качественное и количественное влияние на контур линии сильных и слабых по скоростям столкновений с рассеянием поглощающих молекул на большие и малые углы соответственно. Показано, что в диффузионной модели контура, известной как модель «слабых» столкновений, рассеяние на большие углы вносит существенный вклад, сопоставимый с таковым в модели сильных столкновений. Различие этих традиционных моделей заключается лишь в математических формах представления интеграла столкновений, интегральной и дифференциальной, и следующих из них аналитических выражений для контуров. Получены и апробированы простые приближенные формулы для контура, в котором одновременно учтены сильные и слабые столкновения.

This note provides a citable reference to a database reconciliation effort for ozone pure rotational intensities. The permanent dipole moment and theoretical adjustments for centrifugal distortion are utilized in a predictive calculation that is compared to experimental measurements. This prediction has been available in the JPL spectral line catalog since 2005, but has been at odds with the HITRAN database, which was originally based on an atlas provided by Flaud (HITRAN 1992) and subsequently scaled by 4% (HITRAN 2004). Using a modified partition function and isotopic abundance factor, the JPL 2005 prediction has now been utilized to create a self-consistent entry as an interim update to the HITRAN2016 database. Ramifications of the intensity change for users of HITRAN versions 2004–2012 are discussed. New pure rotational intensity measurements were carried out supporting the validity of the JPL 2005 database.

We present an experimental study of the absorption, between 40 and 640 cm⁻¹, by CO₂, CH₄ and H₂ gases as well as by H₂ + CO₂ and CH₄ + CO₂ mixtures at room temperature. A Fourier transform spectrometer associated to a multi-pass cell, whose optics were adjusted to obtain a 152 m path length, were used to record transmission spectra at total pressures up to about 0.98 bar. These measurements provide information concerning the collision-induced absorption (CIA) bands as well as about the wing of the CO₂ 15 µm band. Our results for the CIAs of pure gases are, within uncertainties, in agreement with previous determinations, validating our experimental and data analysis procedures. We then consider the CIAs by H₂ + CO₂ and CH₄ + CO₂ and the low frequency wing of the pure CO₂ 15 µm band, for which there are, to our knowledge, no previous measurements. We confirm experimentally the theoretical prediction of Wordsworth et al. (2017) that the H₂ + CO₂ and CH₄ + CO₂ CIAs are significantly stronger in the 50–550 cm⁻¹ region than those of H₂ + N₂ and CH₄ + N₂, respectively. However, we find that the shape and the strength of these recorded CIAs differ from the aforementioned predictions. For the pure CO₂ line-wings, we show that both the χ-factor deduced from measurements near 4 μm and a line-mixing model very well describe the observed strongly sub-Lorentzian behavior in the 500–600 cm⁻¹ region. These experimental results open renewed perspectives for studies of the past climate of Mars and extrasolar analogues.

We present the first results for resolving methane (CH4) line transition frequencies down to the kilohertz level for overlapping lines using comb-linked cavity ring-down spectroscopy, while most available laboratory measurements, having resolution at the megahertz level, cannot separate merged lines. To demonstrate the technique, Lamb-dip spectra and linear-absorption spectra were used to identify overlapped lines of vibration-rotation spectra in the R9 multiplet of the 2v3 band. Three new weak lines were found for the first time. The experimental methods are extensible to other important bands of CH4 and many other gas-phase molecules, and should provide a more detailed understanding of molecular structure and line parameters for future high-precision studies.

Semantic Web services (SWS) have been hailed for their role in realizing the potential of composing services in the context of service-oriented computing. However, many application domains, such as astrophysics, require a major rethinking of how service composition should take place despite his potential. In this paper, we describe an approach for automatic, user-friendly SWS composition for the astrophysics domain that features certain particularities like correlated or optional inputs, aggregates, and inclusion of non-Web services. The approach selects the best SWSs using non-functional requirements along with users’ previous experience feedback and is demonstrated using some real astrophysics services.

The high resolution infrared spectra of dideuterated hydrogen sulfide D₂S were recorded with a Bruker IFS 125HR Fourier transform infrared spectrometer (Zürich prototype ZP2001) and analyzed in the ν₂ fundamental band region, 750–1200 cm^-1. The 1742 transitions (which is more than two times more than in the preceding analogous studies) were assigned in the experimental spectra to the ν2 band (the maximum values of the quantum numbers are  J^max=30 and K^max_a=21). The subsequent weighted fit of experimentally assigned transitions was made with the Watson Hamiltonian, resulting in a set of 34 parameters which reproduces the initial 535 infrared ro–vibrational energy values from 1742 experimental line positions with a root mean square deviation d_rms=1.31*10^-4 cm^-1. An analysis of 280 experimental ro–vibrational line intensities (324 transitions) of the ν₂ band was made using the Hartmann–Tran profile of individual lines, and the results were applied then in the fit of parameters of the effective dipole moment operator. Isotopic relations for the dipole moment parameters were derived and used for the fit procedure. The obtained “model dependent” parameters reproduce the initial line strengths with the d_rms=2.5%. A list of 1742 experimental transitions of D₂S is generated together with the presentation of their individual line strengths calculated on the basis of the obtained effective dipole moment parameters.

Linestrengths, self-broadening and narrowing coefficients for 8 absorption transitions of CO₂ near 1.43 µm were measured using the wavelength modulation direct absorption spectroscopy (WM-DAS) at 300–1000 K and 5–20 kPa. The SNR was enhanced to 1500 for the peak absorbance around 5% at room temperature and remains at 550 for the peak absorbance around 1% at high temperatures by use of the WM-DAS method. The Voigt, Rautian, Galatry and quadratic speed-dependent Voigt profiles were used to recover the absorbance and retrieve the best-fit spectroscopic parameters and their temperature dependence. The quadratic speed-dependent Voigt profile was found to give the best combination of accuracy and robust lineshape parameters. The measured linestrengths and self-broadening coefficients compare well with the available values listed in the HITRAN/HITEMP database. The self-narrowing coefficients were also determined for GP, RP and qSDVP with analyses of the uncertainties in these spectroscopic parameters.

The IR absorption spectra of pure carbon dioxide in the region of the forbidden ν₂ + ν₃ vibrational transition at 3004 cm⁻¹ have been recorded using a Fourier-transform spectrometer. A multipass-optical cell with the path length of 100 m was used in the study. The data were taken at room temperature of 294.8 K with a resolution of 0.02 cm⁻¹ over the spectral region 2500–3500 cm⁻¹. A sample pressures varied from 207 to 463 kPa (2.04–4.57 atm). The measured binary absorption coefficients provide the band integrated intensity value of (2.39 ± 0.04) ∗ 10⁻⁴ cm⁻² amagat⁻². The result is compared with those from previous works. The observed band profile features are discussed.

The very weak absorption spectrum of the minor isotopologues of carbon dioxide near 1.74 µm (5702–5879 cm⁻¹) is studied by high sensitivity cavity ring down spectroscopy (CRDS) with an ¹⁸O enriched sample. The investigated spectral region corresponds to a transparency window of very weak opacity which is of particular interest for Venus. Very weak lines with intensity value as low as 10⁻³⁰ cm/molecule at 296 K are measured. On the basis of the predictions of the effective Hamiltonian models, 3202 lines of nine carbon dioxide isotopologues - ¹²C¹⁶O₂, ¹⁶O¹²C¹⁸O, ¹⁶O¹²C¹⁷O, ¹⁶O¹³C¹⁸O, ¹⁶O¹³C¹⁷O, ¹⁷O¹²C¹⁸O, ¹⁷O¹³C¹⁸O, ¹²C¹⁸O₂ and ¹³C¹⁸O₂ - were rovibrationnally assigned to 59 bands, 44 of which were observed for the first time. The accurate spectroscopic parameters of 53 bands are determined from standard band-by-band analysis (typical rms deviations of the line positions are 8 × 10⁻⁴ cm⁻¹). Three bands are found to be strongly perturbed by resonance first order Coriolis interaction. The new measured line intensities allowed determining or improving the ΔP = 8 sets of the effective dipole moment (EDM) parameters for five non-symmetrical isotopologues - ¹⁶O¹²C¹⁸O, ¹⁶O¹²C¹⁷O, ¹⁶O¹³C¹⁸O, ¹⁶O¹³C¹⁷O and ¹⁷O¹²C¹⁸O - and ΔP = 9 sets for the ¹⁶O¹²C¹⁸O and ¹²C¹⁸O₂ isotopologues (P = 2V₁+ V₂+ 3V₃ is the polyad number, V_i being the vibrational quantum numbers). The set of EDM parameters available for eleven isotopologues is used to discuss their isotopic dependence.

These newly observed bands provide critical validation tests for the most recent spectroscopic databases. The comparison to the Carbon Dioxide Spectroscopic Databank (CDSD-296), HITRAN2016 database and ab initio Ames line list is presented. Deficiency is evidenced for the weak 41104–00001 band of ¹⁶O¹²C¹⁸O in the HITRAN2016 list and identified as due to inaccurate CDSD intensities which were preferred to ab initio intensities.

The use of machine learning is becoming ubiquitous in astronomy^1–3, but remains rare in the study of the atmospheres of exoplanets. Given the spectrum of an exoplanetary atmosphere, a multi-parameter space is swept through in real time to find the best-fit model^4–6. Known as atmospheric retrieval, this technique originates in the Earth and planetary sciences⁷. Such methods are very time-consuming, and by necessity there is a compromise between physical and chemical realism and computational feasibility. Machine learning has previously been used to determine which molecules to include in the model, but the retrieval itself was still performed using standard methods8. Here, we report an adaptation of the ‘random forest’ method of supervised machine learning^9,10, trained on a precomputed grid of atmospheric models, which retrieves full posterior distributions of the abundances of molecules and the cloud opacity. The use of a precomputed grid allows a large part of the computational burden to be shifted offline. We demonstrate our technique on a transmission spectrum of the hot gas-giant exoplanet WASP-12b using a five-parameter model (temperature, a constant cloud opacity and the volume mixing ratios or relative abundances of molecules of water, ammonia and hydrogen cyanide)¹¹. We obtain results consistent with the standard nested-sampling retrieval method. We also estimate the sensitivity of the measured spectrum to the model parameters, and we are able to quantify the information content of the spectrum. Our method can be straightforwardly applied using more sophisticated atmospheric models to interpret an ensemble of spectra without having to retrain the random forest. A method of atmospheric retrieval for exoplanets that uses supervised ‘random forest’ machine learning, less time-consuming than standard techniques, is presented. Tests on Hubble spectra of WASP-12b give results consistent with standard atmospheric retrievals.

References
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3. Pearson, K. A., Palafox, L. & Griffith, C. A. Searching for exoplanets using artificial intelligence. Mon. Not. R. Astron. Soc. 474, 478–491 (2018).
4. Madhusudhan, N. & Seager, S. A temperature and abundance retrieval method for exoplanet atmospheres. Astrophys. J. 707, 24–39 (2009).
5. Benneke, B. & Seager, S. Atmospheric retrieval for super-Earths: uniquely constraining the atmospheric composition with transmission spectroscopy. Astrophys. J. 753, 100 (2012).
6. Line, M. R. et al. Information content of exoplanetary transit spectra: an initial look. Astrophys. J. 749, 93 (2012).
7. Rodgers, C. D. Inverse Methods for Atmospheric Sounding: Theory and Practice (World Scientific, Singapore, 2000).
8. Waldmann, I. P. Dreaming of atmospheres. Astrophys. J. 820, 107 (2016).
9. Ho, T. K. The random subspace method for constructing decision forests. IEEE Trans. Pattern Anal. Mach. Intell. 20, 832–844 (1998).
10. Breiman, L. Random forests. Mach. Learn. 45, 5–32 (2001).
11. Heng, K. & Kitzmann, D. The theory of transmission spectra revisited: a semi-analytical method for interpreting WFC3 data and an unresolved challenge. Mon. Not. R. Astron. Soc. 470, 2972–2981 (2017).

ExoCross is a Fortran code for generating spectra (emission, absorption) and thermodynamic properties (partition function, specific heat etc.) from molecular line lists. Input is taken in several formats, including ExoMol and HITRAN formats. ExoCross is efficiently parallelized showing also a high degree of vectorization. It can work with several line profiles such as Doppler, Lorentzian and Voigt and support several broadening schemes. Voigt profiles are handled by several methods allowing fast and accurate simulations. Two of these methods are new. ExoCross is also capable of working with the recently proposed method of super-lines. It supports calculations of lifetimes, cooling functions, specific heats and other properties. ExoCross can be used to convert between different formats, such as HITRAN, ExoMol and Phoenix. It is capable of simulating non-LTE spectra using a simple two-temperature approach. Different electronic, vibronic or vibrational bands can be simulated separately using an efficient filtering scheme based on the quantum numbers.

The Voigt profile is important for spectroscopy, astrophysics, and many other fields of physics, but is notoriously difficult to compute. McLean et al. [1] [J. Electron Spectrosc. & Relat. Phenom., 1994] have proposed an approximation using a sum of Lorentzians. Our assessment indicates that this algorithm has significant errors for small arguments. After a brief survey of the requirements for spectroscopy we give a short list of both efficient and accurate codes and recommend implementations based on rational approximations.

The amplitude, the temperature dependence, and the physical origin of the water vapour absorption continuum are a long-standing issue in molecular spectroscopy with direct impact in atmospheric and planetary sciences. In recent years, we have determined the self-continuum absorption of water vapour at different spectral points of the atmospheric windows at 4.0, 2.1, 1.6, and 1.25µm, by highly sensitive cavity-enhanced laser techniques. These accurate experimental constraints have been used to adjust the last version (3.2) of the semi-empirical MT_CKD model (Mlawer-Tobin_Clough-Kneizys-Davies), which is widely incorporated in atmospheric radiative-transfer codes. In the present work, the self-continuum cross-sections, C_S, are newly determined at 3.3µm (3007cm⁻¹) and 2.0µm (5000cm⁻¹) by optical-feedback-cavity enhanced absorption spectroscopy (OFCEAS) and cavity ring-down spectroscopy (CRDS), respectively. These new data allow extending the spectral coverage of the 4.0 and 2.1µm windows, respectively, and testing the recently released 3.2 version of the MT_CKD continuum. By considering high temperature literature data together with our data, the temperature dependence of the self-continuum is also obtained.

We report experimental results on the broadening and shifting coefficients in a large interval of J quantum numbers in the fundamental and first overtone vibration–rotation bands of the HCl molecule in mixtures with helium. Many of the values, especially for the overtone transition, are novel. The uncertainties for the isotope-averaged broadening coefficients amount to 2% on average for the fundamental and 1.5% for the overtone bands. Shifts have a typical uncertainty of 3%.
 

In the present study, we report highly accurate air-induced broadening and shift coefficients for the nitrous oxide (N₂O) 00⁰2–00⁰0 band at 2.26 μm of the main isotopologue retrieved from high-resolution Fourier transform infrared (FTIR) measurements with metrologically determined pressure, temperature, absorption path length and chemical composition. Most of our retrieved air-broadening coefficients agree with previously generated datasets within the expanded (confidence interval of 95%) uncertainties. For the air-shift coefficients our results suggest a different rotational dependence compared to literature. The present study benefits from improved measurement conditions and a detailed metrological uncertainty description. Comparing to literature, the uncertainties of the previous broadening and shift coefficients are improved by a factor of up to 39 and up to 22, respectively.

The ν₁ fundamental band of N₂O is examined by a novel spectrometer that relies on the frequency locking of an external-cavity quantum cascade laser around 7.8 µm to a near-infrared Tm:based frequency comb at 1.9 µm. Due to the large tunability, nearly 70 lines in the 1240–1310 cm⁻¹ range of the ν₁ band of N₂O, from P(40) to R(31), are for the first time measured with an absolute frequency calibration and an uncertainty from 62 to 180 kHz, depending on the line. Accurate values of the spectroscopic constants of the upper state are derived from a fit of the line centers (rms ≈ 4.8 × 10⁻⁶ cm⁻¹ or 144 kHz). The ν₁ transitions presently measured in a Doppler regime validate high accuracy predictions based on sub-Doppler measurements of the ν₃ and ν₃-ν₁ transitions.

An expression was developed that correctly models the temperature dependence of the half-width over large temperature ranges and the temperature dependence of the line shift, even for cases where the line shift changes sign. The expression was derived from the expansion of the collisional cross-sections in a series of powers of the relative velocity of the radiator and perturber. Cutting off at two terms yields a complex double power law (DPL) expression, where the real and imaginary parts describe the temperature dependence of the half-width and line shift, respectively. Data were collected for more than 100 thousand transitions and the standard power law expression for the half-width and line shift were compared with the new double power law expression. It is shown that the double power law works well for all transitions, even those that exhibit unusual structure, which the standard power law cannot model. The DPL expression gives better results than the standard power law for all transitions studied and the DPL model gives good results for the temperature dependence of the line shift when it changes sign. The DPL model for the temperature dependence of the line shift was compared with the linear model, which is currently used on the HITRAN database. In all cases the DPL model gave much better results than the linear model no matter what temperature range was considered. The new formalism allows a substantial reduction in the number of parameters that need to be stored in databases and the same expression can be utilized in radiative transfer and simulation codes for both the half-width and line shift.

Spherical-top tetrahedral species like CH₄, SiH₄, CF₄, … possess no permanent dipole moment. Therefore, probing their pure rotation spectrum is very challenging since only a very weak dipole moment can be induced by centrifugal distortion and/or rovibrational interaction. If some Q branch lines have been recorded thanks to microwave techniques, R branch lines in the THz region have been poorly explored until recently. In previous studies, we have reported the pure rotation THz spectrum of cold and hot band lines of methane recorded at the SOLEIL Synchrotron facility. Here, we present the first recorded THz spectrum of the R branch of CF₄, a powerful greenhouse gas, in its state. This Fourier transform spectrum covers the to line clusters, in the cm⁻¹ spectral range. It was recorded thanks to a 150 m multiple path cell at room temperature. We could estimate the vibration-induced dipole moment value and also include the recorded line positions in a global fit of many CF₄ transitions.

A tubular furnace is combined with a diode laser spectrometer to record the high temperature near infrared absorption spectrum of methane at a pressure of 80 Torr. The investigated spectral range covers the 5693–6257 cm⁻¹ (1.75–1.60 µm) range of the tetradecad dominated by the 2ν₃ band near 6000 cm⁻¹. Various determinations (thermocouples, Doppler line broadening, rotational temperature) provide a value of about 964 K for the gas temperature. Lines with intensity larger than 5 × 10⁻²⁴ cm/molecule at 1000 K are detected. As a result of the high temperature, high-J rovibrational transitions up to J ≈ 20 and hot bands are identified in the spectrum. The recorded spectra provide tests of various methane line lists recently released in the literature: HITRAN2016, experimental list derived from emission spectra, the MeCaSDa empirical line list and the TheoReTs and ExoMol theoretical line lists. The agreement with the TheoReTs line list is found to be very good in the studied region.

In this paper, we report the vibration-rotation energy levels of methane (¹²CH₄) calculated using the latest version of the global effective Hamiltonian developed in Dijon [B. AMYAY et al.. J. Chem. Phys., 148, 134–306 (2018)]. 238,429 vibration-rotation energy levels are calculated rotationally up to 50 and vibrationally up to the Tetradecad ( ≈  6200 cm). The corresponding wavefunctions mixings are also investigated in this work. The knowledge of both energy levels and wavefunctions mixings are essential for simulating high-resolution spectra of methane of astrophysical and atmospheric interests. An evidence of distinct regular and oscillatory contributions, is observed in the number of vibration-rotation levels of methane. This can be fully understood using the generating functions presented by Sadovskií and Zhilinskií [J. Chem. Phys. 103, 10–520 (1995)].

Monitoring ozone concentrations in the Earth's atmosphere using spectroscopic methods is a major activity which undertaken both from the ground and from space. However there are long-running issues of consistency between measurements made at infrared (IR) and ultraviolet (UV) wavelengths. In addition, key O₃ IR bands at 10 μm, 5 μm and 3 μm also yield results which differ by a few percent when used for retrievals. These problems stem from the underlying laboratory measurements of the line intensities. Here we use quantum chemical techniques, first principles electronic structure and variational nuclear-motion calculations, to address this problem. A new high-accuracy ai dipole moment surface (DMS) is computed. Several spectroscopically-determined potential energy surfaces (PESs) are constructed by fitting to empirical energy levels in the region below 7000 cm^-1 starting from an ai PES. Nuclear motion calculations using these new surfaces allow the unambiguous determination of the intensities of 10 muu band transitions, and the computation of the intensities of 10 μm and 5 μm bands within their experimental error. A decrease in intensities within the 3 μm is predicted which appears consistent with atmospheric retrievals. The PES and DMS form a suitable starting point both for the computation of comprehensive ozone line lists and for future calculations of electronic transition intensities.

The positions and intensities of 1936 lines observed in the range 7400– of two absorption spectra of ammonia recorded at high resolution using Fourier transform spectroscopy are reported. The accuracy of these line positions is estimated to range from 0.001 to from the lower to the upper limits of the spectral range considered, while the accuracy of the line intensities is estimated to be around 10% or better. Also reported are less-accurately measured positions and intensities of 1985 lines retrieved from these two spectra or from only one of them. These results are compared with the data measured recently in a spectrum recorded in 1980 at the Kitt Peak National Solar Observatory [Barton et al., J. Mol. Spectrosc. 325, 7 (2016)] and provided in HITRAN 2016, as well as line positions and intensities measured in this work in the same Kitt Peak spectrum.

The high resolution infrared spectra of SiD4 were recorded with Bruker IFS120 and IFS125 HR Fourier transform infrared spectrometers at an optical resolution of 0.002 and 0.0021 cm⁻¹ and analyzed in the region of 1480–1700 cm⁻¹ where the stretching bands ν₃ and ν₁ are located. The 2676 transitions with J_max. = 44 were assigned to the ν₃ band.The subsequent weighted fit of experimentally assigned transitions was made with the Hamiltonian model which takes the resonance interactions between the (0010) and (1000) vibrational states into account. As the result, a set of 18 fitted parameters was obtained which reproduces the initial 2676 ro–vibrational transitions with the drms=3.71×10⁻⁴ cm⁻¹.

The strengths of 619 experimentally recorded spectral lines (J^max = 24) of the ν₄ and ν₂ bands of ²⁸SiD₄ were determined from the fit of their line shapes with a Hartmann–Tran line profile and were used then in the weighted fit for determination of the effective dipole moment parameters of these bands. The obtained set of four parameters reproduce the initial experimental line intensities with the d_rms=5.61%. A list of transitions with their line intensities is generated up to the value of quantum number J=37. The half–widths analysis was made on the basis of the multi–spectrum fit with the Hartmann-Tran line profile, and self–pressure broadening coefficients were estimated for 60 lines of the dyad.

Представлен подход, использованный при разработке и реализации модуля, выполняющего бинарные операции над данными в ИС «Молекулярная спектроскопия». Приводится формализация бинарных операций над наборами спектроскопических данных с учетом особенностей предметной области. Описываются алгоритм действий и интерфейс пользователя для проведения бинарных операций – единые для имеющихся баз данных по различным веществам и нескольким типам спектроскопических данных.

New methods of integrating scientific data on the properties of substances and materials that apply modern information technologies are analysed. The capabilities of systems created using the Semantic Web and Big Data are explored. Despite some differences in the tasks that are solved, both approaches are oriented towards working with large arrays of web-distributed, structurally heterogeneous data. Several data-integration platforms that have been developed in recent years, including a system designed by the authors, are studied. It is concluded that currently none of the integration systems can fully satisfy specific the requirements of scientific data. Nevertheless, several software elements and technological solutions are of interest and can support the implementation of a project to integrate scientific data on properties of substances and materials.

(Original Russian Text A.O. Erkimbaev, V.Yu. Zitserman, G.A. Kobzev, A.V. Kosinov, 2018, published in Nauchno-Tekhnicheskaya Informatsiya, Seriya 2: Informatsionnye Protsessy i Sistemy, 2018, No. 10, pp. 11–19. INFORMATION ANALYSIS)

We report the results of ab initio investigation of the S and O branches of the hydrogen molecule perturbed by helium atom. The calculations, based on close-coupling scheme, were performed for vibrational bands from v = 0 to v = 5, and rotational levels up to j = 5. We provide the pressure broadening and shifting coefficients and the real and imaginary parts of Dicke contribution to the Hess profile. The results are important for astrophysical studies, for example as a reference data for studying the gas giants’ atmospheres.

We show in this paper that requantized classical molecular dynamics simulations (rCMDSs) are capable of predicting various refined spectral-shape parameters of absorption lines of CO₂ broadened by N₂ with high precision. Combining CMDSs and a requantization procedure, we computed the auto-correlation function of the CO₂ dipole moment responsible for the absorption transition. Its Fourier-Laplace transform directly yields the spectrum. Calculations were made for two temperatures, 200 and 296 K, at 1 atm and for a large range of Doppler widths, from the near-Doppler to the collision-dominant regimes. For each temperature and each line, the spectra calculated for various Doppler widths were simultaneously fit with the Hartmann-Tran (HT) profile. This refined profile, which takes into account the effects of the speed dependent collisional line broadening, the Dicke narrowing, and the collisional line mixing, was recommended as a reference model to be used in high-resolution spectroscopy (instead of the simplified Voigt model). The HT parameters retrieved from the rCMDS-calculated spectra were then directly compared with those deduced from high-precision measurements [J. S. Wilzewski et al., J. Quant. Spectrosc. Radiat. Transfer 206, 296–305 (2018)]. The results show a very good agreement, even for those parameters whose influence on the spectra is very small. Good agreement is also obtained between measured and predicted temperature dependences of these parameters. This demonstrates that rCMDS is an excellent tool, highly competitive with respect to high quality measurements for precise line-shape studies.

A new line list for AlH is produced. The WYLLoT line list spans two electronic states X¹Σ⁺ and A¹Π⁠. A diabatic model is used to model the shallow potential energy curve of the A¹Π state, which has a strong pre-dissociative character with only two bound vibrational states. Both potential energy curves are empirical and were obtained by fitting to experimentally derived energies of the X¹Σ⁺ and A¹Π electronic states using the diatomic nuclear motion codes dpotfit and duo. High-temperature line lists plus partition functions and lifetimes for three isotopologues ²⁷AlH, ²⁷AlD, and ²⁶AlH were generated using ab initio dipole moments. The line lists cover both the X–X and A–X systems and are made available in electronic form at the cds and exomol data bases.

The performances of a multi-spectral fit for the spectra of pressure-broadened overlapping lines (R₉F₁, R₉F₂) of ¹²CH₄ in binary mixtures with N₂ were studied by applying different lineshape models, from the simplest Voigt profile (VP) to the Harmann-Tran profile (HTP). Line-mixing was approximated in the first order in the spectral fits. Data were acquired using a high-resolution cavity ring-down spectrometer of minimum detectable absorption coefficient of 2.8 × 10⁻¹² cm⁻¹. The lines were observed with a signal-to-noise ratio of 19 365 for pressures from 5 to 40 kPa. The study reveals that the multi-spectral fits using the HTP and the speed-dependent Nelkin–Ghatak profile (SDNGP) yield the best among all tested. The two models gave the maximum relative residuals of less than 0.065 %. All things considered, the HTP and the SDNGP appear to be the most reliable models for treating the present case of multi-spectral fitting of unresolved dual-component spectra.

In this work, we report calculated vibrational energy levels of the methane molecule up to 10 300 cm⁻¹. Two potential energy surfaces constructed in quite different coordinate systems with different analytical representations are employed in order to evaluate the uncertainty of vibrational predictions. To calculate methane energy levels, we used two independent techniques of the variational method. One method uses an exact kinetic energy operator in internal curvilinear coordinates. Another one uses an expansion of Eckart-Watson nuclear motion Hamiltonian in rectilinear normal coordinates. In the Icosad range (up to five vibrational quanta bands–below 7800 cm⁻¹), the RMS standard deviations between calculated and observed energy levels were 0.22 cm⁻¹ and 0.41 cm⁻¹ for these two quite different approaches. For experimentally well-known 3v₃ sub-levels, the calculation accuracy is estimated to be ∼1 cm⁻¹. In the Triacontad range (7660-9188 cm⁻¹), the average error of the calculation is about 0.5 cm⁻¹. The accuracy and convergence issues for higher energy ranges are discussed.

The dependence of the intermolecular interaction potentials on the vibrational quantum numbers of the H₂O molecule is derived for the H₂O–Ne, H₂O–Kr, and H₂O–Xe systems. The broadening γ and shift δ coefficients are calculated for seven vibrational bands ν₁, ν₂, ν₃, 2ν₂, ν₁ + ν₂, ν₂ + ν₃, and ν₁ + ν₂ + ν₃ of the H₂O molecule from the absorption region 640–9550 cm⁻¹. An analytical formula is suggested for calculation of the broadening coefficients γ at T = 296 K. It is shown that the excitation of stretching modes of the vibrations in the H₂O molecule increases the broadening coefficients. The influence of the bending vibrations on γ is insignificant.

Thirty well isolated ro-vibrational transitions of the 30011e – 00001e band of ¹²C¹⁶O₂ at 1.54 μm have been recorded with a laser-locked cavity ring-down spectrometer. The line intensities were obtained with accuracies better than 0.85%. Comparisons of the line intensities determined in this work with literature experimental values and those from HITRAN2016, AMES, UCL-IAO and CDSD-296 line lists are given.

The very weak absorption spectrum of natural CO₂ near 1.74 µm (5702–5879 cm⁻¹) is studied at high sensitivity. The investigated region corresponds to a transparency window of very weak opacity which is of particular interest for Venus. Very weak lines with intensity value as low as 10⁻³⁰ cm/molecule at 296 K are detected by Cavity Ring Down Spectroscopy. On the basis of the predictions of effective Hamiltonian models, 1135 lines of six carbon dioxide isotopologues - ¹²C¹⁶O₂, ¹³C¹⁶O₂, ¹⁶O¹²C¹⁸O, ¹⁶O¹²C¹⁷O, ¹⁶O¹³C¹⁸O and ¹⁶O¹³C¹⁷O - were rovibrationnally assigned to 26 bands. The accurate spectroscopic parameters of 16 bands are determined from standard band-by-band analysis (typical rms deviations of the line positions are 8 × 10⁻⁴ cm⁻¹).

These newly observed bands include perturbed bands, weak hot bands and bands of minor isotopologues (in particular ¹⁶O¹²C¹⁸O in natural abundance) and provide critical validation tests for the most recent spectroscopic databases. The comparison to the Carbon Dioxide Spectroscopic Databank (CDSD), HITRAN2016 database and recent ab initio line lists is presented. Deficiencies are evidenced for some weak perpendicular bands of the HITRAN2016 list and identified as due to inaccurate CDSD intensities which were preferred to ab initio intensities. While Ames and UCL ab initio intensities are believed to be accurate within a few % for the strong unperturbed bands, the reported measurements allow testing important (>50%) differences between ab initio values of some weak perturbed bands.

A set of high-resolution absorption spectrometers based on TDLAS was used to determine the impact of combustion-relevant gases on the pressure shift and broadening of H2O, CO2, C2H2 and CH4 absorption lines in the near-infrared spectral region. In particular, self- and foreign-broadening coefficients induced by CO2, N2, O2, air, C2H2 and CH4 were measured. The absorption lines under investigation are suitable to measure the respective species in typical combustion environments via laser absorption spectroscopy. Additionally, species-dependent self- and foreign-induced pressure shift coefficients were measured and compared to the literature. The experiments were performed in two specifically designed absorption cells over a wide pressure range from 5 to 180 kPa. Different sources of uncertainty were identified and quantified to achieve relative measurement uncertainties of 0.7–1.5% for broadening coefficients and 0.6–1.6% for pressure shift coefficients.

Both ontology builders and users need a way to evaluate ontologies in terms of usability, but existing ontology evaluation approaches do not fit this purpose. We propose the Ontology Usability Scale (OUS), a ten-item Likert scale derived from statements prepared according to a semiotic framework and an online poll in the Semantic Web community to provide a practical way of ontology usability evaluation. Case studies were conducted to bookkeep current usability evaluation results for ontologies expecting revisions in the future, and discussions of the poll results are presented to help proper use and customization of the OUS.

The infrared spectrum of ammonia has proven to be highly problematic for effective Hamiltonian analysis. The most complete previous study of the 3ν₂ and ν₄+ν₂ bands achieved the accuracy of 0.0069 cm⁻¹ as reflected by the root-mean-square error of their fit, which is slightly more than 10 times the experimental accuracy. In the present study, we performed a global fit of the existing 2141 literature data involving 3ν₂, ν₄+ν₂, 3ν₂-ν₂, (ν₄+ν₂)-ν₂ together with 1281 new data involving 3ν₂-2ν₂, 3ν₂-3ν₂ and (ν₄+ν₂)-(ν₄+ν₂) using an effective Hamiltonian together with the Pickett suite of program SPFIT/SPCAT. The new dataset consists of three spectra recorded at the SOLEIL synchrotron facility. The effective Hamiltonian model proposed for 3ν₂/ν₄+ν₂ has achieved experimental accuracy. This success combined with our previous success of the 2ν₂/ν₄ analysis leads us to believe that the vibrational states higher than 3ν₂/ν₂+ν₄ may be analyzed with effective Hamiltonians as well.

Positions and intensities for transitions in the 1←0 bands of the four CO isotopologues (¹²C¹⁶O, ¹³C¹⁶O, ¹²C¹⁸O and ¹³C¹⁸O) were retrieved from analyses of spectra of different low-pressure pure samples and high-pressure air-broadened mixtures (1940–2260 cm⁻¹) in two different multispectrum fittings involving selected groups of 21 (for ¹³C¹⁶O) and 20 (for ¹²C¹⁸O) spectra. Air-broadened half-width and air-shift coefficients, their temperature dependences, line mixing via off-diagonal relaxation matrix element coefficients for CO-air collision systems, and quadratic speed dependence parameters were measured for ¹³C¹⁶O and ¹²C¹⁸O transitions. In both the fittings, two low-pressure room-temperature spectra of a high purity natural sample of CO recorded with the Kitt Peak FTS were included to retrieve the positions and intensities of ¹²C¹⁶O transitions. All other spectra in the fittings were obtained with either ¹³C-enriched or ¹⁸O-enriched samples using the JPL Bruker IFS-125HR FTS. Four absorption cells with path lengths between 0.5131(5) and 20.38(2) cm were used to record the data. The cells are temperature controlled, except for the shortest cell. Positions and intensities for the 1←0 band transitions were determined from the retrieved ro-vibrational constants (G, B, D and H), band intensity and Herman-Wallis parameters by applying the theoretical quantum mechanical expressions. The band strengths of ¹²C¹⁶O, ¹²C¹⁸O and ¹³C¹⁸O are very close (∼0.3%) to HITRAN2012 values but for ¹³C¹⁶O the band strength is ∼4.8% larger than the HITRAN2012 and 2.6% larger than the HITRAN2016 value.

The collision-induced broadening (2γ_OH-A) and shift (δ_OH-A) parameters of hydroxyl radical (OH) with two collisional partners - argon and nitrogen - and their associated temperature-dependence coefficients (n_A and m_A, respectively), have been measured in a series of shock tube experiments. The Q₁(5) OH transition, a member of the A²Σ – X²Π (0, 0) rovibronic band with a line-center wavelength near 308.6 nm, represents an ideal target for quantitative spectroscopy in combustion applications, owing to its strength and degree of relative spectral isolation. Narrow-width tunable UV light was used to sample the Q₁(5) lineshape profile across 8–10 wavelengths. The data were subsequently fit to the Voigt lineshape model at the fixed temperature, pressure and mixture composition. Measurements are presented for 2γ_OH-Ar, δ_OH-Ar, n_Ar, and m_Ar, recommended for T = 1300–2000 K, as well as 2γ_OH-N2, δ_OH-N2, n_N2, and m_N2, recommended for T = 1600–2000 K. The Q₁(5) lineshape was also measured at pressures of 45 and 95 atm, for which application of the Voigt model yielded values of 2γ_OH-Ar and δ_OH-Ar that were consistent with lower-pressure measurements, supporting the validity of the lineshape model and, particularly, the diagnostic in question at such pressures.

In this work, we measured the absorption by CO₂+H₂O mixtures from 2400 to 2600 cm⁻¹ which corresponds to the spectral region beyond the ν3 band head of CO₂. Transmission spectra of CO2 mixed with water vapor were recorded with a high-resolution Fourier-transform spectrometer for various pressure, temperature and concentration conditions. The continuum absorption by CO₂ due to the presence of water vapor was determined by subtracting from measured spectra the contribution of local lines of both species, that of the continuum of pure CO₂ as well as of the self- and CO₂-continua of water vapor induced by the H₂O-H₂O and H₂O-CO₂ interactions. The obtained results are in very good agreement with the unique previous measurement (in a narrower spectral range). They confirm that the H₂O-continuum of CO₂ is significantly larger than that observed for pure CO₂. This continuum thus must be taken into account in radiative transfer calculations for media involving CO₂ + H₂O mixture. An empirical model, using sub-Lorentzian line shapes based on some temperature-dependent correction factors χ is proposed which enables an accurate description of the experimental results.

The absorption spectrum of water vapor enriched in oxygen-17 has been recorded by a continuous-wave cavity ring-down spectrometer (CW-CRDS) at room temperature in the 12,277–12,894 cm⁻¹ region. The typical sensitivity of 2 × 10−10 cm⁻¹ allowed the detection of water vapor transitions with intensities larger than 1 × 10 ⁻²⁸ cm⁻¹ /(molecule cm⁻²). In total, more than 3400 lines were observed in the recorded spectra with a typical frequency accuracy of 0.002 cm⁻¹. In which more than 3400 transitions were ro-vibrationally assigned to five water isotopic species (H₂¹⁷O, H₂¹⁶O, H₂¹⁸O, HD¹⁶O, and HD¹⁷O) using the known empirical energy levels combined with the calculated variational line lists based on the results of Partridge and Schwenke. About 1300 transitions of H₂¹⁷O were assigned, leading to the determination of new energy levels of 17 vibration states. Those assigned H217 O transitions are involved with the upper vibration states of (013), (023), (032), (051), (061), (070), (080), (090), (112), (131), (150), (160), (211), (230), (301), (310), and (320). The maximum values of the rotational numbers J and Ka were 16 and 9, respectively. The 5ν1 band of HD¹⁷O was assigned for the first time as well. The line positions and energy levels determined in this work were compared with literature, and it shows a significant improvement of the line positions of H₂ ¹⁷O and HD¹⁷O in the 12,277–12,894 cm⁻¹ region.

Room temperature NH3 absorption spectra recorded at the Kitt Peak National Solar Observatory in 1980 are analyzed. The spectra cover two regions in the visible: 15,200 – 15,700 cm^-1 and 17,950 – 18,250 cm^-1. These high overtone rotation-vibration spectra are analyzed using both combination differences and variational line lists. Two variational line lists were computed using the TROVE nuclear motion program: one is based on an ab initio potential energy surface (PES) while the other used a semi-empirical PES. Ab initio dipole moment surfaces are used in both cases. 95 energy levels with J=1-7 are determined from analysis of the experimental spectrum in the 5νNH (red) region and 46 for 6νNH (green) region. These levels span four vibrational bands in each of the two regions, associated with stretching overtones.

The spectra of the Н₂¹⁶О and Н₂¹⁸О vapor have been recorded between 16,460 and 17,200 cm⁻¹ by a Fourier transform spectrometer with spectral resolution of 0.05 cm⁻¹ using high luminance LED light source and 60 cm multipath cell with a path length of 3480 cm. A high signal-to-noise ratio (S/N ≈ 5000) enable us to register the lines with intensities of 1.54 × 10⁻²⁴ to 2.0 × 10⁻²⁷ cm/molecule. More than 1300 lines were recorded in the spectrum of the natural abundance water vapor and over 1800 lines in the spectrum of the vapor enriched by ¹⁸O. 422 rotation-vibration energy levels of the H₂¹⁸O molecule have been assigned to twenty vibrational states. The majority of these energies was attributed to the (241), (321), (340), (420), (401), (500), and (123) states. 43 energy levels were tentatively assigned to the (043), (142), (302), (161), (260), and (062) states. Eleven energy levels were labeled as belonging to the (280), (081), (190), (0 10 0), (1 10 0), (0 11 0), and (0 12 0) states. The recorded spectra were compared with the simulations based on the HITRAN2016 database and variational lists.

N₂ pressure broadening and shifting coefficients are presented for about 300 strongest water vapor lines in the 16,600–17,060 cm⁻¹ spectral region. The spectra have been recorded with a spectral resolution of 0.05 cm⁻¹ at room temperature by a Fourier transform spectrometer using a high luminance LED light source. A high signal-to-noise ratio (S/N ≈ 10 000) permits the analyses of the lines with intensities from 1.54 × 10⁻²³ to 2.0 × 10⁻²⁶ cm/molecule. The multi-spectrum fitting procedure was used to fit line parameters of the ν₁+ 4ν₂+ 2ν₃, 3ν₁+ 2ν₂+ ν₃, 4ν₁+ ν₃, 4ν₁+ 2ν₂, 5ν₁ bands for the temperature T = 297 K. Line broadening and shifting calculations are performed using a semi-empirical method, which is based on the impact theory of broadening, and includes the correction factors whose parameters were determined by fitting the broadening coefficients of 12 lines to the experimental data. The method was further developed for the estimate of line profiles using the an harmonic wave functions.

A new study of ¹²CH₄ line positions and intensities was performed for the Tetradecad regions 5550,000–5695.250, 5718.8–5724.250 and 5792.36–5814.290 cm⁻¹ using long path (202 m, 602 m, 1604 m and 1804 m) spectra of normal samples of CH₄ at different pressures recorded with a Fourier transform spectrometer in Reims, France. Line positions and intensities were retrieved by least squares curve-fitting procedures and analyzed using the effective Hamiltonian and the effective dipole moment expressed in terms of irreducible tensor operators adapted to spherical top molecules. An 80 K spectrum recorded in Jet Propulsion Laboratory (JPL), Pasadena, of enriched ¹²CH₄ was used for low-J line positions. Another 80 K spectrum of enriched ¹³CH₄ from JPL was used to discern the isotopic lines. A new measured linelist contains positions and intensities for 5819 features. Quantum assignments were made for more than 3400 transitions, which represent ∼95% of the integrated line intensity observed in this region. All assigned 3445 line positions were fitted with RMS standard deviations of 0.0024 cm⁻¹. The sum of observed intensities between 5550 and 5695 cm⁻¹ fell within 2% of the predicted value from ab initio variational calculations reported in the TheoReTS database (http://theorets.univ-reims.fr; http://theorets.tsu.ru).

Variationally computed infrared spectra in the range [0-5000] cm^-1 are reported for the deuterated PH₂D and PHD₂ molecules from accurate potential energy and dipole moment surfaces initially derived for the major isotopologue PH₃(C_3v ). Energy level and line intensity calculations were performed by using a normal-mode model combined with isotopic and symmetry transformations for the H → D substitutions. Theoretical spectra were computed at 296 K up to J_max = 30 and will be made available through the TheoReTS information system (http://theorets.univ-reims.fr, http://theorets.tsu.ru). For the very first time, ab initio intensity predictions of PH₂D/PHD₂ are in good qualitative agreement with the literature. This work will be useful for spectral intensity analysis for which accurate spectral intensity data are still missing.

The emission spectrum of the 0-0; 1-1 and 2-2 bands of the C²Σ⁺ -  X²Π system in the CD molecule have been obtained using a stainless steel hollow-cathode lamp with two anodes and filled with a mixture of He buffer gas and CD₄. The emission from the discharge was observed with high accuracy dispersive optical spectroscopy using a plane-grating spectrograph and recorded by a photomultiplier tube. In total, 428 transition frequencies belonging to the three bands were precisely measured and rotationally analyzed. The current data were elaborated with the help of precise ro-vibrational and equilibrium ground state parameters reported by Zachwieja et al. (2012) from investigation of the A²Δ - X²Π transition. The spin-rotation interaction constants γ_v and γ_D;v of the C²Σ⁺ v = 0,1,2 levels were obtained for the first time. Moreover, the main equilibrium parameters of the third excited state were obtained as follows: T_e = 31,825.944ð12 cm^-1, ω_e = 2078.803(27) cm^-1, ω_ex_e = 59.558(12) cm^-1, B_e = 7:86810ð23 cm^-1, α_e = 0.25315ð58 cm^-1 and γ_e = 0.01518ð28 cm^-1.

We present a theoretical study of the effects of collisions with water vapor molecules on the absorption, around 4 μm, in both the high frequency wing of the CO₂ ν₃ band and the collision-induced fundamental band of N₂. Calculations are made for the very first time, showing that predictions based on classical molecular dynamics simulations enable, without adjustment of any parameter, very satisfactory agreement with the few available experimental determinations. This opens the route for a future study in which accurate temperature-dependent (semi-empirical) models will be built and checked through comparisons between computed and measured atmospheric spectra. This is of interest since, as demonstrated by simulations, neglecting the humidity of air can lead to significant modifications of the atmospheric transmission (and thus also emission) between 2000 and 2800 cm⁻¹.

The high-resolution FTIR spectrum of the 2v₂ band (3250–3380 cm⁻¹) of D₂¹³CO was recorded at an unapodized resolution of 0.0063 cm⁻¹. A total of 747 rovibrational transitions have been assigned and fitted up to J″ = 32 and K_a″ = 10 using the Watson’s A-reduced Hamiltonian in the I^r representation. A set of accurate upper state (v₂= 2) rovibrational constants, three rotational and five quartic centrifugal distortion constants, were determined for the first time. The band center of the 2v₂ band was found to be 3326.765109 ± 0.000079 cm⁻¹. The rms deviation of the rovibrational fit was 0.00096 cm⁻¹.

The consistency of all data that have been published to date on the rovibrational line centers of the hydrogen chloride molecule HCl is analyzed. It was revealed that a number of corrections are needed because of systematic inaccuracies in the line center determination. A simultaneous fit of rovibrational transition frequencies was performed in the region from 7.4 to 18075 cm^–1. The isotopically independent spectroscopic parameters for calculating rovibrational energy levels in the ground electronic state are determined. The calculated line centers are compared with the HITRAN data. The obtained spectroscopic parameters are used to calculate the turning points (rmin and rmax) of RKR-potentials of HCl isotopologues. The use of experimental data, including the highest vibrational state with V_max = 8 that lies approximately at half the potential well depth allowed the pointwise potentials to be calculated up to Vmax = 20.

The FAIR guiding principles for research data stewardship (findability, accessibility, interoperability, and reusability) look set to become a cornerstone of research in the life sciences. A critical appraisal of these principles in light of ongoing discussions and developments about data sharing is in order. The FAIR principles point the way forward for facilitating data sharing more systematically — provided that a number of ethical, methodological, and organisational challenges are addressed as well.

The non-relativistic variational calculation of a complete set of ro-vibrational states in the H⁺₂ molecular ion supported by the ground 1sσ adiabatic potential is presented. It includes both bound states and resonances located above the n = 1 threshold. In the latter case we also evaluate a predissociation width of a state wherever it is significant. Relativistic and radiative corrections are discussed and effective adiabatic potentials of these corrections are included as supplementary files.

We present an accurate measurement of the weak quadrupole S(2) 2-0 line in self-perturbed D₂ and theoretical ab initio calculations of both collisional line-shape effects and energy of this rovibrational transition. The spectra were collected at the 247–984 Torr pressure range with a frequency-stabilized cavity ring-down spectrometer linked to an optical frequency comb (OFC) referenced to a primary time standard. Our line-shape modeling employed quantum calculations of molecular scattering (the pressure broadening and shift and their speed dependencies were calculated, while the complex frequency of optical velocity-changing collisions was fitted to experimental spectra). The velocity-changing collisions are handled with the hard-sphere collisional kernel. The experimental and theoretical pressure broadening and shift are consistent within 5% and 27%, respectively (the discrepancy for shift is 8% when referred not to the speed averaged value, which is close to zero, but to the range of variability of the speed-dependent shift). We use our high pressure measurement to determine the energy, ν₀, of the S(2) 2-0 transition. The ab initio line-shape calculations allowed us to mitigate the expected collisional systematics reaching the 410 kHz accuracy of ν₀. We report theoretical determination of ν₀ taking into account relativistic and QED corrections up to α⁵. Our estimation of the accuracy of the theoretical ν₀ is 1.3 MHz. We observe 3.4σ discrepancy between experimental and theoretical ν₀.

The technique of frequency-stabilized comb-calibrated cavity ring-down spectroscopy was used to observe the weak R(1) transition of the deuturated molecular hydrogen (HD) first overtone band in the near infrared. Like molecular hydrogen, HD is a benchmark system to test quantum electrodynamics, looking for new physics beyond the standard model. The spectral line shape was measured with an extremely high fidelity at relatively low gas pressures. The use of a very refined line-shape model allowed us to retrieve the unperturbed line-center frequency of the R(1) line with a global uncertainty of about 100 kHz (δν/ν=5×10−10). Our value may solve the ambiguity that recently emerged for this line from a pair of sub-Doppler experiments. We also determined other parameters of interest, such as the line strength, the transition dipole moment, and the pressure-broadening coefficien

The methane absorption spectrum is studied at 297 K and 80 K in the center of the Tetradecad between 5695 and 5850 cm⁻¹. The spectra are recorded by differential absorption spectroscopy (DAS) with a noise equivalent absorption of about α_min≈ 1.5 × 10⁻⁷ cm⁻¹. Two empirical line lists are constructed including about 4000 and 2300 lines at 297 K and 80 K, respectively. Lines due to ¹³CH₄ present in natural abundance were identified by comparison with a spectrum of pure ¹³CH₄ recorded in the same temperature conditions. About 1700 empirical values of the lower state energy level, E_emp, were derived from the ratios of the line intensities at 80 K and 296 K. They provide accurate temperature dependence for most of the absorption in the region (93% and 82% at 80 K and 296 K, respectively). The quality of the derived empirical values is illustrated by the clear propensity of the corresponding lower state rotational quantum number, J_emp, to be close to integer values. Using an effective Hamiltonian model derived from a previously published ab initio potential energy surface, about 2060 lines are rovibrationnally assigned, adding about 1660 new assignments to those provided in the HITRAN database for ¹²CH₄ in the region.

We report measurement results for line positions, intensities, half-width, and pressure-induced shift coefficients and line mixing coefficients for N2O broadened by air in the ν3 band. The high signal-to-noise ratio spectra have been recorded at high resolution using the McMath-Pierce Fourier transform spectrometer formerly located at the National Solar Observatory on Kitt Peak, Ariz., USA. The spectra were analyzed using a multispectrum nonlinear least-squares curve-fitting technique employing the speed-dependent Voigt profile with a Rosenkranz (weak) line mixing component. The speed dependence parameters were calculated as suggested in the study of Kochanov (J. Quant. Spectrosc. Radiat. Transf. 189, 18 (2017). doi:10.1016/j.jqsrt.2016.11.007). Several comparisons have been performed between the retrieved parameters and previously published results. For |m| ≤ 40, our results for line positions, broadening, and line mixing coefficients agree best with the results of Loos et al. (J. Quant. Spectrosc. Radiat. Transf. 151, 300 (2015). doi:10.1016/j.jqsrt.2014.10.008). Also, we compared the obtained line positions and intensities with the corresponding values in HITRAN2016 and GEISA-2015 databases. No significant or systematic differences were noticed. The precision of our line positions was estimated to be 3 × 10⁻⁵ cm⁻¹. The reported line positions, intensities, and air-broadening coefficients are accurate to better than 2%. The accuracy of air-pressure-induced line shifts and line mixing coefficients is better than 5%. The line mixing coefficients and air-broadening coefficients were also calculated using the exponential power gap scaling law, and these calculated values were found to be in good agreement with the experimental results.

Pure CO₂ spectra recorded at room temperature and different pressures (0.2–140 Torr) have been analyzed with the help of a fitting routine that takes into account asymmetries arising in the spectral lines due to pressure induced effects such as line mixing. The fitting procedure used in this study allows one to adjust the ro-vibrational constants for the band rather than fitting for individual line parameters. These constrained parameters greatly reduce the measurement uncertainties and allow us to observe the behavior of the weak lines corresponding to high J quantum numbers. We have also calculated line mixing parameters using approximations based on exponential nature of the energy difference between ground and upper vibrational states involved in the ro-vibrational band transitions. The calculated results show good agreement when compared with the experimentally determined parameters.

(J, K)-line broadening and shift coefficients with their temperature-dependence characteristics are computed for the perpendicular (ΔK = ±1) ν₆ band of the ¹²CH₃D-N₂ system. The computations are based on a semi-empirical approach which consists in the use of analytical Anderson-type expressions multiplied by a few-parameter correction factor to account for various deviations from Anderson's theory approximations. A mathematically convenient form of the correction factor is chosen on the basis of experimental rotational dependencies of line widths, and its parameters are fitted on some experimental line widths at 296 K. To get the unknown CH₃D polarizability in the excited vibrational state v₆ for line-shift calculations, a parametric vibration-state-dependent expression is suggested, with two parameters adjusted on some room-temperature experimental values of line shifts. Having been validated by comparison with available in the literature experimental values for various sub-branches of the band, this approach is used to generate massive data of line-shape parameters for extended ranges of rotational quantum numbers (J up to 70 and K up to 20) typically requested for spectroscopic databases. To obtain the temperature-dependence characteristics of line widths and line shifts, computations are done for various temperatures in the range 200–400 K recommended for HITRAN and least-squares fit procedures are applied. For the case of line widths strong sub-branch dependence with increasing K is observed in the R- and P-branches; for the line shifts such dependence is stated for the Q-branch.

Paper is dedicated to the new approach to distributed industrial systems (IS) sustainability/vulnerability assessment. This approach is based on the unitary multiset grammars (UMG) as a flexible and convenient tool designed specially for large systems analysis and optimization. UMG description of IS technological base as well as multiset representation of order completed by the IS, its resource base and impact on the IS are presented. Criterion for recognition of IS sustainability to the impact is formulated. UMG extension for natural disasters impacts (NDI) representation is introduced, and criterion for recognition of IS sustainability to the NDI is also presented. The solution of the reverse problem, concerning part of the order, which may be completed by the affected IS, is described. Implementation issues are considered.

This paper describes a Virtual Research Environment (VRE) based on a web GIS platform ‘­Climate+’, which provides an access to analytic instruments processing 19 collections of ­meteorological and climate data of several international organizations. This environment ­provides ­ystematization  sof spatial data and related climate information and allows a user getting ­analysis results using geoinformation technologies. The ontology approach to this ­ s ystematization is described, ­making it possible to match semantics of meteorological and climate parameters presented in different collections and used in solving various applied problems.

A low-resolution (0.5 cm⁻¹) Fourier transform infrared (FTIR) spectrum of formaldehyde-d₂ (D₂¹²CO) in the 2500–4500 cm⁻¹ region was recorded to study the combination bands in this region. The bands ν₂+ν₄, ν₂+ν₆, ν₂+ν₃, ν₁+ν₂, ν₂+ν₅, ν₂+ν_{5 ,} 3ν₃, 2ν₂ and 2ν₅ were identified and their band centers (with an uncertainty of ± 0.1 cm⁻¹) and band types were determined. Furthermore, the high-resolution FTIR spectrum of the 2ν₂ overtone band (3315–3440 cm⁻¹) of D₂¹²CO was recorded at an unapodized resolution of 0.0063 cm⁻¹ and its infrared lines were analyzed. A total of 970 rovibrational transitions have been assigned and fitted up to J′ = 35 and K_a′ = 14 using the Watson’s A-reduced Hamiltonian in the I^r representation. Upper state (ν₂= 2) rovibrational constants inclusive of three rotational and five quartic centrifugal distortion constants were accurately determined for the first time. The band center of the 2ν₂ band was determined as 3385.200666 ± 0.000035 cm⁻¹. The rms deviation of the rovibrational fit was 0.00093 cm⁻¹. From the fitting of 451 ground state combination differences (GSCDs) of D₂¹²CO which were derived from the infrared transitions of the 2ν₂ band of this work, together with 360 microwave frequencies from a previous study, new and accurate ground state constants of D₂¹²CO up to three octic terms were obtained. The combination and overtone bands and the newly assigned high-resolution infrared lines of the 2ν₂ band in the 2500–4500 cm⁻¹ region can be used to detect D₂¹²CO in this infrared region. In addition, the results derived from this study give information on the rovibrational molecular structure of D₂¹²CO.

An absorption spectrum of H₂¹⁶O at 1950 K is recorded in a premixed methane/air flat flame using a cavity-enhanced optical frequency comb-based Fourier transform spectrometer. 2417 absorption lines are identified in the 6250–6670 cm^-1 region with an accuracy of about 0.01 cm^-1. Absolute line intensities are retrieved using temperature and concentration values obtained by tunable diode laser absorption spectroscopy. Line assignments are made using a combination of empirically known energy levels and predictions from the new POKAZATEL variational line list. 2030 of the observed lines are assigned to 2937 transitions, once blends are taken into account. 126 new energy levels of H₂¹⁶O are identified. The assigned transitions belong to 136 bands and span rotational states up to J=27.

The water vapour line broadening and shifting for 97 lines in the ν₁ + ν₂ + ν₃ band induced by hydrogen pressure are measured with Bruker IFS 125 HR FTIR spectrometer. The measurements were performed at room temperature, at the spectral resolution of 0.01 cm⁻¹ and in a wide pressure range of H₂. The calculations of the broadening γ and shift δ coefficients were performed in the semi-classical method framework with use of an effective vibrationally depended interaction potential. Two potential parameters were optimised to improve the quality of calculations. Good agreements with measured broadening coefficients were achieved. The comparison of calculated broadening coefficients γ with the previous measurements is discussed. The analytical expressions that reproduce these coefficients for rotational, ν₂, ν₁, and ν₃ vibrational bands are presented.