Vladimir Tyuterev

• Professor
• Senior researcher at National Research Tomsk State University

In this work, we provide the most complete to date reference data for 28 572 rovibrational levels of the electronic ground state of the ozone ¹⁶O3 molecule up to the maximum rotational quantum numbers J = 80, Ka = 29 determined from 75 290 experimental transitions covering the range (0.3–7999) cm⁻¹. These energy levels belong to 98 vibrational stat...

High-resolution spectra corresponding to the rotational and the ν 2 –ν 2 bands of the two most abundant isotopic species of ozone with one heavy ¹⁸ O oxygen atom were recorded using SOLEIL synchrotron radiation source in the range 30–200 cm ⁻¹ . Additionally, the ν 2 vibrational-rotational bands were recorded between 550 and 880 cm ⁻¹ using a class...

Energies and lifetimes of vibrational resonances were computed for $^{18}$O-enriched isotopologue $^{50}$O$_3$= \{$^{16}$O$^{16}$O$^{18}$O and $^{16}$O$^{18}$O$^{16}$O\} of the ozone molecule using hyperspherical coordinates and the method of complex absorbing potential. Various...

Recent results of a long-term effort of Tomsk-Reims research teams on accurate intensity data obtained from high-resolution absorption spectra of ozone suitable for the atmospheric remote sensing in a wide IR range are summarized. This includes vibronic bands corresponding to the transitions towards triplet electronic states near 1 µm, and vibratio...

Due to its major interest for the chemistry of planetary atmospheres and exobiology, accurate spectroscopy data of phosphine are required for the search of signatures of this molecule in astronomical observations. In this work, high resolution infrared laboratory spectra of phosphine were analyzed for the first time in the full Tetradecad region (3...

In this work, a series of potential energy surfaces (PESs) of S2O was constructed in order to get the most accurate ab initio band origins of this massive molecule. The convergence of the coupled cluster energies with respect to both basis set size [aug-cc-pCVXZ, X=T, Q, 5, and 6] and the order of the excitation [CC(n), n = 2, 3, and 4] was analyze...

Far infrared spectra of ozone, with natural and 17O- or 18O-enriched ozone isotopologues, was recorded in the 50-850 cm-1 spectral range at 0.001 cm-1 resolution on the AILES Beamline at Synchrotron SOLEIL. This study extends previous works [1-3] devoted to the analysis of the 50–150 cm-1 region to higher energy range (up to 200 cm-1) and permits o...

Ro-vibrational energy levels of acetylene are reported using variational nuclear motion calculations from new ab initio and empirically optimized full six-dimensional potential energy surfaces in the ground electronic state of the acetylene molecule. The calculations account for the triple, quadruple and quintuple excitations as well as relativisti...

The paper describes methods and fast computational algorithm for building effective Hamiltonians in molecular physics using perturbative approach. Separations of fast and slow variables are considered in the framework of contact transformations (CT). The particular focus is on a systematic derivation of effective models for rovibrational spectrosco...

The present Letter shows that the formation of ozone in ternary collisions O+O_{2}+M-the primary mechanism of ozone formation in the stratosphere-at temperatures below 200 K (for M=Ar) proceeds through a formation of a temporary complex MO_{2}, while at temperatures above ∼700 K, the reaction proceeds mainly through a formation of long-lived vibrat...

Internal vibrational and rotational partition functions are calculated for nine molecules that are abundant in the terrestrial atmosphere and some are also observed in planetary and exoplanet atmospheres. These molecules are often observed in non-local thermodynamic equilibrium (NLTE) conditions. Calculations are made for all isotopologues of these...

The first part of this review is a brief reminder of general information concerning atmospheric ozone, particularly related to its formation, destruction, observations of its decrease in the stratosphere, and its increase in the troposphere as a result of anthropogenic actions and solutions. A few words are said about the abandonment of the Airbus...

Four spectra of methane in natural isotopic abundance in the 4100-4300 cm⁻¹ region were recorded by using a Fourier transform spectrometer in Reims, France at long paths (202 m, 602 m, 1604 m and 1804 m) and different pressures. Additional spectra of ¹²CH4 covering the same region were obtained at 100-123 K for different pressures, 93 m path length...

The absorption spectrum of the ¹⁸O3 isotopologue of ozone was recorded by cavity-ring down spectroscopy between 7920 and 7985 cm⁻¹ with a routine noise equivalent absorption, αmin, on the order of a few 10⁻¹¹ cm⁻¹. This permitted to detect and analyze an extremely weak vibrational band assigned as 7ν1+ν3 following predictions from the ab initio pot...

Absorbing UV radiation, ozone protects life on Earth and plays a fundamental role in Earth's temperature balance. The formation of ozone occurs through the ternary recombination reaction: O$_2$+O+M $\rightarrow$ O$_3$+M, where M can be N$_2$, O$_2$ or Ar. Here, we developed a theoretical approach capable of modeling the formation of ozone molecules...

The paper presents the results of the analysis of experimental FTS infrared vibration-rotation spectra of ¹⁶O3 ozone isotopologue recorded in Reims University in the range from 900 to 5600 cm⁻¹, which was used for the current version of the S&MPO database and web-accessible information system (http://smpo.iao.ru; http://smpo.univ-reims.fr). The maj...

The HITRAN database is a compilation of molecular spectroscopic parameters. It was established in the early 1970s and is used by various computer codes to predict and simulate the transmission and emission of light in gaseous media (with an emphasis on terrestrial and planetary atmospheres). The HITRAN compilation is composed of five major componen...

The Franck-Condon factors were calculated for vertical electronic transitions between the ground singlet (X1A1) and 3A2, 3B2, and 3B1 excited triplet states associated with the Wulf band of the ozone molecule O3. The XMCQDPT2 ab initio method including the static and dynamic electronic correlations was used with the aug-cc-pVQZ basis set. Along wit...

This paper describes the 2020 release of the GEISA database (Gestion et Etude des Informations Spectroscopiques Atmosphériques: Management and Study of Atmospheric Spectroscopic Information), developed and maintained at LMD since 1974. GEISA is the reference database for several current or planned Thermal and Short-Wave InfraRed (TIR and SWIR) spac...

Accurate knowledge of line parameters, and particularly line intensities is of primary importance for satellite, ground based and balloon measurements of the ozone concentration in the atmosphere. Self-consistency in absolute band intensities of ozone in various spectral intervals is necessary to avoid discrepancies in the atmospheric ozone retriev...

The first accurate and complete theoretical room-temperature rotationally resolved spectra in the range 300-3000 cm-1 are reported for the three most abundant isotopologues (32SF6, 33SF6 and 34SF6) of the sulfur hexafluoride molecule. The literature reports that SF6 is widely used as a prototype molecule for studying the multi-photon excitation pro...

Total internal partition sums (TIPS) are reported for the 181 isotopologues of 57 molecules important in planetary atmospheres. Molecules 1 to 55, with the exception of #34 atomic oxygen, are taken from the HITRAN2020 list, and for some molecules additional isotopologues are considered. Molecules 56 and 57 are C3H4, CH3, respectively. New to TIPS a...

Multiphoton spectroscopy of monodeuterated water is employed to determine more than 210 new energy levels of HDO in the 25 000 – 35 000 cm−1 region. These new empirical energy levels are used to fit a potential energy surface (PES) valid between 20 000 cm−1 and 35 000 cm−1. Using this PES and an accurate lower energy PES as starting points, an ener...

The pump-probe technique for investigating vibrationally excited states via high resolution Raman spectroscopy was applied to ¹³CH4 methane isotopologue. The dipole transitions between A1 totally symmetric vibrational states are not active in IR spectra but these states can be efficiently studied using selective high resolution Raman spectroscopy....

Thirteen bands of the CS symmetry ¹⁶O¹⁸O¹⁸O ozone isotopic species were observed in spectra generated from ¹⁶O2/¹⁸O2 mixtures recorded between 950 and 3500 cm⁻¹. Experimentally and theoretically this work is similar to the one on the ¹⁶O¹⁶O¹⁸O isotopologue analysis, recently published [Barbe A, et al. J. Quant. Spectrosc. Radiat. Transfer, 2018;218...

Vibrational energy levels of H2CO are reported using variational nuclear motion calculations from new ab initio and empirically optimized full 6-dimensional ab initio potential energy surfaces in the ground electronic state of the formaldehyde molecule. Ab initio calculations were carried out using extended electronic structure coupled-cluster calc...

Mass-dependent diagonal Born-Oppenheimer corrections (DBOCs) to the ab initio electronic ground state potential energy surface for the main 16O3 isotopologue and for homogeneous isotopic substitutions 17O3 and 18O3 of the ozone molecule are reported for the first time. The system being of strongly multiconfigurational character, multireference conf...

Ozone formation and depletion play a key role in various physical and chemical atmospheric processes which remain to be understood in more detail. The modeling of such phenomena based on ozone dynamics calculations requires a detailed knowledge of quantum states, transition probabilities, and ozone potential energy surface (PES) near the dissociati...

This paper presents an overview of the current status of the Virtual Atomic and Molecular Data Centre (VAMDC) e-infrastructure, including the current status of the VAMDC-connected (or to be connected) databases, updates on the latest technological development within the infrastructure and a presentation of some application tools that make use of th...

This paper presents an overview of the current status of the Virtual Atomic and Molecular Data Centre (VAMDC) e-infrastructure, including the current status of the VAMDC-connected (or to be connected) databases, updates on the latest technological development within the infrastructure and a presentation of some application tools that make use of th...

In this paper, we report a series of transformations for the construction of a Hamiltonian model for nonrigid polyatomic molecules in the framework of the Hougen–Bunker–Johns formalism (HBJ). This model is expressed in normal mode coordinates for small vibrations and in a specific coordinate ρ to describe the large amplitude motion. For the first t...

A 15-dimensional analytical form for the potential energy and dipole moment surfaces of the SF6 molecule in the ground electronic state is obtained using ab initio methods. In order to calculate the equilibrium S-F distance, we applied coupled cluster CCSD(T) method and several versions of the correlation consistent basis sets - from valence triple...

Knowledge of highly excited rovibrational states of ozone isotopologues is of key importance for modelling the dynamics of exchange reactions, for understanding longstanding problems related to isotopic anomalies of the ozone formation, and for analyses of extra-sensitive laser spectral experiments currently in progress. This work is devoted to new...

Four spectra of normal samples of CH4 in the 4300-4600 cm⁻¹ region were recorded by using a Fourier transform spectrometer in Reims, France at long paths (202 m, 602 m, 1604 m, and 1804 m) and different pressures. Additional spectra of ¹²CH4 covering the same region were obtained at 80-123 K, and 93 m path length at SOLEIL Synchrotron in Paris for...

div>Mass-dependent diagonal Born-Oppenheimer corrections (DBOC) to the ab initio electronic ground state potential energy surface for tseveral isotopologues of the ozone molecule are reported for the first time. The comparison with experimental band centers shows a significant improvement of the accuracy with respect to the best Born-Oppenheimer (B...

A methane line list for the HITEMP spectroscopic database, covering 0-13,400 cm-1 (>746 nm), is presented. To create this compilation, ab initio line lists of 12CH4 from Rey et al. ApJ, 847, 105 (provided at separate temperatures in the TheoReTS information system), are now combined with HITRAN2016 methane data to produce a single line list suitabl...

The study of quantum states near the dissociation threshold is necessary both to understand the formation of molecules and to explore accurately chemical reactions. Quantum calculations of highly excited states can be complemented by methods of nonlinear classical mechanics that help revealing the stable modes of molecular vibrations and their tran...

A methane line list for the HITEMP spectroscopic database, covering 0-13,400 cm$^{-1}$ ($>$746 nm), is presented. To create this compilation, ab initio line lists of $^{12}$CH$_{4}$ from Rey et al. (2017) ApJ, 847, 105 (provided at separate temperatures in the TheoReTS information system), are now combined with HITRAN2016 methane data to produce a...

This work continues our investigation on the high resolution infrared ¹³C-enriched spectrum of methane recorded on a Bruker IFS-125HR Fourier transform spectrometer at 80 K in the 4970–6200 cm⁻¹ range. In this paper we report the results of assignment and modelling of the line positions and intensities of ¹³CH4 in the range between 5471 and 5852 cm...

In this work we report first global modeling of NF3 line positions and intensities up to the Tetradecad range of interacting bands (< 2200 cm⁻¹). The calculations are based on our ab initio potential energy and dipole moment surfaces of NF3 which are used to compute initial theoretical line lists. The technique of six order contact transformations...

We consider the time-dependent dynamics of the isotope exchange reaction in collisions between an oxygen molecule and an oxygen atom: ¹⁶O¹⁶O + ¹⁸O → ¹⁸O¹⁶O + ¹⁶O. A theoretical approach using the Multiconfiguration Time-Dependent Hartree method was employed to model the time evolution of the reaction. Two potential surfaces available in the literat...

Reduced matrix elements (RMEs) for collisionally induced transitions are an important component of semi-classical line shape calculations. They give the quantum mechanical probability for a transition in the radiating molecule occurring due to a collision with one of the bath molecules. The RMEs for both the radiating and perturbing molecules are p...

In this paper, we report accurate first-principles variational rovibrational spectra predictions for the three double deuterated ethylene isotopologs denoted as cis, trans, and as-¹²C2H2D2. Calculations were performed in the framework of the normal-mode approach using our ab initio ¹²C2H4 (D2h) Born-Oppenheimer potential energy and dipole moment su...

Ozone spectroscopic data such as absorption cross sections in the visible and UV spectral ranges or line parameters in the IR and MW domains are at the heart of in-situ and remote sensing of atmospheric ozone and are a necessity for new developments in multispectral remote sensing [1]. However, the reactivity of the ozone molecule makes experimenta...

Reliable ozone spectral data consistent over several spectral ranges are a challenge for both experiment and theory. We present ab initio calculations for strong lines that lead to consistent results from the microwave to mid-infrared regions. The results agree well with established microwave line lists and our new measurements in the fundamental a...

This work continues the investigation of high resolution infrared spectra of ¹⁷ O and ¹⁸ O enriched ozone isotopomers in the 10 µm spectral range. Spectra are recorded by the Reims Fourier Transform Spectrometer. In a mixture of 18 isotopic species of ozone including ¹⁷ O, ¹⁶ O and ¹⁸ O oxygen atoms, two ν 3 bands are analyzed for the first time: t...

The Fourier transform spectrum of CF4 in the 1600–1800 cm−1 was recorded in Reims by using a White-type multi-pass cell to provide a path length of 8.262 m. In the present work, all spectrum analyses and fits were realized using the MIRS software based on tetrahedral tensorial formalism. By combining non-empirical contact transformation Hamiltonian...

Spectra of hot methane were recorded using a tube furnace and a high-resolution Fourier transform spectrometer. We obtained experimental absorption spectra in the 1.85-1.11 μm near-infrared region at eight temperatures ranging from 295 K up to 1000 K. We have converted these into an atlas of absorption cross sections at each temperature for the met...

The isotopic exchange reaction, ¹⁶O + ¹⁸O¹⁸O → ¹⁶O¹⁸O + ¹⁸O, involving excited ozone, O3, as intermediate complex, was investigated by means of a time independent quantum mechanical approach using the TKTHS potential energy surface (PES) [V. G. Tyuterev et al., J. Chem. Phys. 139, 134307 (2013)] of ozone. State-to-state integral cross sections were...

Eight spectra of normal samples of CH4 in the 3760–4100 cm⁻¹ region were recorded by using a Fourier transform spectrometer in Reims, France at long paths (202 m, 602 m, 1604 m and 1804 m) and different pressures. Additional spectra of ¹²CH4 covering the same region were obtained at 100 K and very low sample pressures, which was used for low-J line...

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 3 v ). Energy level and line intensity calculations were performed by using a normal-mode model combined with iso...

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 tw...

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 intens...

Fluorine containing molecules have particularly long atmospheric lifetime and their very big estimated global warming potentials are expected to rapidly increase in future. This work is focused on global theoretical...

Fifteen bands of the most abundant asymmetric ozone isotopomer ¹⁶O¹⁶O¹⁸O were observed in new spectra generated from various ¹⁸O2/¹⁶O2 mixtures in the 950–3850 cm⁻¹ range. These bands were fully analyzed, leading to the assignment of a total of 9976 transitions, corresponding to 7030 upper state rovibrational energy levels. The analyses include als...

The ESA project „SEOM-Improved Atmospheric Spectroscopy Databases (IAS)“ will improve the spectroscopic database for retrieval of the data products CO, CH4, O3 and SO2 column amounts measured by the TROPOMI instrument (TROPOspheric Monitoring Instrument) aboard the Sentinel-5 Precursor. The project was launched in February 2014 with 3 years duratio...

The question whether a Berry phase should be included in the calculation of rovibronic states of the ozone molecule in its electronic ground state has been addressed in the present work. Since several conical intersections connect the three lowest singlet states, a phase of π generated by a symmetry-demanded conical intersection between states 2 an...

We show, by performing exact time independent quantum molecular scattering calculations, that the quality of the ground electronic state global potential energy surface appears to be of utmost importance in accurately obtaining even as strongly averaged quantities as kinetic rate constants. The oxygen isotope exchange reaction, 18O + 32O2, motivate...

The spectrum of methane is very important for the analysis and modeling of Titan’s atmosphere but its insufficient knowledge in the near infrared, with the absence of reliable absorption coefficients, is an important limitation. In order to help the astronomer community for analyzing high-quality spectra, we report in the present work the first acc...

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 1...

This paper describes the contents of the 2016 edition of the HITRAN molecular spectroscopic compilation. The new edition replaces the previous HITRAN edition of 2012 and its updates during the intervening years. The HITRAN molecular absorption compilation is composed of five major components: the traditional line-by-line spectroscopic parameters re...

A new study of ¹²CH4 line positions and intensities was performed for part of the Tetradecad region between 5300 and 5550 cm⁻¹ using four 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 b...

In this study, we present our latest measurement and theoretical results for self- and air-broadened transitions in the methane octad range. For this project, we have used a set of 14 spectra of pure methane and lean mixtures of methane and air, recorded at the Jet Propulsion Laboratory. The spectra were analyzed using a multispectrum fit program....

Accurate rovibrational analysis of the upper part of the Tetradecad ¹²CH4 spectrum in the 5855-6250 cm⁻¹ region is reported for J ≤ 10. The analysis uses the WKLMC experimental line list previously obtained in Grenoble by Cavity Ring Down Spectroscopy and Differential laser Absorption Spectroscopy at T= 296 K. Based on a previously published ab ini...

In this work, we report first-principle theoretical predictions of methane spectral line intensities that are competitive with (and complementary to) the best laboratory measurements. A detailed comparison with the most accurate data shows that discrepancies in integrated polyad intensities are in the range of 0.4% - 2.3%. This corresponds to estim...

Improved analysis of positions and intensities of phosphine spectral lines in the Octad region 2733-3660 cm⁻¹ is reported. Some 5768 positions and 1752 intensities were modelled with RMS deviations of 0.00185 cm⁻¹ and 10.9%, respectively. Based on an ab initio potential energy surface, the full Hamiltonian of phosphine nuclear motion was reduced to...

Ab initio dipole moment surfaces (DMSs) of the ozone molecule are computed using the MRCI-SD method with AVQZ, AV5Z, and VQZ-F12 basis sets on a dense grid of about 1950 geometrical configurations. The analytical DMS representation used for the fit of ab initio points provides better behavior for large nuclear displacements than that of previous st...

Two atmospheric trace gases, namely methane and carbon monoxide have been considered in this study. Fourier transform absorption spectra of the 2–0 band of ¹²C¹⁶O mixed with CO2 have been recorded at total pressures from 156 to 1212 hPa and at 4 different temperatures between 240 K and 283 K. CO2 pressure-induced line broadening and line shift coef...

Nine-dimensional potential energy surface (PES) and dipole moment surface (DMS) of the germane molecule are constructed using extended ab initio CCSD(T) calculations at 19882 points. PES analytical representation is determined as an expansion in non-linear symmetry adapted products of orthogonal and internal coordinates involving 340 parameters up...

Full 9-dimensional ab initio potential energy surfaces for the methane molecule are constructed using extended electronic structure coupled-cluster calculations with various series of basis sets following increasing X cardinal numbers: cc-pVXZ (X = 3, 4, 5, 6), aug-cc-ACVXZ (X = 3, 4, 5), and cc-pCVXZ-F12 (X = 3, 4). High-order dynamic electron cor...

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−...

Energies and lifetimes (widths) of vibrational states above the lowest dissociation limit of $^{16}$O$_3$ were determined using a previously-developed efficient approach, which combines hyperspherical coordinates and a complex absorbing potential. The calculations are based on a recently-computed potential energy surface of ozone determined with a...

Energies and lifetimes (widths) of vibrational states above the lowest dissociation limit of $^{16}$O$_3$ were determined using a previously-developed efficient approach, which combines hyperspherical coordinates and a complex absorbing potential. The calculations are based on a recently-computed potential energy surface of ozone determined with a...