2nu3 band of 12CF4 and its simultaneous analysis with nu3

Abstract A nearly Doppler-limited spectrum of the 2ν 3 band of the 12 CF 4 molecule between 2536.0 and 2599.8 cm −1 was recorded at T = 77 K using difference-frequency laser spectroscopy. The simultaneous analysis of the ground (G.S.), ν 3 = 1, and ν 3 = 2 states was performed using an isolated band model to sixth order in the tetrahedral formalism. Fourteen hundred seventy-five transitions were assigned through J = 35 to the F 2 and E vibrational components of the ν 3 = 2 level. A total of 1864 transition frequencies were fit simultaneously (1000 2ν 3 - G.S. newly assigned transitions together with 575 ν 3 - G.S. and 289 ν 3 - ν 3 transitions already reported in the literature). The ground…

Nitrogen broadening of SF6 transitions in the nu3 band

Abstract Nitrogen induced pressure-broadened halfwidths of a number of ν3 transitions of SF6 are calculated using the complex Robert–Bonamy (CRB) formalism. The calculations are made at 200, 250, 296 and 350 K and the temperature dependence of the halfwidths are determined. The intermolecular potential is taken as a sum of the leading electrostatic and Lennard-Jones [6] , [7] , [8] , [9] , [10] , [11] , [12] atom–atom components. The dynamics of the collision process are correct to second order in time. The calculated halfwidths are used to simulate the ν3 spectrum, which is compared to a simulation made using the HITRAN96 halfwidths and measurements made at the Universite Pierre et Marie C…

Calculated helium-broadened line parameters in the nu4 band of 13CH4

International audience; Helium line-broadening coefficients for transitions in the nu4 band of 13CH4 have been calculated using a semi-classical model. This model is analogous to the one that we have used in a previous study on argon line-broadening coefficients for transitions in the nu3 band of 12CH4. For the present study, over 270 room temperature measurements were considered. The J, symmetry and fine structure dependences of the data are satisfactorily reproduced, although deficiencies of the semi-classical model are evidenced.

Model, software and database for line-mixing effects in the ν3 and ν4 bands of CH4 and tests using laboratory and planetary measurements-I: N2(and air) broadenings and the earth atmosphere

International audience; Absorption spectra of the infrared ν3 and ν4 bands of CH4 perturbed by N2 over large ranges of pressure and temperature have been measured in the laboratory. A theoretical approach accounting for line mixing is proposed to (successfully) model these experiments. It is similar to that of Pieroni et al. [J Chem Phys 1999;110:7717–32] and is based on state-to-state rotational cross-sections calculated with a semi-classical approach and a few empirical parameters. The latter, which enable switching from the state space to the line space, are deduced from a fit of a single room temperature spectrum of the ν3 band at 50 atm. The comparisons between numerous measured and ca…

Le méthane dans l'atmosphère de Titan. De la spectroscopie fondamentale à la planétologie

Le méthane (CH4) joue sur Tian, le plus gros satellite de Saturne, un rôle similaire à celui de l'eau sur Terre. Il y est de plus à l'origine d'une chimie organique complexe. La spectroscopie étant la technique privilégiée pour mesurer le CH4 dans les atmosphères planétaires, des modèles précis de l'absorption de la lumière par cette molécule doivent être développés. Les résultats récents obtenus dans ce domaine à l'Institut Carnot de Bourgogne, en collaboration étroite avec des planétologues, permettent notamment de contribuer à l'interprétation des résultats de la mission Cassini-Huygens.

Nanotubes de carbone alignés synthétisés par CCVD : optimisation de rendement de synthèse et extension sur grandes surfaces pour matériaux multifonctionnels

International audience

Etat de l'Art des Analyses Raie par Raie des Spectres du Méthane

The methane Raman spectrum up to 5500 cm-1. Application to the diagnostic of temperature in combustion media

The methane Raman spectrum from 1200 to 5500 cm(-1): A first step toward temperature diagnostic using methane as a probe molecule in combustion systems

International audience; We present a study of the spontaneous Raman spectra of (CH4)-C-12 from 1200 to 5500 cm(-1) at various temperatures. This study is of interest from a fundamental as well as from a practical point of view with regards to the temperature diagnostic in hydrocarbon combustion. The present investigation shows that the spontaneous (CH4)-C-12 Raman spectra are very sensitive to temperature and that the complexity of methane spectra is not an obstacle to use methane as a probe molecule in laser-diagnostic techniques. Our study consists in determining the polarisability parameters of methane (CH4)-C-12, unknown at the present time, from spontaneous Raman spectra recorded at pr…

N2-, O2- and air-broadened half-widths and line shifts for transitions in the nu3 band of methane in the 2726- to 3200-cm-1 spectral region

International audience; Complex Robert-Bonamy calculations of the pressure-broadened half-width and the pressure-induced line shift are made for some 4000 transitions in the [nu]3 band of methane with N2, O2, and air as the perturbing gases. This work focuses on A and F symmetry transitions in the spectral range 2726 to 3200 cm-1. More work is needed on the intermolecular potential before calculations can be made for the E-symmetry transitions. The calculations are made at 225 and 296 K in order to determine the temperature dependence of the half-width. The calculations are compared with measurements. These data are to support remote sensing of the Earth and Titan atmospheres.

Model, software and database for line-mixing effects in the nu3 and nu4 bands of CH4 and tests using laboratory and planetary measurements - II : H2 (and He) broadening and the atmospheres of Jupiter and Saturn

International audience; The absorption shapes of the nu(2), nu(3) and nu(4) infrared bands of CH4 perturbed by H-2 in large ranges of pressure and temperature have been measured in the laboratory. In order to model these spectra, the theoretical approach accounting for line-mixing effects proposed for CH4-N-2 and CH4-air and successfully tested in the companion paper (1), is used. As before, state-to-state rotational rates are used together with some empirical parameters that are deduced from a fit of a single room temperature spectrum of the nu(3) band at about 50 atm. The comparisons between measured and calculated spectra in the nu(3) and nu(4) regions under a vast variety of conditions …

Symmetry-adapted tensorial formalism to model rovibrational and rovibronic spectra of molecules pertaining to various point groups

International audience; We present a short review on the tensorial formalism developed by the Dijon group to solve molecular spectroscopy problems. This approach, originally devoted to the rovibrational spectroscopy of highly symmetrical species (spherical tops) has been recently extended in several directions: quasi-spherical tops, some symmetric and asymmetric tops, and rovibronic spectroscopy of spherical tops in a degenerate electronic state. Despite its apparent complexity (heavy notations, quite complex mathematical tools), these group theoretical tensorial methods have a great advantage of flexibility: a systematic expansion of effective terms for any rovib- rational/rovibronic probl…

Speed-dependent broadening and line mixing in CH4 perturbed by Ar and N2 from multispectrum fits

International audience; Speed-dependent broadenings and shifts have been determined for the P and R branches of the nu3 band of CH4 perturbed by Ar and N2 using a multispectrum fitting analysis of high-resolution tunable difference-frequency laser spectra recorded at pressures 3, the tetrahedral fine structure components in each J manifold are collisionally coupled and exhibit significant interference. The coupled lines are treated using a speed-dependent first-order line-mixing profile and are compared to a speed-independent full relaxation matrix inversion procedure with off-diagonal coupling elements calculated from an atom-atom Lennard-Jones potential model.

Line broadening coefficient calculations for methane perturbed by nitrogen

Abstract We report semiclassical line broadening calculations for methane perturbed by nitrogen at room temperature. For this, we have developed a symmetrized version of the Robert and Bonamy theory. The interaction potential was built from electrostatic (octopole and hexadecapole for methane, quadrupole for nitrogen) and atom–atom contributions. The relative (classical) trajectories of the molecules were computed in the frame of the usual parabolic model, through analytical formula. High orders of developments had to be used for the short range molecular interactions. As a consequence, a combination of symbolic computation and source code generation was employed to implement practical calc…

Measurement of rotational relaxation in the ground state of methane perturbed by argon at low temperature

International audience; Relaxation processes at low temperature in methane perturbed by argon have been investigated on the basis of new measurements. Diode laser absorption spectra of methane in the region of the dyad nu2/nu4 in supersonic expansions have been recorded. The time of relaxation of the ground state mean rotational energy was derived from the observed dependences of the rotational temperature on the concentration in the jet. A semi-classical model was used to calculate the state-to-state relaxation rate constants at room temperature. The evaluation of the time of relaxation of the mean rotational energy using semi-empirical temperature dependence laws is presented and discusse…

Spectroscopic tools for remote sensing of greenhouse gases CH4, CF4 and SF6

International audience; Highly symmetrical molecules such as CH4, CF4 or SF6 are known to be atmospheric pollutants and greenhouse gases. High-resolution spectroscopy in the infrared is particularly suitable for the monitoring of gas concentration and radiative transfers in the earth's atmosphere. This technique requires extensive theoretical studies for the modeling of the spectra of such molecules (positions, intensities and shapes of absorption lines). Here, we have developed powerful tools for the analysis and the simulation of absorption spectra of highly symmetrical molecules. These tools have been implemented in the spherical top data system (STDS) and highly-spherical top data syste…

Pressure‐induced widths and shifts for the ν3 band of methane

International audience; Widths and shifts of methane lines perturbed by nitrogen are calculated using a complex-valued implementation of Robert-Bonamy (RB) theory. The static intermolecular potential is described as a sum of electrostatic forces and Lennard-Jones (6-12) atom-atom terms, using literature values for all physical parameters. Vibrational dependence of the isotropic potential is obtained from the polarizability of methane assuming a dispersion interaction. The repulsive part of the Lennard-Jones accounts for the greatest part of widths, while dispersion interactions are largely responsible for shifts. Although the average error between calculated and observed linewidths (up to J…

Self and N2 Collisional Broadening of Methane in the THz Region Measured at the SOLEIL Synchrotron

Argon-broadened line parameters in the nu3 band of 12CH4

International audience; Prompted by improved measurements of collisional line shapes in the nu3 band P, Q and R branches of 12CH4, we have performed semi-classical line broadening calculations for methane perturbed by argon. We have used the theoretical approach developed by Robert and Bonamy as an extension of the well-known Anderson-Tsao-Curnutte theory. The semi-classical theory as reformulated here is shown to fully account for the tetrahedral symmetry of methane type molecules. The variation of argon-broadened linewidth coefficients in the nu3 band of 12CH4 with the branch, J, symmetry and energy level fine structure is discussed.

Experimental and theoretical study of line mixing in methane spectra. III. The Q branch of the Raman nu(1) band

International audience; The shape of the nu(1) Raman Q branch of CH4 perturbed by Ar and He at room temperature has been studied. Stimulated Raman spectroscopy (SRS) experiments have been made in the 2915-2918 cm(-1) spectral region for total pressures from 0.4 to 70 atm and mixtures of approximate to 5% CH4 with He and Ar. Analysis of the spectra demonstrates that the shape of the Q branch is significantly influenced by line mixing and much narrower than what is predicted by the addition of individual line profiles. For the first time, a model is proposed for the calculation and analysis of the effects of collisions on the considered spectra. In this approach, the rotational part of the re…

Methane in Titan's atmosphere: from fundamental spectroscopy to planetology

The methane molecule (CH4) is relatively abundant in the Universe and in particular in our Solar System. On Earth, it is the main compound of natural gas and is also the second greenhouse gas of anthropic origin. On Saturn's satellite Titan it plays a role similar to water on Earth and leads to a complex chemistry.

Le méthane dans l’atmosphère de Titan - De la spectroscopie fondamentale à la planétologie

Le methane (CH4) joue sur Tian, le plus gros satellite de Saturne, un role similaire a celui de l'eau sur Terre. Il y est de plus a l'origine d'une chimie organique complexe. La spectroscopie etant la technique privilegiee pour mesurer le CH4 dans les atmospheres planetaires, des modeles precis de l'absorption de la lumiere par cette molecule doivent etre developpes. Les resultats recents obtenus dans ce domaine a l'Institut Carnot de Bourgogne, en collaboration etroite avec des planetologues, permettent notamment de contribuer a l'interpretation des resultats de la mission Cassini-Huygens.

Helium and Argon Line Broadening in the nu2 Band of CH4

Abstract The spectra of the gaseous mixtures CH 4 –He and CH 4 –Ar were obtained in the spectral region 1400–1750 cm −1 with a resolution up to 0.003 cm −1 . Helium and argon pressure broadenings for the vibration–rotation lines of the ν 2 band of CH 4 have been estimated at room temperature for some lines in the P , Q , and R branches. These values were also calculated using the theoretical approach developed by Robert and Bonamy, extended to the case of tetrahedral molecules. The helium data have been found to be in a satisfactory agreement whereas a divergence of calculated and measured broadening coefficients has been evidenced in the case of argon. Simulations of the ν 2 band shapes of…

Estimation of line parameters under line mixing effect: the nu3 band of CH4 in helium

International audience; Spectra of CH4-He mixtures were measured in the P and R branch regions of nu3 vibration-rotation band at lower pressures of 0.26-1.0 bar and for the whole band at higher pressures up to 90 bar. The line broadening coefficients were found from lower pressure data for the lines of the P branch. These coefficients were calculated in the framework of the Robert and Bonamy semi-classical approach. In general, they agree with the experimental ones, but a small J-dependent deviation was observed. Line mixing effects were observed at all pressures. At higher pressures they were interpreted in terms of the adjusted branch-coupling model. At lower pressures line mixing effects…

Self and N-2 collisional broadening of far-infrared methane lines measured at the SOLEIL synchrotron

International audience; Following our recent study devoted to measurements of intensities of pure rotation lines of methane, room temperature far infrared spectra of methane diluted in nitrogen at five total pressures between 100 and 800 hPa have been recorded at the AILES beamline of the SOLEIL synchrotron. One hundred and five N-2 broadening coefficients of methane pure rotation lines have been measured in the 83-261 cm(-1) spectral range using multi-spectrum non-linear least squares fitting of Voigt profiles. Pressure-induced line shifts were not needed to fit the spectra to the noise level and line mixing effects were neglected. One hundred and seventy-six self broadening coefficients h…

Etude des effets collisionnels dans les molécules tétraédriques. Applications au méthane perturbé par l'argon

This thesis is devoted to the study of relaxational and collisional line-broadening processes in the first vibrational polyads of tetrahedral molecules. In a first part, the particular internal dynamics of such molecules is discussed. The second chapter reviews the literature on phenomena induced by intermolecular interactions involving this type of molecules. More theoretical aspects are developed in the second part. The so-called tetrahedral tensorial formalism adapted to the construction of Hamiltonians and transition moments of tetrahedral molecules is described. Main features of the infrared line-shapes theories and of semi-classical line-broadening and line-shifting calculations are a…

Femtosecond Raman Spectroscopy of C2H4 and CH4 molecules

Methane line parameters in HITRAN

Abstract Two editions of the methane line parameters (line positions, intensities and broadening coefficients) available from HITRAN in 2000 and 2001 are described. In both versions, the spectral interval covered was the same (from 0.01 to 6184.5 cm −1 ), but the database increased from 48,033 transitions in 2000 to 211,465 lines in 2001 because weaker transitions of 12 CH 4 and new bands of 13 CH 4 and CH3D were included. The newer list became available in 2001 in the “Update” section of HITRAN. The sources of information are described, and the prospects for future improvements are discussed.

Near-infrared radiative transfer modelling with different CH4 spectroscopic databases to retrieve atmospheric methane total amount

International audience; Atmospheric methane content can be retrieved from measurements of solar radiation attenuated by the atmosphere in the near infrared spectral region where the space-borne and ground-based spectrometers carry out regular measurements. It is shown, in the present work, that the different spectroscopic databases can give significantly different results for both forward simulations of the atmospheric transmittance and the inverse problem solution to retrieve the CH4 total content in the atmosphere using spectra measured by ground-based FTIR spectrometer in the near infrared spectral region. These discrepancies and the problem of the reduction of their influence on the atm…

Calculated line broadening parameters for methane perturbed by diatomic molecules

International audience; We report semiclassical line broadening calculations for methane perturbed by diatomic molecules: nitrogen, N2, oxygen, O2 and hydrogen, H2, at room temperature. For this, we have developed a symmetrized version of the Robert and Bonamy theory. The interaction potential was built from electrostatic (octopole and hexadecapole for methane, quadrupole for the diatomic molecules) and atom-atom contributions. The relative (classical) trajectories of the molecules were computed in the frame of the usual parabolic model, through analytical formula. High orders of developments had to be used for the short range molecular interactions in the case of N2 and O2. For H2, a lower…

Hydrogen CARS thermometry in H2-N2 mixtures at high pressure and medium temperatures: influence of linewidths models

International audience; In order to improve the accuracy of H2 CARS thermometry, H2 Q-branch CARS spectra have been recorded for various H2-N2 mixtures in a high-pressure cell at different pressures and temperatures (up to 40 bar and 875 K). Due to the low spectral resolution of broadband CARS experiments, the relevant spectral lineshape factor is the linewidth ratio G(Q(3))/G(Q(1)), since Q(1) and Q(3) are the most intense lines of the Q-branch spectrum in this temperature range. For the first time, the speed-inhomogeneous effects are accounted for in the simulation of the CARS profiles. The evaluated temperatures are in good agreement with reference values obtained by thermocouples. The s…

Calculated Line Broadening Coefficients in the nu2 Band of CH3D Perturbed by Helium

International audience; Line broadening coefficients have been calculated, at room temperature, for lines in the P and R branches of the nu2 band of monodeuterated methane. A properly symmetrized semiclassical model with parabolic relative trajectories has been used. Two interaction potential models have been considered. The first is a Lennard-Jones type atom-atom potential, while the second one was derived from ab initio calculations. The calculated line widths were compared to the available experimental data and a satisfactory agreement was found, although the model contains no other adjustable parameters than the four atomic Lennard-Jones ones. Nonetheless, failures of calculations have …

CARS spectroscopy of CH4 for implication of temperature measurements in supercritical LOX/CH4 combustion

International audience; Experimental and theoretical investigations of coherent anti-Stokes Raman spectroscopy of CH4 have been carried out. Experimental spectra were measured in a heated high-pressure test cell and compared with numerical simulations. Good agreement was obtained for the temperature and the pressure dependence of CARS spectra in the ranges 300-1100 K and 0.1-5.0 MPa. The observed dependencies provide useful guidance for CARS thermometry, allowing quantitative measurements of temperature in high-pressure combustors. Application of multiplex CH4 CARS thermometry for single-shot measurements in a LOX/CH4 combustion at high pressure was demonstrated at supercritical conditions …

Line parameters and shapes of high clusters: R-branch of the nu3 band of CH4 in He mixtures

International audience; The IR absorption spectra of CH4 in pure gas and in mixture with helium were studied in the region of nu3 band at higher J line clusters R(17)-R(22). The frequencies and intensities of rotation-vibration lines were estimated from the experimental spectra at Doppler shape conditions. The line frequencies and intensities were calculated and used for the attribution of overlapped lines in clusters. The calculated line intensities are close to the experimental values. The calculated frequency structure of the higher J manifolds are somewhat wider than the observed one. The shapes of helium-broadened line clusters were compared with those calculated accounting for line mi…

Experimental and theoretical study of line mixing in methane spectra. III. The Q branch of the Raman ν1 band

The shape of the ν1 Raman Q branch of CH4 perturbed by Ar and He at room temperature has been studied. Stimulated Raman spectroscopy (SRS) experiments have been made in the 2915–2918 cm−1 spectral region for total pressures from 0.4 to 70 atm and mixtures of ≈5% CH4 with He and Ar. Analysis of the spectra demonstrates that the shape of the Q branch is significantly influenced by line mixing and much narrower than what is predicted by the addition of individual line profiles. For the first time, a model is proposed for the calculation and analysis of the effects of collisions on the considered spectra. In this approach, the rotational part of the relaxation matrix is constructed, with no adj…

Spherical Top Theory and Molecular Spectra

In this article, we present an overview of the present state of the art of the theory of high-resolution spherical-top spectra in the framework of the effective Hamiltonian approach. We describe the specific features of this class of molecules to explain the basic concepts of the theoretical methods used for the analysis (line positions and intensities) and the simulation of absorption (including pure rotation) and Raman spectra of such species. The non conventional formalism that we use is essentially based on irreducible tensor methods and is especially adapted to computational treatments and global analyses of complex interacting band systems. We give examples concerning mainly methane (…

Near-Infrared Radiative Transfer Modeling with Different CH4 Databases to Retrieve Atmospheric Methane Total Amount

Multispectrum fits for line mixing in the ν3 band Q branch of methane

International audience; First-order line-mixing coefficients and model relaxation matrix element scaling factors have been obtained for allowed transitions in the nu3 band Q branch of CH4 broadened by H2, He, N2, O2, Ar, and CH4. The broadening, shifting, Dicke-narrowing, and line-mixing parameters are determined by simultaneous least-squares fitting of spectra at pressures from 0.014 to 66.66 kPa recorded with a high-resolution difference-frequency laser. These results confirm, improve, and extend a previous analysis of the lower pressure (613.3 kPa) data [A.S. Pine, J. Chem. Phys. 97 (1992) 773] which yielded averaged coefficients of individually fit spectra where adjacent broadened lines…

Methane line parameters in the HITRAN2012 database

International audience; The compilation of methane molecular line parameters was updated to include new global analyses and measurements for 12CH4, 13CH4 and 12CH3D. Over 70% of the methane parameters in HITRAN2008 were replaced; existing parameters retained were the microwave lines and the Dyad of 13CH4 near 7 μm and ν6 of 13CH3D near 8.7 μm, 12CH3D (7-4076 cm-1), hot bands of 12CH4 (1887-3370 cm-1) and normal sample CH4 (4800-5550 cm-1 and 8000-9200 cm-1). With a minimum intensity at 296 K in units of cm-1/(molecule cm-2) set to 10-37 for the far-IR and 10-29 for the mid- and near-IR, the methane database increased from 290,091 lines in HITRAN2008 to 468,013 lines, and three-fourths of th…

CARS methane spectra: Experiments and simulations for temperature diagnostic purposes

International audience; CARS laboratory experiments were done in the 2905-2925 cm(-1) range, in the vicinity of the v, band of the methane molecule, for pressures ranging from I to 50 bar, and temperatures up to 1100 K. These experiments were carried out in order to retrieve the pressure evolution of the CH4 spectrum, as well as to confirm its temperature dependance. After a brief recall on the theory used to compute pressure broadening coefficients and relaxation rates, we consider the v(3) and v(4) infrared bands of methane for benchmark calculations purposes. Next, we present recent experimental CARS spectra and calculated ones. Lastly, we discuss flame experiments as well as comparisons…