First analysis of the ν3+ν5 combination band of SF6 observed at Doppler-limited resolution and effective model for the ν3+ν5-ν5 hot band

Abstract Sulfur hexafluoride is a greenhouse gas with a long lifetime in the atmosphere and an important tracer for air mass circulation atmospheric models. The IR spectrum of this heavy species, however, features many hot bands at room temperature (at which only 30% of the molecules lie in the ground vibrational state), especially those originating from the lowest, v 6 and v 5 = 1 vibrational states. Using a cryogenic long path cell with variable optical path length and temperatures regulated between 168 and 163 K, coupled to Synchrotron Radiation and a high resolution interferometer, Doppler-limited spectra of the very weak ν 3 + ν 5 band near 1450 cm−1 have been recorded. Low temperature…

High-Resolution Spectroscopy and Preliminary Analysis of the ν1/ν8 Dyad of SF535Cl

Abstract The Fourier transform infrared spectrum of monoisotopic SF 5 35 Cl has been recorded in the 650- to 960-cm −1 region at a temperature of 203 K, a pressure of 0.2 mbar, and an instrumental bandwidth of 0.002 cm −1 . The ν 1 /ν 8 dyad near 900 cm −1 has been analyzed with an effective Hamiltonian developed up to the fourth order and the help of a recently developed set of programs called C 4 v TDS ( C 4 v Top Data System, http://www.u-bourgogne.fr/LPUB/C4VTDS.html ); 1346 transitions for ν 1 , 351 transitions for ν 8 , and 406 ground state combination differences have been assigned and fitted. A global fit has been obtained with an rms of 0.00082 cm −1 for the ν 1 ( a 1 ) band, of 0.…

The SO2F2 quasi-spherical top: Correspondence between tensorial and Watson's formalisms

Abstract The SO2F2 quasi-spherical top molecule with C2v symmetry is considered as a distorted spherical top deriving from the SO 4 2 − tetrahedral ion. We present here a detailed correspondence between the tensorial formalism using the Td⊃C2v reorientation and the usual Hamiltonian of Watson. We have also performed ab initio calculations in order to determine the centrifugal distorsion constants in the vibrational ground state.

Analyse Globale en Fréquences et en Intensités des Raies de 12CH4 dans la Région 0–4800 cm-1

Dynamical Stark Effect in the nu(2)/nu(4) Vibrational Polyad of SiH(4): Theory and Observation.

We report a theoretical and experimental investigation of the dynamical Stark effect in a tetrahedral molecule, silane (SiH(4)). We use a tetrahedral formalism and Floquet theory to calculate the absorption spectra for the molecule dressed by an intense nonresonant pulsed laser. Experimentally, the dynamical Stark effect is observed for transitions of the nu(2)/nu(4) vibrational polyad of SiH(4) by means of nanosecond diode laser absorption spectroscopy and a Nd:YAG laser excitation. Copyright 2000 Academic Press.

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.

Development of the Hamiltonian and transition moment operators of symmetric top molecules using the O(3)⊃C∞v⊃C3v group chain

Abstract We present a development of the Hamiltonian, dipole moment, and polarizability operators for XY3Z molecules. These rovibrational operators are written with the aid of a tensorial formalism derived from the one already used in Dijon and adapted to the XY3Z symmetric tops in a recent paper [A. El Hilali, V. Boudon, M. Loete, J. Mol. Spectrosc. 234 (2005) 166–174]. We use the O (3) ⊃ C∞v ⊃ C3v group chain. Expressions for the matrix elements are derived for these operators.

The vibrational levels of methane obtained from analyses of high-resolution spectra

International audience; Methane and its tetrahedral isotopologues are spherical-top molecules whose high-resolution rovibrational spectra can only be analyzed in detail, thanks to sophisticated symmetry-adapted tensorial models. However, the effective Hamiltonian parameters of such models do not give direct access to the positions of the vibrational sublevels. In this paper, we present a calculation of the vibrational level positions for 12CH4, 13CH4, 12CD4 and 13CD4 performed using the effective Hamiltonian parameters obtained through recent analyses. We also include the results of a re-analysis of the octad system of 12CH4 performed with a higher order of the development which slightly im…

High-Resolution Spectroscopy and Preliminary Global Analysis of C–H Stretching Vibrations of C2H4 in the 3000 and 6000 cm-1 Regions

International audience; Ethylene (ethene, H2C=CH2) is a naturally occurring compound in ambient air that affects atmospheric chemistry and global climate. The C2H4 spectrum is available in databases only for the 1000 and 3000 cm−1 ranges. In this work, the ethylene absorption spectrum was measured in the 6030- 6250 cm−1 range with the use of a high resolution Bruker IFS 125HR Fourierspectrometer and a two-channel opto-acoustic spectrometer with a diode laser. As a secondary standard of wavelengths, the methane absorption spectrum was used in both cases. A preliminary analysis was realized thanks to the tensorial formalism developed by the Dijon group that is implemented in the XTDS software…

Measurement and Analysis of the Raman Intensities of 12CD4

0022-2852; The stimulated Raman spectrum of 12CD4 was recorded at high resolution, in the spectral range 1963 to 2260 cm(-1). Intensities of the rovibrational transitions were estimated by fitting the line profiles. The recorded elementary spectrum was 1 cm(-1) wide; all recordings were then intensity calibrated. Afterward, the relative Raman intensities were analyzed by using a polarizability model developed previously [A. Boutahar and M. Loete, Can. J. Phys. 69, 26-35 (1991); J. P. Champion, M. Loete, and G. Pierre, in ''Spectroscopy of the Earth's Atmosphere and Interstellar Molecules'' (K. Narahari Rao and A. Weber, Eds.), pp. 388-397, Academic Press, Boston. 1992]. The investigated reg…

Stark Effect Using Tensorial Formalism in the D2h Group: Application to the C2H4 Molecule

Spherical Top Spectra

The ground state rotational spectrum of SO2F2

Abstract The analysis of the ground state rotational spectrum of SO 2 F 2 [K. Sarka, J. Demaison, L. Margules, I. Merke, N. Heineking, H. Burger, H. Ruland, J. Mol. Spectrosc. 200 (2000) 55] has been performed with the Watson’s Hamiltonian up to sextic terms but shows some limits due to the A and S reductions. Since SO 2 F 2 is a quasi-spherical top, it can also be regarded as derived from an hypothetical XY 4 molecule. Thus we have developed a new tensorial formalism in the O (3)⊃ T d ⊃ C 2 v group chain (M. Rotger, V. Boudon, M. Loete, J. Mol. Spectrosc. 216 (2002) 297]. We test it on the ground state of this molecule using the same experimental data (10 GHz–1 THz region, J up to 99). Bot…

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

High-Resolution Ethylene Absorption Spectrum Between 6035 and 6210 cm-1

The Hot Bands of Methane between 5 and 10 μm

Experimental line intensities of 1727 transitions arising from nine hot bands in the pentad-dyad system of methane are fitted to first and second order using the effective dipole moment expansion in the polyad scheme. The observed bands are nu3 - nu2, nu3 - nu4, nu1 - nu2, nu1 - nu4, 2nu4 - nu4, nu2 + nu4 - nu2, nu2 + nu4 - nu4, 2nu2 - nu2, and 2nu2 - nu4, and the intensities are obtained from long-path spectra recorded with the Fourier transform spectrometer located at Kitt Peak National Observatory. For the second order model, some of the 27 intensity parameters are not linearly independent, and so two methods (extrapolation and effective parameters) are proposed to model the intensities …

Microwave Fourier Transform Spectroscopy of Rovibrational Transitions in the ν 2 /ν 4 Dyads of Methane- 12 C and - 13 C

The ν2/ν4 dyad-dyad spectra of 12CH4 and 13CH4 molecules in the (8÷20) GHz region have been predicted including line strengths. All transitions with γmax > 810-12 cm-1 have been observed directly using a MWFT spectrometer: six F-type transitions for 12CH4 and nine for 13CH4.

Spectroscopy of XY5Z (C4v) Molecules: A Tensorial Formalism Adapted to the O(3) ⊃ Oh ⊃ C4v Chain

Abstract A tensorial formalism adapted to the case of XY 5 Z symmetric tops has been developed as an extension of the usual one for the octahedral molecules. We use the O (3) ⊃ O h ⊃ C 4 v group chain. All the coupling coefficients and formulas for the computation of matrix elements are given for this chain. Such relations are also deduced in the C 4 v group itself.

Spectroscopy of XY5Z (C4v) Molecules: Development of the Hamiltonian and the Transition Moment Operators Using a Tensorial Formalism

We present a development of the Hamiltonian, dipole moment, and polarizability operators of XY(5)Z (C(4v)) molecules using a tensorial formalism derived from the one developed previously in Dijon for XY(6) molecules. These operators are involved in the calculation of the energies and intensities of rovibrational transitions and are essential for spectrum simulations. Expressions for the matrix elements are derived for all these operators. Copyright 2000 Academic Press.

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…

D2hTDS-ST Software for Stark Spectrum Simulation of X2Y4 Asymmetric-Top Molecules

Abstract We present the D 2 h TDS-ST ( D 2 h -Top Data System for Stark effect) program suite with the aim to simulate Stark spectra of any IR active rovibrational polyad of X 2 Y 4 ( D 2 h ) asymmetric-top molecules. D 2 h TDS-ST consists in a series of FORTRAN programs called by scripts. For calculation of Stark spectra, we obtained the expressions of the dipole moment and polarizability operators of X 2 Y 4 molecules using a tensorial formalism. For convenience, we integrated the D 2 h TDS-ST programs into the D 2 h TDS package. The D 2 h TDS suite (including the D 2 h TDS-ST programs) is freely available at the URL: http://icb.u-bourgogne.fr/OMR/SMA/SHTDS/D2HTDS.html .

Spectroscopy of X2Y4 (D2h) molecules: tensorial formalism adapted to the O(3)⊃D2h chain, Hamiltonian and transition moment operators

Abstract A tensorial formalism adapted to the case of the X2Y4 molecules with D2h symmetry has been developed in the same way as in the previous works on XY4 (Td) and XY6 (Oh) spherical tops and XY5Z (C4v) symmetric tops. Here, we use the O(3)⊃D2h group chain. All the coupling coefficients and formulas for the computation of matrix elements are given for this chain and used in the case of the Hamiltonian and transition moment operators.

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…

Observation and analysis of the SF6 ν2+ν4−ν5 band: Improved parameters for the v5= 1 state

Abstract In this paper, we present the high resolution analysis of the weak ν 2 + ν 4 - ν 5 band of SF6 around 735 cm−1. The spectra were recorded on the AILES Beamline at the SOLEIL Synchrotron facility using a cryogenic multipass cell coupled to a Bruker 125HR spectrometer with a maximum resolution of 0.00102 cm−1. For this band, we worked with 4 mbar of SF6 at a temperature of 223 ± 2  K. The optical path length was fixed to 141 m and the spectrum recorded with 0.001 cm−1 of resolution. A new, cold spectrum of the ν 2 + ν 4 band was also collected at 153 K, 15-m path length, and 0.0015 cm−1 resolution. The analysis was performed by using the Dijon group XTDS and SPVIEW software, based on…

29SiH4 and 30SiH4: Dipole moment parameters of the dyad from Stark effect observations with laser sidebands

Abstract The linear Stark effect within the ν 2 ν 4 dyad of 29SiH4 and 30SiH4 has been investigated by applying the infrared sideband technique at microwave modulation frequencies. Two vibration-induced dipole moment parameters have been measured for each isotopomer on natural abundance samples.

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.

Stark Spectrum Simulation of X2Y4 Asymmetric Molecules: Application to Ethylene in a MFI-Type Host Zeolithe

C3v Top Data System (C3vTDS) software for spectrum simulation of XY3Z symmetric-top molecules using the group chain

Abstract The C3v Top Data System (C3vTDS) program suite has been developed with the aim of studying any rovibrational band or polyad of XY3Z (C3v) symmetric-tops molecules in a singlet electronic state. It is developed in the same way as similar programs for various molecular symmetries (Td, Oh, C4v, C2v and D2h). We work in the O ( 3 ) ⊃ C ∞ v ⊃ C 3 v group chain and this choice has consequences on the method used to specify the input parameters for Hamiltonian and transition moment calculations. One example concerning the ν 2 band of the CH 3 12 D symmetric-top molecule is presented. This package consists in a series of FORTRAN programs called by scripts. The whole package is freely acces…

First Assignment and Line Strengths of the 4ν4 Band of 12CH4 near 1.9 μm

Abstract The investigation of the methane spectrum in the region 1.6–2 μm has provided the first assignment and analysis of the 4ν 4 band near 1.9 μm. Hamiltonian and dipole moment operators written in tetrahedral formalism and adapted to the extrapolation method have been used to fit the spectra recorded at the Kitt Peak National Observatory/National Solar Observatory. Nearly 190 line positions and 160 measured intensities have been modeled with standard deviations of 0.107 cm −1 and 18.5%, respectively.

Simulation du Spectre Stark des Molécules X2Y4 : Application à l'Ethylène dans les Zéolithes

The bending triad of the quasi-spherical top molecule SO2F2 in the 550 cm(-1) region

International audience; The analysis of the v(3)/v(7)/v(9) bending triad of SO2F2 has been recently performed with the Watson's Hamiltonian up to octic terms employing 79 rovibrational parameters but including only the first order Coriolis interaction terms, fixed to ab initio values [H. Burger, J. Demaison, F. Hegelund, L. Margules, I. Merke, J. Mol. Struct. 612 (2002) 133-141]. Since SO2F2 is a quasi-spherical top, it can also be considered as derived from the SO42- sulfate ion. We have thus developed a new tensorial formalism in the O(3) > Td > C2v group chain [M. Rotger, V. Boudon, M. Loete, J. Mol. Spectrosc. 216 (2002) 297-307]. This approach allows a systematic development of rovibra…

Line strengths of the ν2 + ν3 and ν3 − ν2 bands of methane (12CH4)

Abstract The individual linestrengths of two related bands of 12 CH 4 , ν 2 + ν 3 near 4545 cm −1 and ν 3 − ν 2 near 1484 cm −1 , were measured with accuracies of 3% and 5%, respectively. In the analysis, an eight-term expansion of the dipole moment through second order was required to fit the strengths of transitions up to J ′ = 10 in ν 2 + ν 3 and J ′ = 12 in ν 3 − ν 2 and to explain the considerable perturbations observed. Application of this model reduced the rms deviations from 68% (zero-order) to 6.3% with the 248 selected lines of ν 2 + ν 2 and from 37% to 5.8% with 186 lines of ν 3 − ν 2 . The integrated bandstrengths for the two bands, respectively, are 1.84(5) and 0.0085(4) cm −2 …

Tensorial development of the rovibronic Hamiltonian and transition moment operators for octahedral molecules

Abstract We present a development of the Hamiltonian, dipole moment and polarizability operators of octahedral XY 6 molecules in a degenerate electronic state. These rovibronic operators are written with the aid of a tensorial formalism derived from the one already used in Dijon in the case of molecules in a non-degenerate electronic state. Electronic operators are defined from the group theory properties. Transition moment operators are introduced in order to consider rovibronic transitions. Spectrum simulations are made thanks to a new version of the HTDS sofware [J. Quant. Spectrosc. Radiat. Transfer 66 (2000) 16] used for the calculation of rovibrational spectra.

A Tensorial Formalism Adapted to the Rovibronic Couplings in the Colored Hexafluorides: Application to the nu(5)(F(2g)) and nu(3)(F(1u)) Modes.

A tensorial formalism adapted to the case of transition-metal hexafluorides in a degenerate electronic state has been developed on the basis of preceding works about spherical-top molecules in a nondegenerate electronic state. We have introduced electronic operators constructed using group theory features and some physical considerations. Vibronic couplings (Jahn-Teller effect, etc.) have been reviewed for the triply degenerate vibrational modes nu(5)(F(2g)) and nu(3)(F(1u)) leading to the identification of the main vibronic parameters. For the first time, an effective rovibronic Hamiltonian as well as the effective transition moment operators (dipole moment and polarizability) for rovibron…

Spectroscopy of XY3Z (C3v) molecules: A tensorial formalism adapted to the O(3)⊃C∞v⊃C3v group chain

Abstract A tensorial formalism adapted to the case of XY3Z symmetric tops has been developed. We use the O (3) ⊃ C∞v ⊃ C3v group chain. All the coupling coefficients and formulas for the computation of the matrix elements are given for this chain. Such relations are also deduced in C3v group itself.

Expressions of Effective Hamiltonian Parameters of XY4 Molecules in the Tetrahedral Formalism

We have derived expressions of second-order effective Hamiltonian parameters of XY4 molecules in the tetrahedral formalism (1992, J. P. Champion et al., "Spectroscopy of the Earth's Atmosphere and Interstellar Medium: Spherical Top Spectra," Academic Press, San Diego). They are written as a function of the force constants of the potential expanded in terms of the dimensionless normal coordinates. These expressions can be used in the isolated band scheme as well as in the polyad one. The ambiguity of the effective Hamiltonian parameters is treated. Relations between the parameters for q2 and q4 terms and Hecht's anharmonicity constants (1960, K. T. Hecht, J. Mol. Spectrosc. 5, 355-389) in th…

High-resolution spectroscopy and preliminary global analysis of C–H stretching vibrations of C2H4 in the 3000 and 6000cm−1 regions

Abstract Ethylene (ethene, H2C=CH2) is a naturally occurring compound in ambient air that affects atmospheric chemistry and global climate. The C2H4 spectrum is available in databases only for the 1000 and 3000 cm−1 ranges. In this work, the ethylene absorption spectrum was measured in the 6030–6250 cm−1 range with the use of a high resolution Bruker IFS 125HR Fourier-spectrometer and a two-channel opto-acoustic spectrometer with a diode laser. As a secondary standard of wavelengths, the methane absorption spectrum was used in both cases. A preliminary analysis was realized thanks to the tensorial formalism developed by the Dijon group that is implemented in the XTDS software package [39] .…

Tensorial Development of the Rovibronic Hamiltonian and Dipole Moment Operators for XY3Z Molecules with a Degenerate Electronic State. Preliminary Application to the CH3O Radical

Abstract We present a development of the Hamiltonian and transition moment operators of XY3Z ( C 3 v ) symmetric tops molecules in a degenerate electronic state with the aid of a tensorial formalism developed in a recent paper [A. El Hilali, V. Boudon, M. Loete, J. Mol. Spectrosc. 239 (2006) 41–50]. Electronic operators are defined from group theory properties. They provide a new approach to build an effective rovibronic Hamiltonian as well as an effective dipole moment operator for rovibronic transition of XY3Z molecules. This model is studied qualitatively thanks to the tensorial algebra properties. Expressions of the matrix elements are derived for these operators. A first simple applica…

Spectroscopy of XY3Z (C3v) radicals with an odd number of electrons: A tensorial formalism adapted to the group chain

Abstract A tensorial formalism adapted to the case of XY 3 Z symmetric tops with half integer angular momenta is proposed as an extension of the formalism for the group chain O  (3) ⊃  C ∞ v  ⊃  C 3 v developed in a recent paper [A. El Hilali, V. Boudon, M. Loete, J. Mol. Spectrosc. 234 (2005) 113–121]. We use the chain SU ( 2 ) ⊗ C I ⊃ C ∞ v S ⊃ C 3 v S , where G S ( G being C ∞ v or C 3 v ) is the G point group with its spinorial representations. Coupling coefficients and formulas for the computation of matrix elements of the tensor operators are derived for this chain. A deduction of coupling coefficients (Clebsch-Gordan, 6 C , 9 C , …) and similar formulas is proposed for the group C 3 …

Development of the Dipole Moment and Polarizability Operators of Octahedral Molecules

We present a development of the dipole moment and polarizability operators of octahedral molecules, using a tensorial formalism analogous to the one developed for tetrahedral molecules. These operators are involved in the calculation of the intensities of rovibrational transitions as well as in the calculation of the Stark effect. Expressions for the matrix elements are derived. Two simplified models for the study of the Stark effect in such molecules are also proposed and discussed. Copyright 1999 Academic Press.

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.

Simulation de l'Effet Stark dans la Bande ν12 de l'Ethylène

The high overtone and combination levels of SF6 revisited at Doppler-limited resolution: A global effective rovibrational model for highly excited vibrational states

Abstract Sulfur hexafluoride is an important prototypal molecule for modeling highly excited vibrational energy flow and multi quanta absorption processes in hexafluoride molecules of technological importance. It is also a strong greenhouse gas of anthropogenic origin. This heavy species, however, features many hot bands at room temperature (at which only 30% of the molecules lie in the ground vibrational state), especially those originating from the lowest, v 6 =1 vibrational state. Using a cryogenic long path cell with variable optical path length and temperatures regulated between 120 and 163 K, coupled to Synchrotron Radiation and a high resolution interferometer, Doppler-limited spectr…

Calculated rJ2-type effective dipole moment parameters for fundamental bands of tetrahedral XY4 molecules

Abstract Formulas in terms of basic molecular constants are presented for effective dipole moment parameters which are responsible for second-order corrections to the line intensities of fundamental bands of tetrahedral XY 4 molecules. Two cases have been considered. In the first case all bands were considered as separate bands. In the second case the ν 2 and ν 4 bands were considered as interacting bands. The influence of effective Hamiltonian transformations on effective dipole moment parameters has been studied. Numerical calculations of effective dipole moment parameters for the ν 2 and ν 4 bands of 12 CH 4 have been performed. There is reasonable agreement between calculated and fitted…

Spectroscopy of XY2Z2 (C2v) Molecules: A Tensorial Formalism Adapted to the O(3)⊃Td⊃C2v Chain. Application to the Ground State of SO2F2

Abstract A tensorial formalism adapted to the case of quasi-spherical XY 2 Z 2 asymmetric tops such as SO 2 F 2 has been developed as an extension of the usual one for the tetrahedral molecules. We use the O (3)⊃ T d ⊃ C 2 v group chain. All the coupling coefficients and formulas for the computation of matrix elements are given for this chain. Such relations are then deduced in the C 2 v group itself. We also present a development of the Hamiltonian, dipole moment, and polarizability operators for the molecules under consideration using this formalism. These operators are involved in the calculation of the energies and intensities of rovibrational transitions and are essential for spectrum …

Linestrengths of the ν2 and ν4 bands of 12CH4 and 13CH4

Absorption spectra recorded on the high-resolution Fourier transform spectrometer at Kitt Peak National Observatory/National Solar Observatory were used to measure individual line strengths of the nu(2) and nu(4) bands of (C-12)H4 and (C-13)H4. The measurements were used to obtain expressions that could be used to correctly predict individual line strengths through five orders of magnitude of absorption strength and high values of J-prime. Transition strengths were modeled using the dyad formalism of two interacting bands and a seven-term second-order dipole-moment expansion. The successful fitting of these data indicates that the method can be used to model measurements of 2- to 5-percent …

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 (…

Algebraic approach to vibrational spectra of tetrahedral molecules. First order infrared intensity model.

International audience; The algebraic approach we have proposed to describe the vibrational stretching modes of polyatomic molecules (Leroy and Michelot, J. Mol. Spectrosc. 151, 71–96 (1992); Can. J. Phys. 72, 274–289 (1994)) is applied to the silane molecule for up to seven quanta. We then suggest a form of the dipole operator adapted to the (n000) local states by combining the strength of group theory method with the necessity of a compact formulation.

Global analysis of the high resolution infrared spectrum of methane 12CH4 in the region from 0 to 4800 cm-1

International audience; We report the global analysis of methane (12CH4) lines from high resolution rovibrational spectra including accurate line positions and intensities in the region 0–4800 cm−1. This covers four polyads: The Ground State Monad (rotational levels), the Dyad (940–1850 cm−1, 2 vibrational levels, 2 sublevels), the Pentad (2150–3350 cm−1, 5 vibrational levels, 9 sublevels) and the Octad (3550–4800 cm−1, 8 vibrational levels, 24 sublevels) and some of the associated hot bands (Pentad−Dyad and Octad−Dyad). New Fourier transform infrared (FTIR) spectra of the Pentad and Octad regions have been recorded with a very high resolution (better than 0.001 cm−1 instrumental bandwidth,…

Resolving the forbidden band of SF6

Sulfur hexafluoride is an important molecule for modeling thermophysical and polarizability properties. It is also a potent greenhouse gas of anthropogenic origin, whose concentration in the atmosphere, although very low is increasing rapidly; its global warming power is mostly conferred by its strong infrared absorption in the ν3 S-F stretching region near 948 cm(-1). This heavy species, however, features many hot bands at room temperature (at which only 31% of the molecules lie in the ground vibrational state), especially those originating from the lowest, v6 = 1 vibrational state. Unfortunately, the ν6 band itself (near 347 cm(-1)), in the first approximation, is both infrared- and Raman…

Simultaneous Determination of Force Constants and Dipole Moment Derivatives of Methane.

The expressions of the effective Hamiltonian and dipole moment spectroscopic parameters in the tetrahedral formalism are used simultaneously to fit the force field and dipole moment derivatives of the methane molecule. Data, the so-called "observed parameters," are the values of the spectroscopic parameters determined from the frequencies and line strengths analyses. The ambiguities of most parameters (in the polyad scheme) are treated consistently with the Hamiltonian reduction chosen in the frequency analyses. As an illustration, the method is applied to the tetrahedral XY4 isotopic species only. The quadratic and cubic force field constants have been determined in addition to the linear …

New assignments in the 2μm transparency window of the 12CH4 Octad band system

Abstract This paper reports new assignments of rovibrational transitions of 12 CH 4 bands in the range 4600–4887  cm −1 which is usually referred to as a part of the 2 μm methane transparency window. Several experimental data sources for methane line positions and intensities were combined for this analysis. Three long path Fourier transform spectra newly recorded in Reims with 1603 m absorption path length and pressures of 1, 7 and 34 hPa for samples of natural abundance CH 4 provided new measurements of 12 CH 4 lines. Older spectra for 13 CH 4 (90% purity) from JPL with 73 m absorption path length were used to identify the corresponding lines. Most of the lines in this region belong to th…

Double modulation sideband spectroscopy: μ0, μ24, and μ44 of 28SiH4

Abstract The linear Stark effect within the ν 2 ν 4 dyad of the main isotopomer of silane, 28 SiH 4 , has been investigated by applying the saturation technique as well as IR-IR double resonance. From 35 transitions, two vibration-induced dipole moment parameters and the centrifugal distortion moment have been determined as μ 0 = 1.357(12) × 10 −5 D, μ 24 = 2.391(31) × 10 −2 D, and μ 44 = −1.261(17) × 10 −2 D employing the Stark coefficients calculated by the procedure of Loete.