Minières, "ateliers" et hypogées. Étude de l’organisation du territoire dans les marais de Saint-Gond (Marne)

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Doppler-free two-photon spectrum of SF_6 for metrological purposes

We report on our systematic investigation of strong Doppler-free two-photon absorption in the middle infrared. The absorption frequencies for two counterpropagating waves of identical frequencies are predicted. Five of these transitions were observed with sub-Doppler resolution with a sideband CO(2) laser and were measured with 10-kHz accuracy. Knowledge of these strong two-photon absorptions frequencies will allow the improvement of secondary frequency standards in the infrared.

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…

Analysis of the infrared Fourier transform spectrum of the Dyad of 116SnH4

Abstract The FTIR spectrum of monoisotopic 116SnH4 has been recorded with the Bruker 120 HR interferometer at Giessen, West Germany, in the ν 2 ν 4 range extending from 600 to 850 cm−1. The resolution (FWHM) was 2.1 × 10−3 cm−1. The Dyad ν 2 ν 4 (0100, 0001) was analyzed using a sixth-order Hamiltonian. The analysis of infrared transitions enabled us to determine 10 ground state parameters, 9 ν2 parameters, 17 ν4 parameters, and 18 interaction parameters. Of 3800 calculated transitions assigned to observed lines, 1183 unblended lines have been selected for the data refinement. For J ≤ 19, the value of the standard deviation is of the order of magnitude of the estimated experimental accuracy…

Spherical Top Spectra

HIGH RESOLUTION STIMULATED RAMAN SPECTROSCOPY WITH A 3 MHz ACCURACY WAVEMETER

The hot bands of silane between 2120 and 2270cm−1

Abstract The infrared spectrum of the SiH 4 molecule has been recorded between 2040 and 2320 cm −1 using the high-resolution Fourier interferometer of the Laboratoire de Photophysique Moleculaire ( Orsay , France ). The resolution was 5.4 × 10 −3  cm −1 . In this region, many lines were previously analyzed and assigned to the ν 1 / ν 3 stretching dyad of 28 SiH 4 , 29 SiH 4 , and 30 SiH 4 molecules [J. Mol. Spectrosc. 143 (1990) 35]. However, several lines in the spectrum were not assigned. The results obtained in our previous study [J. Mol. Spectrosc. 197 (1999) 307] of the infrared spectrum of 28 SiH 4 , in the bending-stretching tetrad region at 3100 cm −1 , enabled us to assign 204 of t…

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…

Analysis of Infrared and Raman-Spectra of 116SnH4 in the 1900 cm-1 Region - Study of the 1000, 0010 Interacting States

0022-2852

Simultaneous Analysis of the ν2 Raman and ν2 + ν6 Infrared Spectra of the SF6 Molecule

High-resolution Raman spectra of the nu(2) band of SF(6) have been recorded at a temperature of 195 K (dry ice) and a pressure of 39 mbar. These spectra were analyzed using a new set of programs specially written for XY(6) molecules. These programs, called HTDS (highly spherical top data system) in reference to the set of programs called STDS (spherical top data system written for XY(4) molecules) can be freely accessible through ftp (user anonymous) at jupiter.u-bourgogne.fr or on the web at the URL http://www.u-bourgogne.fr/LPUB/shTDS.html. The study of nu(2) was made using a Hamiltonian developed through the third order. Four parameters were determined. The standard deviation obtained us…

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…

Study of the Fundamental Bands of 70GeD4 by High-Resolution Raman and Infrared Spectroscopy: First Experimental Determination of the Equilibrium Bond Length of Germane

Abstract The four fundamental bands of 70 GeD 4 have been analyzed using the STDS software developed in Dijon (http://www.u-bourgogne.fr/LPUB/sTDS.html). Both infrared and Raman spectra were used to observe all fundamental bands. Infrared spectra of monoisotopic 70 GeD 4 were recorded in the regions 600 and 1500 cm −1 using the Bruker 120HR interferometer at Wuppertal. The resolution (1/maximum optical path difference) was between 2.3 and 3.3×10 −3 cm −1 for the ν 3 and ν 4 infrared-active fundamental bands as well as for the interacting ν 2 band. A high-resolution stimulated Raman spectrum of the ν 1 band has been recorded in Madrid. The instrumental resolution of the Raman spectrum was 3.…

Analysis of the Infrared Fourier Transform Spectrum of the Spectra of Silane in the Range 2930-3300 cm(-1).

The infrared spectrum of (28)SiH(4) between 2930 and 3300 cm(-1) was recorded using the Laboratoire de Physique Moleculaire et Applications (LPMA.) Fourier transform spectrometer. The instrumental response function width chosen makes it possible to obtain a Doppler-limited spectrum. The observed spectrum belongs to the tetrad built with one quantum of stretching mode (nu(1) or nu(3)) and one quantum of bending mode (nu(2) or nu(4)). The excited states are formed from eight vibrational sublevels: nu(1) + nu(2)(E), nu(1) + nu(4)(F(2)), nu(2) + nu(3)(F(1) + F(2)), and nu(3) + nu(4)(A(1) + E + F(1) + F(2)). The intricacy of the upper states was resolved using the variations of the line strength…

High-Resolution Stimulated Raman-Spectroscopy with a 3 MHz Accuracy Wavemeter

0302-0738

High-Resolution Jet-Cooled Spectroscopy of SF6: The ν2+ ν6Combination Band of32SF6and the ν3Band of the Rare Isotopomers

The Fourier transform infrared spectrum of SF6 was recorded in a supersonic expansion jet of an SF6/argon mixture. The SF6:Ar seeding ratio was 2:3. The instrumental bandwidth was 0.005 cm-1. A globar source and an MCT detector were used. A rotational temperature of approximately 30 K was achieved. The nu2 + nu6 combination band of 32SF6 was analyzed using a modified version of the spherical top data system (STDS) programs developed in Dijon. A very good fit was obtained for this band with an rms of 0.0036 cm-1. The effective Hamiltonian was developed up to fourth order for the nu2 + nu6 part, to second order for the nu2 and ground state parts, and to first order for the nu6 part. Five hund…

High-Resolution Spectroscopy and Analysis of the nu(4) Bending Region of SF(6) near 615 cm(-1).

The high-resolution Fourier transform spectrum of the nu(4) bending region of SF(6) near 615 cm(-1) has been recorded at 213 K. We were able to perform a simultaneous analysis of the nu(4) and nu(4) + nu(6) - nu(6) bands of the main isotopomer, namely (32)SF(6). This is the first detailed analysis of a hot band for this molecule. The nu(4) band of (34)SF(6) was also analyzed and the Q branch of the nu(4) band of (33)SF(6) was identified. In both cases we used the HTDS software developed in Dijon. Copyright 2001 Academic Press.

Highly-spherical Top Data System (HTDS) software for spectrum simulation of octahedral XY6 molecules

Abstract The Spherical Top Data System (STDS) program suite developed in Dijon has been extended into two directions. First, the vibrational extrapolation is now possible for any kind of polyad scheme, this one being fully specified in the input parameters of the programs for hamiltonian and transition moment model calculations. This was not the case of the preceding version which was based on the polyad scheme of methane. Secondly, it is now possible to study any band and polyad of XY 6 molecule for which a complete treatment in the O h group is made. Up to now, only some vibrational levels of these molecules ( F 1u levels in particular) could be studied using equivalences with the T d gro…

Study of interacting bands of silane: Analysis of infrared and Raman spectra

Abstract The ν 1 ν 3 interacting bands of natural silane have been studied by Fourier transform spectroscopy and stimulated Raman spectroscopy, respectively, in the regions 2040–2320 and 2180–2187 cm−1. These data combined with available microwave observations have been analyzed using a reduced effective Hamiltonian developed through the fifth order for 28SiH4 and through the fourth order for 29SiH4 and 30SiH4. The observed infrared and Raman transitions have been very well reproduced with a standard deviation of about 0.0004 cm−1 for 28SiH4. Some anomalies in the Hamiltonian expansion have been found, but they did not perturb the analysis.

High resolution Fourier transform infrared spectroscopy and analysis of the ν 6 band of jet-cooled Mo(CO) 6

Abstract Rovibrational FTIR spectra of Mo(CO) 6 have been recorded in supersonic argon expansions at 0.004 cm −1 resolution. Rotational constants have been determined for the ν 6 fundamental band of Mo( 12 CO) 6 and for the parallel band of the symmetric top isotopomer Mo( 13 CO)( 12 CO) 5 . From these results, a precise estimate of the Coriolis parameter for the ν 6 band of the main isotopomer Mo( 12 CO) 6 is derived, necessary for the analysis of the ν 6 spectrum. The observation of an octahedral splitting clearly resolved for the highest J-lines in the R branch prompted the use of a specific treatment based on the tensorial formalism developed by J.P. Champion, M. Loete, G. Pierre (Spher…

Coriolis interaction parameters of the (2100; F2) bands of SiH4 and GeH4. A test of local mode models

Abstract The high-resolution spectra of the (2100; F 2 , N ), N = 1 and 2, bands of SiH 4 and GeH 4 have been recorded and preliminary analyzed. The Coriolis interaction parameter 2 Bζ 3 is obtained; it provides a test of three widely used models: the harmonically coupled anharmonic oscillators model with two different kinds of variables, and the normal mode model with Darling-Dennison resonance included.

Orientation of O(3) and SU(2)⊗CI representations in cubic point groups (Oh,Td) for application to molecular spectroscopy

Abstract We propose a detailed method for the symmetrization of the standard O (3) or SU (2)⊗ C I basis | j τ , m 〉 ( τ = g or u ) into the O h or T d point group. This is realized by means of an orientation matrix called G . The oriented basis obtained in this way allows matrix element calculations for rovibronic spectroscopic problems concerning octahedral or tetrahedral molecules. Particular attention has been put on careful phase choices. A numerical calculation of all the G matrix elements for both integer and half-integer j values up to 399/2 has been performed. Such high angular momentum values are necessary for the case of heavy molecules with high rotational excitation. To calculat…

Study of the v3 = 1 State of 80SeF6 by Fourier Transform Spectroscopy

The Fourier transform infrared spectrum of monoisotopic 80SeF6 has been recorded in the 760-792 cm-1 region with an effective resolution of ca. 2.3 x 10(-3) cm-1. The 80SeF6 sample was prepared by burning monoisotopic 80Se powder (99.2%) in an excess of fluorine. The analysis of infrared transitions of the nu3 band enabled the determination of parameters of the Hamiltonian developed up to the third order and the fourth order. The standard deviation obtained is equal to 4 x 10(-4) cm-1 for the third-order development and 3.2 x 10(-4) cm-1 for the fourth-order development. In the two analyses, 2900 lines were assigned and fitted. Copyright 1997 Academic Press. Copyright 1997Academic Press

Revised Analysis of the Structure of the v1 Band of Methane

Abstract The CARS spectrum of the v 1 band of 12 CH 4 at a pressure of 14 mbar was recorded using cw excitation in the cavity of a ring argon ion laser. The analysis of the intensity profile of the obarred spectrum led to the detection of inconsistencies with the hitherto proposed calculated positions of transitions with J = 7 to J = 10 and to a relocation of the corresponding lines.

High-Resolution Stimulated Raman Spectroscopy of Methane 13CD4 in the Pentad Region

Abstract We present the first Raman spectrum of 13CD4 recorded at room temperature in the pentad region by inverse Raman spectroscopy, thus including the ν1 (A1), 2ν2 (A1), 2ν4 (A1), and ν2 + ν4(F1 + F2) Q branches. It is noteworthy that the overtone bands 2ν2 and 2ν4 are observed for the first time in a methane-like molecule by a coherent Raman process. The wide frequency range investigated, covering 45 cm−1 in three parts, contains more than 300 lines with uncertainty less than 10−3 cm−1 in most cases. These Raman data are combined with high-resolution infrared data in a weighted least-squares fit of the vibration-rotation constants of the pentad, thanks to a relevant partially reduced ef…

Study of ν1/ν3 interacting bands of silane : analysis of infrared and Raman spectra

International audience; The ν1/ν3 interacting bands of natural silane have been studied by Fourier transform spectroscopy and stimulated Raman spectroscopy, respectively, in the regions 2040–2320 and 2180–2187 cm−1. These data combined with available microwave observations have been analyzed using a reduced effective Hamiltonian developed through the fifth order for 28SiH4 and through the fourth order for 29SiH4 and 30SiH4. The observed infrared and Raman transitions have been very well reproduced with a standard deviation of about 0.0004 cm−1 for 28SiH4. Some anomalies in the Hamiltonian expansion have been found, but they did not perturb the analysis.

Organization of Quantum Bifurcations: Crossover of Rovibrational Bands in Spherical Top Molecules

Qualitative changes in the rotational structure of a finite particle quantum system are studied. The crossover phenomenon is explained from the point of view of consecutive quantum bifurcations. The generic organization of bifurcations is related to the stratification of the space of dynamical variables imposed by the invariance group of the Hamiltonian.

New Accurate Fit of an Extended Set of Saturation Data for the ν3 Band of SF6: Comparison of Hamiltonians in the Spherical and Cubic Tensor Formalisms

An extended set of 321 frequencies of vibration-rotation lines of the nu(3) band of SF(6) has been measured by saturation spectroscopy using various isotopic species of CO(2). A least-squares fit of these data has been performed using an effective Hamiltonian written either with a spherical tensor or with a cubic tensor formalism. We have derived correspondence formulas between the parameters in the two approaches and checked that both formalisms give the same results up to the seventh order. Corrected parameters are given for the fit with a fifth-order Hamiltonian. An accurate representation of the band is obtained at the tenth order (standard deviation approximately 12 kHz) with a remarka…

High-resolution Fourier transform infrared spectroscopy and analysis of the ν3 fundamental band of P4

Abstract We present the first high-resolution infrared absorption study of the ν 3 fundamental of white phosphorus, P 4 . This spectrum has been analyzed using the STDS (Spherical Top Data System) software. The band center lies at 466.286 cm −1 . With the approximation ( Bζ ) 3 =− B 0 /2, we found that the ground-state bond length is r 0 =219.58 pm. This value is consistent with that of ab initio studies reported previously but significantly different from a value obtained from a Raman study.