Search results for "TENSORIAL FORMALISM"
showing 10 items of 16 documents
High-resolution spectroscopy and analysis of the nu3/2nu4 dyad of CF4
2011
International audience; CF4 is a strong greenhouse gas of both anthropogenic and natural origin [D.R. Worton et al., Environ. Sci. Technol. 41, 2184 (2007)]. However, high-resolution infrared spectroscopy of this molecule has received only a limited interest up to now. Until very recently, the public databases only contained cross-sections for this species, but no detailed line list. We reinvestigate here the strongly absorbing ν3 region around 7.8 μm. New Fourier transform infrared (FTIR) spectra up to a maximal resolution of 0.0025 cm−1 have been recorded: (i) room-temperature spectra in a static cell and (ii) a supersonic expansion jet spectrum at a 23 K estimated temperature. Following …
The high overtone and combination levels of SF6 revisited at Doppler-limited resolution: A global effective rovibrational model for highly excited vi…
2017
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…
High-resolution spectroscopy and analysis of the V2 + V3 combination band of SF6 in a supersonic jet expansion
2013
International audience; Sulphur hexafluoride is a very strong greenhouse gas whose concentration is increasing in the atmosphere. It is detected through infrared absorption spectroscopy in the strong ν3 fundamental region. Due to the existence of low-lying vibrational states of this molecule, however, many hot bands arise at room temperature and those are still not known. We present here a contribution to the elucidation of this hot band structure, by analysing the ν2 + ν3 combination band. We use a supersonic jet expansion high-resolution spectrum at a rotational temperature of ca. 25 K that was recorded thanks to the Jet-AILES setup at the Source Optimisée de Lumière d'Energie Intermédiai…
The vibrational levels of methane obtained from analyses of high-resolution spectra
2006
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…
Rotational Raman spectroscopy of ethylene using a femtosecond time-resolved pump-probe technique.
2005
154309; Femtosecond Raman-induced polarization spectroscopy (RIPS) was conducted at low pressure (250 mb at 295 K and 400 mb at 373 K) in ethylene. The temporal signal, resulting from the beating between pure rotational coherences, was measured with a heterodyne detection. The temporal traces were converted to the frequency domain using a Fourier transformation and then analyzed thanks to the D2hTDS software (http://www.u-bourgogne.fr/LPUB/shTDS.html) dedicated to X2Y4 molecules with D2h symmetry. The effective Hamiltonian was expanded up to order 2, allowing the determination of five parameters with an rms of 0.017 cm(-1). Special care was taken in the precise modeling of intensities, taki…
XTDS and SPVIEW: Graphical tools for the analysis and simulation of high-resolution molecular spectra
2008
International audience; XTDS is a Java front-end to the different programs implementing the tensorial formalism developed in the Dijon group [see for instance: V. Boudon, J.-P. Champion, T. Gabard, M. Loëte, F. Michelot, G. Pierre, M. Rotger, Ch. Wenger, M. Rey, J. Mol. Spectrosc. 228 (2004) 620–634 ]. It allows the simulation and analysis of polyad systems for molecules of various symmetries (Td and Oh spherical tops like CH4 and SF6, C2v and C4v quasi-spherical tops like SO2F2 and SF5Cl, D2h molecules like C2H4). SPVIEW is a multiplatform Java application that allows graphical assignment of high-resolution molecular spectra. It is possible to load, display and manipulate experimental and …
The methane Raman spectrum from 1200 to 5500 cm(-1): A first step toward temperature diagnostic using methane as a probe molecule in combustion syste…
2005
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…
Rovibrational spectroscopy of ethylene : Stark effect : Application to ethylene in zeolites
2010
The objective of this report is to present a study as complete as possible of the Stark effect in the asymmetric top molecules of X2Y4 type possessing the D2h symmetry group and to apply it to the problem of the spectroscopy of the ethylene molecule trapped in a zeolite. For the first time, a tensorial formalism adapted to the study of the Stark effect for the O(3) D2h group chain was developed. In parallel, a computer package was worked out as a new generation of software called D2hTDS-ST using a simpler basis, allowing an economy in the calculation time. On the basis of the theoretical and computing tools as well as from the experimental spectra, recorded in the laboratory, we made a firs…
Symmetry-adapted tensorial formalism to model rovibrational and rovibronic spectra of molecules pertaining to various point groups
2004
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…
High-resolution far-infrared synchrotron FTIR spectroscopy and analysis of the ν 7 , ν 19 and ν 20 bands of trioxane
2022
Rovibrational bands spectra of three ν20, ν7 and ν19 bands of 1, 3, 5 – trioxane (H2CO)3 were recorded in the 50–650 cm−1 range using a long path absorption cell coupled to a high resolution Fourier transform spectrometer and synchrotron radiation at the AILES beamline of the SOLEIL synchrotron. More than 16 000 lines were assigned with a dRMS better than 0.17 × 10−3 cm−1. Two different formalisms (tensorial and Watson) were used to derive accurate rotational and quartic parameters for the three bands and for the first time, a precise determination of Coriolis parameter and q+ l−doubling constant for both ν20 and ν19 perpendicular bands was obtained. Last, each set of spectroscopic paramete…