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…

Infrared spectroscopy of ruthenium tetroxide and high-resolution analysis of the ν3 band

Abstract RuO 4 is a heavy tetrahedral molecule which has practical uses for several industrial fields. Due to its chemical toxicity and the radiological impact of its 103 and 106 isotopologues, the possible remote sensing of this compound in the atmosphere has renewed interest in its spectroscopic properties. New, higher resolution FTIR spectra have been recorded at room temperature, using an isotopic pure sample of 102 RuO 4 and a sample with all stable isotopes present in natural abundance. We reinvestigate here the strong ν 3 stretching fundamental region and perform new assignments and effective Hamiltonian parameter fits for the five main isotopologues ( 99 RuO 4 , 100 RuO 4 , 101 RuO …

High-resolution stimulated Raman spectroscopy and analysis of the ν 1 band of osmium tetroxide

D.B.P. and R.Z.M. acknowledge the financial support of the Ministry of Science and Innovation through research grant no. FIS2009-08069.

High-Resolution Spectroscopy and Structure of Osmium Tetroxide. A Benchmark Study on 192OsO4

Osmium tetroxide (OsO(4)) is a heavy tetrahedral molecule that constitutes a benchmark for quantum chemistry calculations. Its favorable spin statistics (due to the zero nuclear spin of oxygen atoms) is such that only A(1) and A(2) (T(d) symmetry) rovibrational levels are allowed, leading to a dense but quite easily resolvable spectrum. We reinvestigate here the ν(1)/ν(3) stretching fundamental (940-980 cm(-1)) dyad region and perform new assignments and effective Hamiltonian parameter fits for the main isotopologue ((192)OsO(4)). We also investigate the ν(2)/ν(4) bending fundamental dyad (300-360 cm(-1)) for the first time and perform a preliminary analysis. New experimental data have been…

High-resolution spectroscopy and analysis of the stretching dyad of osmium tetroxide

Abstract OsO4 is a heavy tetrahedral molecule that may constitute a benchmark for quantum chemistry calculations. Its favorable spin statistics (due to the zero nuclear spin of oxygen atoms) is such that only A1 and A2 rovibrational levels are allowed, leading to a dense, but quite easily resolved spectrum. Most lines are single ones, instead of complex line clusters as in the case of other heavy spherical-tops like SF6, for instance. It is thus possible to fully assign and fit the spectrum and to obtain precise experimental effective molecular parameters. The strong ν 3 stretching fundamental has been studied a long time ago as an isolated band [McDowell RS, Radziemski LJ, Flicker H, Galbr…

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

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…

Performance of the AILES THz-Infrared Beamline on SOLEIL for High Resolution Spectroscopy

High-resolution spectroscopy of difference and combination bands of SF6 to elucidate the ν3 + ν1 − ν1 and ν3 + ν2 − ν2 hot band structures in the ν3 region

The strong infrared absorption in the ν3 S–F stretching region of sulphur hexafluoride (SF6) near 948 cm−1 makes it a powerful greenhouse gas. Although its present concentration in the atmosphere is very low, it is increasing rapidly, due to industrial pollution. The ground state population of this heavy species is only 32% at room temperature and thus many hot bands are present. Consequently, a reliable remote-sensing spectroscopic detection and monitoring of this species require an accurate modelling of these hot bands. We used two experimental set-ups at the SOLEIL French synchrotron facility to record some difference and combination bands of SF6: (1) a new cryogenic multiple pass cell w…

Analytical measurements of fission products during a severe nuclear accident

The Fukushima accident emphasized the fact that ways to monitor in real time the evolution of a nuclear reactor during a severe accident remain to be developed. No fission products were monitored during twelve days; only dose rates were measured, which is not sufficient to carry out an online diagnosis of the event. The first measurements were announced with little reliability for low volatile fission products. In order to improve the safety of nuclear plants and minimize the industrial, ecological and health consequences of a severe accident, it is necessary to develop new reliable measurement systems, operating at the earliest and closest to the emission source of fission products. Throug…

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…

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…

On-Line Measurement of Gaseous Iodine Species During a PWR Severe Accident

International audience; Iodine is a highly radio-toxic element, due to its affinity to the thyroid, and represents the major part of the radioactivity released during a nuclear accident. In the context of nuclear safety and radio-protection, we are interested in identifying the iodine gaseous species which are released, in the nuclear power plants, under molecular (I$_2$) and organic (CH$_3$I) forms. Therefore, we are working on providing a spectroscopic database for both species. While the infrared spectrum of the ν6 band of methyl iodide was previously studied, only 4000 lines were assigned. We present the rovibrational analysis of a high quality experimental spectrum, of this band, recor…

The High Resolution Far-Infrared Spectrum of Methane at the SOLEIL Synchrotron

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…

The high-resolution far-infrared spectrum of methane at the SOLEIL synchrotron

International audience; As a tetrahedral molecule, methane has no permanent dipole moment. Its spectrum, however, displays faint absorption lines in the THz region, due to centrifugal distorsion effects. This is important for planetary applications since this region is used to measure methane concentration in some planetary atmospheres, in particular on Titan. Up to now, all measurements relied either on some old low resolution infrared absorption spectra, or on high resolution Stark measurements for low J values only. Even if these results have been reexamined recently [E. H. Wishnow, G. S. Orton, I. Ozier and H. P. Gush, J. Quant. Spectrosc. Radiat. Transfer 103, 102-117 (2007)], it seeme…

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…