The cyclic ground state structure of the HF trimer revealed by far infrared jet-cooled Fourier transform spectroscopy.

International audienceThe rovibrationally resolved Fourier transform (FT) far infrared (FIR) spectra of two intermolecular librations of (HF)3, namely the in-plane ν6 and out-of-plane ν4 bending fundamentals centered, respectively, at about 494 cm(-1) and 602 cm(-1), have been recorded for the first time under jet-cooled conditions using the supersonic jet of the Jet-AILES apparatus. The simultaneous rotational analysis of 245 infrared transitions belonging to both bands enabled us to determine the ground state (GS), ν6 and ν4 rotational and centrifugal distortion constants. These results provided definite experimental answers to the structure of such a weakly bound trimer: firstly the vibrationally averaged planarity of cyclic (HF)3, also supported by the very small value of the inertia defect obtained in the GS, secondly the slight weakening of the hydrogen bond in the intermolecular excited states evidenced from the center of mass separations of the HF constituents determined in the ground, ν6 = 1 and ν4 = 1 states of (HF)3 as well as the decrease of the fitted rotational constants upon excitation. Finally, lower bounds of about 2 ns on ν6 and ν4 state lifetimes could be derived from the deconvolution of experimental linewidths. Such long lifetimes highlight the interest in probing low frequency intermolecular motions of molecular complexes to get rid of constraints related to the vibrational dynamics of coupled anharmonic vibrations at higher energy, resulting in loss of rotational information

First detection of NHD and ND2_2 in the interstellar medium

Deuterium fractionation processes in the interstellar medium (ISM) have been shown to be highly efficient in the family of nitrogen hydrides. To date, observations were limited to ammonia (NH$_2$D, NHD$_2$, ND$_3$) and imidogen radical (ND) isotopologues. We want to explore the high frequency windows offered by the \emph{Herschel Space Observatory} to search for deuterated forms of amidogen radical NH$_2$ and to compare the observations against the predictions of our comprehensive gas-grain chemical model. Making use of the new molecular spectroscopy data recently obtained at high frequencies for NHD and ND$_2$, both isotopologues have been searched for in the spectral survey towards the class 0 IRAS 16293-2422, a source in which NH$_3$, NH and their deuterated variants have been previously detected. We used the observations carried out with HIFI (Heterodyne Instrument for the Far Infrared) in the framework of the key program "Chemical Herschel surveys of star forming regions" (CHESS). We report the first detection of interstellar NHD and ND$_2$. Both species are observed in absorption against the continuum of the protostar. From the analysis of their hyperfine structure, accurate excitation temperature and column density values have been determined. The latter were combined with the column density of the parent species NH$_2$ to derive the deuterium fractionation in amidogen. The amidogen D/H ratio measured in the low-mass protostar IRAS 16293-2422 is comparable to the one derived for the related species imidogen and much higher than that observed for ammonia. Additional observations of these species will give more insights into the mechanism of ammonia formation and deuteration in the ISM. We finally indicate the current possibilities to further explore these species at submillimeter wavelengths.Comment: 11 pages, 5 figures, 7 tables. Accepted for publication in A&

HIGH RESOLUTION FAR INFRARED FOURIER TRANSFORM SPECTROSCOPY OF THE NH2_2 RADICAL.

Author Institution: SOLEIL Synchrotron, AILES beamline, Saint-Aubin, France and Institut des Sciences Moleculaires d'Orsay, ISMO, CNRS, Universite Paris XI, Orsay, France; SOLEIL Synchrotron, AILES beamline, Saint-Aubin, FranceFirst identified toward Sgr B2}, the NH$_2$ radical has recently been detected in the interstellar medium by the HIFI instrument on board of Herschel}. Despite the fact that this radical has not been detected in brown dwarfs and exoplanets yet, it is already included in physical and chemical models of those environments} (temperature higher than 2000 K expected in several objects). Its detection in those objects will depend on the existence of a reliable high temperature and high resolution spectroscopic database on the NH$_2$ radical.The absorption spectrum of NH$_2$ has been recorded between 15 and 700 cm$^{-1}$ at the highest resolution available using the Bruker IFS125HR Fourier transform interferometer connected to the far infrared AILES beamline at SOLEIL (R=0.001~cm$^{-1}$). The radical was produced by an electrical discharge (DC) through a continuous flow of NH$_3$ and He using the White-type discharge cell developped on the beamline (optical path: 24m). Thanks to the brilliance of the synchrotron radiation, more than 700 pure rotational transitions of NH$_2$ have been identified with high N values (N$_{max}$=25) in its fundamental and first excited vibrational modes. By comparison to the previous FT spectroscopic study on that radical in the FIR spectral range}, asymmetric splitting as well as fine and hyperfine structure have been resolved for several transitions

Broadband terahertz heterodyne spectrometer exploiting synchrotron radiation at megahertz resolution

International audienceA new spectrometer allowing both high resolution and broadband coverage in the terahertz (THz) domain is proposed. This instrument exploits the heterodyne technique between broadband synchrotron radiation and a quantum cascade laser (QCL) based molecular THz laser that acts as the local oscillator (LO). Proof of principle for exploitation for spectroscopy is provided by the recording of molecular absorptions of hydrogen sulfide (H 2 S) and methanol (CH 3 OH) around 1.073 THz. Ultimately, the spectrometer will enable to cover the 1-4 THz region in 5 GHz windows at Doppler resolution

Terahertz spectroscopy of hydrogen sulfide

Pure rotational transitions of hydrogen sulfide (H2S) in its ground and first excited vibrational states have been recorded at room temperature. The spectrum comprises an average of 1020 scans at 0.005 cm−1 resolution recorded in the region 45–360 cm−1 (1.4 to 10.5 THz) with a globar continuum source using a Fourier transform spectrometer located at the AILES beamline of the SOLEIL synchrotron. Over 2400 rotational lines have been detected belonging to ground vibrational state transitions of the four isotopologues H232S, H233S, H234S, and H236S observed in natural abundance. 65% of these lines are recorded and assigned for the first time, sampling levels as high as J=26 and Ka=17 for H232S. 320 pure rotational transitions of H232S in its first excited bending vibrational state are recorded and analysed for the first time and 86 transitions for H234S, where some of these transitions belong to new experimental energy levels. Rotational constants have been fitted for all the isotopologues in both vibrational states using a standard effective Hamiltonian approach. Comprehensive comparisons are made with previously available data as well as the data available in HITRAN, CDMS, and JPL databases. The 91 transitions assigned to H236S give the first proper characterization of its pure rotational spectrum

TERAHERTZ ROTATIONAL SPECTROSCOPY OF THE SO RADICAL

Author Institution: Laboratoire de Physico-Chimie de l'Atmosphere, EA 4493, Universite du Littoral Cote d'Opale, 59140 Dunkerque, France; Institut des Sciences Moleculaires d'Orsay, CNRS, UMR 8214, Universite Paris XI, bat. 210, 91405 Orsay Cedex, France; SOLEIL Synchrotron, AILES beamline, L'orme des Merisiers, Saint-Aubin, 91192 Gif-Sur-Yvette, FranceSulfur monoxide SO (X$^3\Sigma^-$) is a well-known interstellar radical identified in a wide variety of astrophysical environments 184, L59 (1973)} which is particularly abundant in star forming regions, \textit{Astrophys. J.} 315, 621 (1987)}. Due to its high reactivity and its role in chemical reactions involving O and S atoms, SO is also a reaction intermediate in combustion processes and chemistry of the Earth atmosphere, \textit{J. Mol. Spectrosc.} 124, 379 (1987)}. %The pure rotational spectrum of SO has been extensively studied in the laboratory from sub-millimeter to THz wavelength, \textit{J. Mol. Speectrosc.} 182, 85 (1997)}. However no far infrared (FIR) broadband investigation on this radical has been reported up to date, and several rotational transitions belonging to the spectral windows of the HIFI instrument (on board of the Herschel satellite) require accurate laboratory measurements. %\vspace{1em} We have recorded pure rotational transitions of SO in the THz spectral range using synchrotron-based Fourier-Transform (FT) FIR and continous wave (CW) THz techniques. A FT-FIR spectrum of SO has been recorded at the AILES beamline of SOLEIL synchrotron in the spectral range 44--93 \wn~using a resolution of 0.001~\wn~allowing an accuracy on line position of 0.00007~\wn~($\sim$ 2 MHz). A multipass absorption discharge cell aligned to an absorption path length of 24 m has been used, \textit{Rev. Sci. Instrum.} 82, 113106 (2011)}. A continuous electrical discharge (1~A / 980~V) in a flowing mixture of H$_2$S, He, H$_2$ and air (respectively at pressure of 0.01, 1.15, 0.14 and 0.06~mbar) was used to produce SO. On this spectrum, 102 transitions of SO have been identified with $N=31$ to $65$. Among the observed lines, 99 are detected for the first time (22 new transitions belong to the HIFI spectral windows). Due to our limited instrumental resolution, transitions involving $N$ ranging from $31$ to $43$ show unresolved fine structure triplets. Recently, in order to observe all fine structure components in the HIFI spectral windows, we have recorded a high resolution CW-THz spectrum of SO, \textit{J. Mol. Struct.} 1006, 13 (2011)}. At the time of the writing, this spectrum was under analysis