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

Gas-phase infrared spectra of cationized nitrogen-substituted polycyclic aromatic hydrocarbons

Gas-phase infrared spectra of several ionized nitrogen substituted polycyclic aromatic hydrocarbons (PANHs) have been recorded in the 600-1600 cm(-1) region via IR multiple-photon dissociation (IRMPD) spectroscopy. The UV photoionized PANH ions are trapped and isolated in a quadrupole ion trap where they are irradiated with an IR free electron laser. The PANHs were studied in their radical cation (PANH(+)) and protonated (H+ PANH) forms, and include quinoline, isoquinoline, phenanthridine, benzo[h] quinoline, acridine, and dibenzo[f,h] quinoline. Experimental IRMPD spectra were interpreted with the aid of density functional theory methods. The PANH(+) IR spectra are found to resemble those of their respective non-nitrogenated PAH cations. The IR spectra of H+ PANHs are significantly different owing to the NH inplane bending vibration, which generally couples very well with the aromatic CH bending and CC stretching modes. Implications of the NPAH (+, H+) laboratory spectra are discussed for the astrophysical IR emissions and, in particular, for the band at 6.2 mu m

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