Author: "Jean-Claude Guillemin" / Publisher: hal ccsd - Searchworks@Jio Institute Digital Library Search Results

Your search keyword '"Jean-Claude Guillemin"' showing total 144 results

Start Over Author "Jean-Claude Guillemin" Publisher hal ccsd

144 results on '"Jean-Claude Guillemin"'

1. Synthesis, Characterization and Chemistry of Tetrakis(Propargylisocyanide) Copper(I) Complex

Author: Alexandre Quelhas, Thierry Roisnel, Jean-Claude Guillemin, Yann Trolez, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Ugi reaction, isocyanide, copper, Organic Chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Biochemistry, cycloaddition
Abstract: International audience; The kinetically unstable propargylisocyanide was reacted with the tetrakis(acetonitrile) copper(I) hexafluorophosphate and the formed complex was then involved in a copper-catalyzed alkyne-azide cycloaddition reaction (CuAAC). After the decomplexation of the adduct, the isocyanide was engaged in a Ugi reaction. By such a complexation, reactions can be carried out on the CC triple bond without the constraint of the instability of the free compound or the competitive reactivity of the isocyanide group.
Published: 2023
Full Text: View/download PDF

2. Spectroscopic and Computational Characterization of 2-Aza-1,3-butadiene, a Molecule of Astrochemical Significance

Author: Ningjing Jiang, Mattia Melosso, Luca Bizzocchi, Silvia Alessandrini, Jean-Claude Guillemin, Luca Dore, Cristina Puzzarini, Alma Mater Studiorum Università di Bologna [Bologna] (UNIBO), University of Naples Federico II = Università degli studi di Napoli Federico II, Scuola Normale Superiore di Pisa (SNS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), This study was supported by the University of Bologna (RFO funds) as well as by the Italian Space Agency (ASI, 'Life in Space' project, N. 2019-3-U.0). N.J. thanks the China Scholarships Council (CSC) for financial support. J.C.G. thanks the Centre National d’Etudes Spatiales (CNES) and the Program 'Physique et Chimie du Milieu Interstellaire' (INSU-CNRS) for grants., Jiang, Ningjing, Melosso, Mattia, Bizzocchi, Luca, Alessandrini, Silvia, Guillemin, Jean-Claude, Dore, Luca, and Puzzarini, Cristina
Subjects: Butadiene, Polarity, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Molecular structure, Energy levels, Spectroscopy, butadiene, heterodienes, spectroscopy, structure, insterstellar medium
Abstract: International audience; Being N-substituted unsaturated species, azabutadienes are molecules of potential relevance in astrochemistry, ranging from the interstellar medium to Titan’s atmosphere. 2-Azabutadiene and butadiene share a similar conjugated π system, thus allowing investigation of the effects of heteroatom substitution. More interestingly, 2-azabutadiene can be used to proxy the abundance of interstellar butadiene. To enable future astronomical searches, the rotational spectrum of 2-azabutadiene has been investigated up to 330 GHz. The experimental work has been supported and guided by accurate computational characterization of the molecular structure, energetics, and spectroscopic properties of the two possible forms, trans and gauche. The trans species, more stable by about 7 kJ/mol than gauche-2-azabutadiene, has been experimentally observed, and its rotational and centrifugal distortion constants have been obtained with remarkable accuracy, while theoretical estimates of the spectroscopic parameters are reported for gauche-2-azabutadiene.
Published: 2022
Full Text: View/download PDF

3. Phosphorescence of Hydrogen-Capped Linear Polyyne Molecules C8H2, C10H2 and C12H2 in Solid Hexane Matrices at 20 K

Author: Tomonari Wakabayashi, Urszula Szczepaniak, Kaito Tanaka, Satomi Saito, Keisuke Fukumoto, Riku Ohnishi, Kazunori Ozaki, Taro Yamamoto, Hal Suzuki, Jean-Claude Guillemin, Haruo Shiromaru, Takeshi Kodama, Miho Hatanaka, Kindai University, Institute of Physical Chemistry [Warsaw], Polish Academy of Sciences, Department III, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: poyyne, phosphorescence, matrix isolation, electronic transition, molecular vibration, [SHS.CLASS]Humanities and Social Sciences/Classical studies
Abstract: Laser-ablated polyyne molecules, H(C≡C)nH, were separated by size in solutions and co-condensed with excess hexane molecules at a cryogenic temperature of 20 K in a vacuum system. The solid matrix samples containing C8H2, C10H2, and C12H2 molecules were irradiated with UV laser pulses and the phosphorescence 0–0 band was observed at 532, 605, and 659 nm, respectively. Vibrational progression was observed for the symmetric stretching mode of the carbon chain in the ground state with increments of ~2190 cm−1 for C8H2, ~2120 cm−1 for C10H2, and ~2090 cm−1 for C12H2. Temporal decay analysis of the phosphorescence intensity revealed the lifetimes of the triplet state as ~30 ms for C8H2, ~8 ms for C10H2, and ~4 ms for C12H2. The phosphorescence excitation spectrum reproduces UV absorption spectra in the hexane solution and in the gas phase at ambient temperature, although the excitation energy was redshifted. The symmetry-forbidden vibronic transitions were observed for C10H2 by lower excitation energies of 25,500–31,000 cm−1 (320–390 nm). Detailed phosphorescence excitation patterns are discussed along the interaction of the polyyne molecule and solvent molecules of hexane.
Published: 2022
Full Text: View/download PDF

4. Millimetre-wave laboratory study of glycinamide and a search for it with ALMA towards Sagittarius B2(N)

Author: Arnaud Belloche, Lech Pszczółkowski, E. Białkowska-Jaworska, Robin T. Garrod, José L. Alonso, Holger S. P. Müller, Jean-Claude Guillemin, Karl M. Menten, Zbigniew Kisiel, Iker León, Elena R. Alonso, L. Kolesniková, Institute of Physics, Polish Academy of Sciences, Polska Akademia Nauk = Polish Academy of Sciences (PAN), Spanish National Research Council (CSIC), Universidad de Valladolid [Valladolid] (UVa), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), University of Virginia, Universität zu Köln = University of Cologne, Max-Planck-Institut für Radioastronomie (MPIFR), National Science Foundation, NSF: AST 19-06489, G61-6, Providence Health Care, PHC, European Research Council, ERC, Deutsche Forschungsgemeinschaft, DFG: 184018867, Centre National d’Etudes Spatiales, CNES, Centre National de la Recherche Scientifique, CNRS, Ministerio de Ciencia e Innovación, MICINN: CTQ2016-76393-P, PID2019-111396GB-I00, Institut de Cardiologie de Montréal, MHI, and Junta de Castilla y León, JCYL: VA077U16, VA244P20
Subjects: Physics, Line: identification, Galactic Center, FOS: Physical sciences, Astronomy and Astrophysics, Astrophysics, Astrophysics - Astrophysics of Galaxies, Molecular physics, Spectral line, ISM: molecules, Rotational energy, Astronomical databases: miscellaneous, Space and Planetary Science, Astrophysics of Galaxies (astro-ph.GA), Excited state, [CHIM]Chemical Sciences, Sagittarius B2, Rotational spectroscopy, Ground state, Astrophysics::Galaxy Astrophysics, Quantum tunnelling, Astrochemistry, ISM: individual objects: Sagittarius B2
Abstract: Glycinamide is considered to be one of the possible precursors of the simplest amino acid glycine. Its only rotational spectrum reported so far has been in the cm-wave region. The aim of this work is to extend its laboratory spectrum into the mm wave region to support its searches in the ISM. Glycinamide was synthesised chemically and was studied with broadband rotational spectroscopy in the 90-329 GHz region. Tunneling across a low energy barrier between two symmetry equivalent configurations of the molecule resulted in splitting of each vibrational state and many perturbations in associated rotational energy levels, requiring careful coupled state fits for each vibrational doublet. We searched for emission of glycinamide in the imaging spectral line survey ReMoCA performed with ALMA toward Sgr B2(N). We report the first analysis of the mm-wave rotational spectrum of glycinamide, resulting in fitting to experimental measurement accuracy of over 1200 transition frequencies for the ground state tunneling doublet, of many lines for tunneling doublets for two singly excited vibrational states, and determination of precise vibrational separation in each doublet. We did not detect emission from glycinamide in the hot core Sgr B2(N1S). We found that glycinamide is at least seven times less abundant than aminoacetonitrile and 1.8 times less abundant than urea in this source. A comparison with results of astrochemical kinetics models for species related to glycinamide suggests that its abundance may be at least one order of magnitude below the upper limit obtained toward Sgr B2(N1S). This means that glycinamide emission in this source likely lies well below the spectral confusion limit in the frequency range covered by the ReMoCA survey. Targetting sources with a lower level of spectral confusion, such as the Galactic Center shocked region G+0.693-0.027, may be a promising avenue. [abridged], Accepted for publication in A&A
Published: 2022
Full Text: View/download PDF

5. High-Resolution Infrared Spectroscopy of DC3N in the Stretching Region

Author: Ningjing Jiang, Mattia Melosso, Filippo Tamassia, Luca Bizzocchi, Luca Dore, Elisabetta Canè, Davide Fedele, Jean-Claude Guillemin, Cristina Puzzarini, University of Bologna, Max Planck Institute for Extraterrestrial Physics (MPE), Max-Planck-Gesellschaft, Istituto Nazionale di Astrofisica (INAF), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Bologna University (RFO funds), MIUR (Project PRIN 2015: STARS in the CAOS) Ministry of Education, Universities and Research (MIUR) [2015F59J3R], China Scholarships Council (CSC), Centre National d'Etudes Spatiales (CNES) Centre National D'etudes Spatiales, Ministry of Education, University and Research (MIUR) Ministry of Education, Universities and Research (MIUR) [L. 232], Ningjing Jiang, Mattia Melosso, Filippo Tamassia, Luca Bizzocchi, Luca Dore, Elisabetta Canè, Davide Fedele, Jean-Claude Guillemin, Cristina Puzzarini, University of Bologna/Università di Bologna, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: cyanoacetylene, 010504 meteorology & atmospheric sciences, lcsh:Astronomy, Infrared, Infrared spectroscopy, Astrophysics::Cosmology and Extragalactic Astrophysics, 01 natural sciences, Spectral line, law.invention, lcsh:QB1-991, Telescope, chemistry.chemical_compound, law, 0103 physical sciences, Cyanoacetylene, [CHIM]Chemical Sciences, infrared spectroscopy, 010303 astronomy & astrophysics, Astrophysics::Galaxy Astrophysics, 0105 earth and related environmental sciences, Physics, Spectrometer, interstellar, lcsh:QC801-809, Astronomy and Astrophysics, cyanoacetylene, interstellar: matter, rovibrational spectroscopy, spectral analysis, infrared spectroscopy, Rotational–vibrational spectroscopy, matter, spectral analysis, Interstellar medium, lcsh:Geophysics. Cosmic physics, chemistry, 13. Climate action, interstellar: matter, Astrophysics::Earth and Planetary Astrophysics, Atomic physics, rovibrational spectroscopy
Abstract: The perspectives opened by modern ground-based infrared facilities and the forthcoming James Webb Telescope mission have brought a great attention to the ro-vibrational spectra of simple interstellar molecules. In this view, and because of the lack of accurate spectroscopic data, we have investigated the infrared spectrum of deuterated cyanoacetylene (DC3N), a relevant astrochemical species. The ν1, ν2, and ν3 fundamentals as well as their hot-bands were observed in the stretching region (1,500–3,500 cm−1) by means of a Fourier transform infrared spectrometer. Supplementary measurements were performed at millimeter-wavelengths (243–295 GHz) with a frequency-modulation spectrometer equipped with a furnace, that allowed to probe pure rotational transitions in the investigated stretching states. Furthermore, since HC3N is observed as by-product in our spectra and suffers from the same deficiency of accurate infrared data, its ro-vibrational features have been analyzed as well. The combined analysis of both rotational and ro-vibrational data allowed us to determine precise spectroscopic constants that can be used to model the infrared spectra of DC3N and HC3N. The importance of accurate molecular data for the correct modeling of proto-planetary disks and exoplanetary atmospheres is then discussed.
Published: 2021
Full Text: View/download PDF

6. Submillimeter wave spectroscopy of propanoic acid (CH3CH2COOH) and its ISM search

Author: Lucie Kolesniková, O. Dorovskaya, Elena R. Alonso, Vadim V. Ilyushin, Laurent Margulès, José Cernicharo, Belén Tercero, Jean-Claude Guillemin, Roman A. Motiyenko, Eugene A. Alekseev, Institute of Radio Astronomy of NASU [Kharkiv] (IRA), National Academy of Sciences of Ukraine (NASU), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS), Physique Moléculaire aux Interfaces (PMI), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Observatorio Astronomico Nacional, Madrid, Universidad de Valladolid [Valladolid] (UVa), Instituto de Física Fundamental [Madrid] (IFF), Consejo Superior de Investigaciones Científicas [Madrid] (CSIC), Ecole Nationale Supérieure de Chimie de Rennes (ENSCR), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), LM/RAM/JCG acknowledge the support of the Programme National 'Physique et Chimie du Milieu Interstellaire' (PCMI) of CNRS/INSU. JCG thanks also the Centre National d’Etudes Spatiales (CNES) for a grant. BT and JC thank Ministerio de Ciencia e Innovación of Spain (MICIU) for funding support through projects AYA2016-75066-C2-1-P, PID2019-106110 GB-I00, PID2019-107115 GB-C21/ AEI/ 10.13039/501100011033, and PID2019-106235 GB-I00. We also thank ERC for funding through grant ERC2013-Syg-610256-NANOCOSMOS., ALMA is a partnership of ESO (representing its member states), NSF (USA), and NINS (Japan) with NRC (Canada), NSC, and ASIAA (Taiwan), and KASI (Republic of Korea), in cooperation with the Republic of Chile. The Joint ALMA Observatory is operated by ESO, AUI/NRAO, and NAOJ. This work was also based on observations carried out with the IRAM 30-meter telescope. IRAM is supported by INSU/CNRS (France), MPG (Germany), and IGN (Spain)., European Project: 610256,EC:FP7:ERC,ERC-2013-SyG,NANOCOSMOS(2014), Centre National de la Recherche Scientifique (France), Centre National D'Etudes Spatiales (France), Ministerio de Economía y Competitividad (España), Ministerio de Ciencia, Innovación y Universidades (España), European Commission, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: Methods: laboratory: molecular, Methyl acetate, Line: identification, Analytical chemistry, laboratory: molecular [Methods], 010402 general chemistry, 01 natural sciences, Ethyl formate, chemistry.chemical_compound, 0103 physical sciences, Molecule, Physical and Theoretical Chemistry, identification [Line], Spectroscopy, Submillimeter: ISM, molecules [ISM], Physics, 010304 chemical physics, Molecular data, Hydroxyacetone, ISM [Submillimeter], Atomic and Molecular Physics, and Optics, ISM: molecules, 0104 chemical sciences, 3. Good health, Interstellar medium, Propanoic acid, chemistry, 13. Climate action, Excited state, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], [SDU.ASTR.GA]Sciences of the Universe [physics]/Astrophysics [astro-ph]/Galactic Astrophysics [astro-ph.GA]
Abstract: 8 pags., 3 figs., 3 tabs., Three compounds with a CHO formula have been detected in the Interstellar Medium (ISM): ethyl formate (CHCHOC(O)H), methyl acetate (CHOC(O)CH) and very recently hydroxyacetone (CHC(O)CHOH). The higher thermodynamic stability of another isomer, the propanoic acid (CHCHC(O)OH), clearly suggests that this molecule should be considered as a possible candidate for ISM detection. To provide reliable predictions for astronomical use in the millimeter and submillimeter wave ranges we performed a new study of propanoic acid rotational spectrum up to 545 GHz. The analysis of large amplitude methyl top torsional motion in this molecule was carried out using the rho axis method and the RAM36 program code. More than 3200 lines corresponding to the rotational transitions in the ground and first excited methyl top torsional states were newly assigned and fit within experimental error. This enabled us to produce new predictions which were used to search for propanoic acid in two high-mass star-forming regions: SgrB2 (public IRAM 30 m) and Orion KL (ALMA Science Verification). We report a non-detection of propanoic acid in these clouds and derive upper limits to the column density., LM/RAM/JCG acknowledge the support of the Programme National “Physique et Chimie du Milieu Interstellaire” (PCMI) of CNRS/INSU. JCG thanks also the Centre National d’Etudes Spatiales (CNES) for a grant. BT and JC thank Ministerio de Ciencia e Innovaci ́on of Spain (MICIU) for funding support through projects AYA2016-75066-C2-1-P, PID2019-106110 GB-I00, PID2019-107115 GB-C21/ AEI/ 10.13039/ 501100011033, and PID2019-106235 GB-I00. We also thank ERC for funding through grant ERC2013-Syg-610256-NANOCOSMOS. This paper makes use of the following ALMA data: ADS/JAO. ALMA⧹♯2011.0.00009.SV. ALMA is a partnership of ESO (representing its member states), NSF (USA), and NINS (Japan) with NRC (Canada), NSC, and ASIAA (Taiwan), and KASI (Republic of Korea), in cooperation with the Republic of Chile. The Joint ALMA Observatory is operated by ESO, AUI/NRAO, and NAOJ. This work was also based on observations carried out with the IRAM 30-meter telescope. IRAM is supported by INSU/CNRS (France), MPG (Germany), and IGN (Spain)
Published: 2021
Full Text: View/download PDF

7. Millimeter- and submillimeter-wave spectrum of trans-formaldoxime (CH2NOH)

Author: Laurent Margulès, Roman A. Motiyenko, Luyao Zou, Jean-Claude Guillemin, Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS), Physique Moléculaire aux Interfaces (PMI), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Physics, Formamide, Astrochemistry, 010304 chemical physics, Spectrometer, Analytical chemistry, Astronomy and Astrophysics, Context (language use), Astrophysics, 7. Clean energy, 01 natural sciences, chemistry.chemical_compound, chemistry, Space and Planetary Science, Excited state, 0103 physical sciences, Structural isomer, Millimeter, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Ground state, 010303 astronomy & astrophysics
Abstract: Context. Among the six atoms of N-containing molecules with the formula of CH3NO, only formamide (H2NCHO), the most stable structural isomer, has been detected in the interstellar medium (ISM). The formaldoxime isomer may be formed, for example, by the reaction of formaldehyde (H2CO) or methanimine (H2CNH) and hydroxylamine (H2NOH), which are all detected in the ISM. The lack of high accuracy millimeter- and submillimeter-wave measurements hinders the astronomical search for formaldoxime. Aims. The aim of this work is to provide the direct laboratory measurement of the millimeter- and submillimeter-wave spectrum of trans-formaldoxime. Methods. Formaldoxime was synthesized and its rotational spectrum was recorded at room temperature in a glass flow cell using the millimeter- and submillimeter-wave spectrometer in Lille. The SPFIT program in the CALPGM suite was used to fit the spectrum. Results. Rotational lines of trans-formaldoxime from both the ground state and v12 = 1 vibrational excited states have been measured and assigned from 150 to 660 GHz. Spectroscopic constants were derived to the tenth order using both Watson’s A and S reduction Hamiltonian.
Published: 2021
Full Text: View/download PDF

8. An efficient photochemical route towards triplet ethynylphosphinidene, HCCP

Author: Arun‐Libertsen Lawzer, Thomas Custer, Jean‐Claude Guillemin, Robert Kołos, Polska Akademia Nauk = Polish Academy of Sciences (PAN), Ecole Nationale Supérieure de Chimie de Rennes (ENSCR), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: phosphapropadiene, Argon, HCCP, 010405 organic chemistry, Chemistry, Photochemistry, Phosphorus, Matrix isolation, chemistry.chemical_element, Rearrangement, General Medicine, General Chemistry, 010402 general chemistry, 01 natural sciences, Catalysis, 3. Good health, 0104 chemical sciences, Phosphinidene, phosphinidene, [CHIM]Chemical Sciences, Dehydrogenation
Abstract: International audience; While the archetypal free phosphinidene, H-P, has been studied for over a century, reports on uncomplexed, univalent phosphorus compounds are very sparse. Here we demonstrate production of HCCP in solid argon through the UV-induced rearrangement and subsequent dehydrogenation of phosphapropyne, CH 3 CP. Migration of H atoms along the CCP backbone of CH 3 CP resulted in production of the previously unobserved species 1-phosphapropadiene, CH 2 =C=PH, followed by ethynylphosphine, HCCPH 2 .
Published: 2021
Full Text: View/download PDF

9. Structural and thermochemical studies of pyrrolidine borane and piperidine borane by gas electron diffraction and quantum chemical calculations

Author: Sarah L. Masters, Conor D. Rankine, João Nunes, Jean-Claude Guillemin, Aliyu M. Ja’o, Derek A. Wann, University of Canterbury [Christchurch], University of York [York, UK], Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Federal University Kashere (Nigeria) through the Tertiary Education Trust Fund (TETFund), EPSRC Engineering and Physical Sciences Research Council (EPSRC) [EP/I004122, EP/1651146], PHC Dumont d'Urville [34165NB], Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: Hydrogen, Amine boranes, 010405 organic chemistry, Chemistry, Gas electron diffraction, chemistry.chemical_element, Boranes, Borane, Hydrogen storage, 010402 general chemistry, Condensed Matter Physics, 7. Clean energy, 01 natural sciences, Bond-dissociation energy, 0104 chemical sciences, Bond length, chemistry.chemical_compound, Computational chemistry, [CHIM]Chemical Sciences, Dehydrogenation, Physical and Theoretical Chemistry
Abstract: International audience; The gaseous structures, thermochemical properties and dehydrogenation reaction energy profiles of the borane complexes of pyrrolidine and piperidine have been investigated using gas electron diffraction (GED) and state-of-the-art computational methods. These complexes are of interest because of their potential as hydrogen storage materials for future onboard transport applications. A comparative structural and thermochemical analysis revealed structures with a slight difference in the essential B-N bond length, with the piperidine borane having a longer bond even though it has a stronger B-N bond according to predicted bond dissociation energies, a trend common with amine boranes. To identify the most favourable dehydrogenation pathway, BH3-catalysed and BH3-uncatalysed dehydrogenation channels have been explored, where the former has been shown to be the favourable process for both complexes. The energy requirements for the hydrogen release reactions are expected to be minimal as evidenced from the calculated dehydrogenation reaction energies, implying their suitability for onboard chemical hydrogen storage.
Published: 2021
Full Text: View/download PDF

10. Passerini and Ugi Reactions Involving Kinetically Unstable Isocyanides

Author: Houda Gazzeh, Yann Trolez, Alexandre Quelhas, Thierry Roisnel, Jean-Claude Guillemin, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Monastir - University of Monastir (UM), Centre National d'Etudes Spatiales (CNES) Centre National D'etudes Spatiales, Ministère de l'Enseignement Supérieur, de la Recherche et de l'Innovation, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: 010405 organic chemistry, Chemistry, Organic Chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, Passerini reaction, 3. Good health, 0104 chemical sciences, Ugi reaction, Organic chemistry, [CHIM]Chemical Sciences, Multicomponent Reaction, Physical and Theoretical Chemistry, Passerini Reaction, Ugi Reaction, Kinetically Unstable Isocyanides
Abstract: International audience; Kinetically unstable isocyanides as vinyl, allenyl and propargyl isocyanides react in Passerini and Ugi reactions faster than they decompose and lead to functionalized alpha-acyloxy amides and alpha-amino amides, respectively, which can subsequently be used in reactions involving the unsaturated substituent.
Published: 2021
Full Text: View/download PDF

11. Hydrogenation of glycolaldehyde to ethylene glycol at 10 K

Author: Lahouari Krim, Jean-Claude Guillemin, Killian Leroux, De la Molécule aux Nanos-objets : Réactivité, Interactions et Spectroscopies (MONARIS), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: Physics, Glycolaldehyde, astrochemistry, Astronomy and Astrophysics, 010402 general chemistry, 01 natural sciences, ISM: molecules, 0104 chemical sciences, chemistry.chemical_compound, molecular processes, chemistry, Space and Planetary Science, 0103 physical sciences, Polymer chemistry, methods: laboratory: solid state, [CHIM]Chemical Sciences, 010303 astronomy & astrophysics, Ethylene glycol, techniques: spectroscopic
Abstract: Glycolaldehyde, the simplest sugar, is a complex organic molecule detected in many regions of the interstellar medium (ISM). Although its synthetic routes are fairly well known and consistent with many laboratory studies, queries still arise about its reactivity and its role in the complex chemistry of the ISM. This study shows the surface and bulk hydrogenation of glycolaldehyde at 10 K in order to confirm or invalidate the astrophysical models which suggest that CHOCH2OH would be a precursor of ethylene glycol through hydrogenation processes occurring on the surface of interstellar dust grains. By coupling IR spectroscopy and mass spectrometry, we show that the formation of HOCH2CH2OH from CHOCH2OH + H solid state reaction occurs, supporting the existence of a chemical link between these two organics in the ISM. This work suggests that while CHO + CH2OH and CH2OH + CH2OH radical recombination would lead to CHOCH2OH and HOCH2CH2OH, respectively, the presence of H-atoms in the ISM would be a secondary source to favour ethylene glycol over glycolaldehyde. These results are in good agreement with different astronomical observations which show simultaneous detections of glycolaldehyde and ethylene glycol with an abundance ratio HOCH2CH2OH/CHOCH2OH ranged between 1 and 15.
Published: 2021
Full Text: View/download PDF

12. Rotational spectroscopic study of S-methyl thioformate: A global laboratory analysis of ground and excited torsional states up to 660 GHz

Author: Isabelle Kleiner, Roman A. Motiyenko, Jean-Claude Guillemin, Laurent Margulès, Belén Tercero, José Cernicharo, Eugene A. Alekseev, Atef Jabri, Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA (UMR_7583)), Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)-Université de Paris (UP), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS), Physique Moléculaire aux Interfaces (PMI), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Université de Lille, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Grant, Centre National d’Etudes Spatiales, ERC-2013Syg-610256-NANOCOSMOS, ERC, AYA2012-32032, MINECO, ASTROMOL CSD 2009-00038, CONSOLIDER-Ingenio, SPECTRORIMI, PCMI/CEA/CNRS, travel Grants, GDR SPECMO 3152, Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), National Science Foundation (US), European Southern Observatory, National Institutes of Natural Sciences (Japan), National Research Council of Canada, Ministry of Science and Technology (Taiwan), Academia Sinica (Taiwan), Korea Astronomy and Space Science Institute, ALMA Observatory, National Astronomical Observatory of Japan, National Radio Astronomy Observatory (US), Institut national des sciences de l'Univers (France), Centre National de la Recherche Scientifique (France), Max Planck Society, Instituto Geográfico Nacional (España), European Commission, Ministerio de Economía y Competitividad (España), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Methyl formate, laboratory: molecular [Methods], methods: laboratory: molecular, Context (language use), Astrophysics, 7. Clean energy, 01 natural sciences, Molecular physics, Article, ISM: abundances, chemistry.chemical_compound, 0103 physical sciences, identification [Line], Spectroscopy, 010303 astronomy & astrophysics, Physics, abundances [ISM], [PHYS]Physics [physics], 010304 chemical physics, Spectrometer, ISM [Submillimeter], Astronomy and Astrophysics, Catalogues, Interstellar medium, chemistry, Space and Planetary Science, Excited state, submillimeter: ISM, Ground state, [PHYS.ASTR]Physics [physics]/Astrophysics [astro-ph], Microwave, line: identification, catalogs
Abstract: 9 pags., 3 figs., 6 tabs., Context. S-methyl thioformate CH3SC(O)H is a monosulfur derivative of methyl formate, a relatively abundant component of the interstellar medium (ISM). S-methyl thioformate being, thermodynamically, the most stable isomer, it can be reasonably proposed for detection in the ISM. Aims. This work aims to experimentally study and theoretically analyze the ground and first torsional excited states for CH3SC(O)H in a large spectral range for astrophysical use. Methods. S-methyl thioformate was synthesized as a result of a reaction of methyl mercaptan with acetic-formic anhydride. The millimeter-wave spectrum was then recorded for the first time from 150 to 660 GHz with the solid-state spectrometer located at Lille. Results. A set of 3545 lines is determined and combined with 54 previously measured lines in the microwave region, belonging to ground state νt = 0 as well as 1391 transitions in the first excited state of torsion ν18 = 1. Some 164 lines were also assigned to ν18 = 2 for the A-species. A global fit was performed using the BELGI-Cs code taking into account the large splitting of A and E lines due to methyl internal rotation motion with a relatively low barrier, V3 = 127.4846(15) cm-1. Conclusions. Using our spectroscopy work, a deep search of S-methyl thioformate was carried out in the IRAM 30 m and ALMA data of different high-mass star-forming regions (Orion KL and Sgr B2). We derived an upper limit to the CH3SC(O)H column density in these regions., This paper makes use of the following ALMA data: ADS/JAO.ALMA #2011.0.00009.SV. ALMA is a partnership of ESO (representing its member states), NSF (USA), and NINS (Japan), together with NRC (Canada), NSC and ASIAA (Taiwan), and KASI (Republic of Korea), in cooperation with the Republic of Chile. The Joint ALMA Observatory is operated by ESO, AUI/NRAO, and NAOJ. The results are also based on observations obtained with the IRAM 30 m telescope supported by INSU/CNRS (France), MPG (Germany), and IGN (Spain). This work was supported by the Programme National Physique et Chimie du Milieu Intestellaire (PCMI) of CNRS/INSU with INC/INP co-funded by CEA and CNES. B.T. and J.C. thank the ERC for support under grant ERC-2013-Syg-610 256- NANOCOSMOS and the Spanish MINECO for funding support under grants AYA2012-32032 and FIS2014-52172-C2, and the CONSOLIDER-Ingenio program “ASTROMOL” CSD 2009-00038. J.-C.G. thanks the Centre National d’Etudes Spatiales (CNES) for a grant.
Published: 2020
Full Text: View/download PDF

13. Submillimeter-wave spectroscopy and the radio-astronomical investigation of propynethial (HC≡CCHS)

Author: Brett A. McGuire, Corey J. Evans, Laurent Margulès, Roman A. Motiyenko, Donald McNaughton, Andy Wong, A. Remijan, Jean-Claude Guillemin, Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS), Physique Moléculaire aux Interfaces (PMI), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), National Radio Astronomy Observatory (NRAO), National Academy of Sciences of Ukraine (NASU), Kharkov National University, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Institut Rayonnement Matière de Saclay (IRAMIS), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay, James Cook University (JCU), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: molecular data, Extrapolation, methods: laboratory: molecular, Astrophysics, 01 natural sciences, Spectral line, chemistry.chemical_compound, symbols.namesake, 0103 physical sciences, Spectroscopy, 010303 astronomy & astrophysics, Astrophysics::Galaxy Astrophysics, Physics, [SDU.ASTR]Sciences of the Universe [physics]/Astrophysics [astro-ph], 010308 nuclear & particles physics, Astronomy and Astrophysics, Quantum number, Propynal, ISM: molecules, Interstellar medium, chemistry, Space and Planetary Science, symbols, submillimeter: ISM, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Hamiltonian (quantum mechanics), [PHYS.ASTR]Physics [physics]/Astrophysics [astro-ph], line: identification, Submillimeter wave
Abstract: Context. The majority of sulfur-containing molecules detected in the interstellar medium (ISM) are analogs of oxygen-containing compounds. Propynal was detected in the ISM in 1988, hence propynethial, its sulfur derivative, is a good target for an ISM search. Aims. Our aim is to measure the rotational spectrum of propynethial and use those measurements to search for this species in the ISM. To date, measurements of the rotational spectra of propynethial have been limited to a small number or transitions below 52 GHz. The extrapolation of the prediction to lines in the milimeter-wave domain is inaccurate and does not provide data to permit an unambiguous detection. Methods. The rotational spectrum was re-investigated up to 630 GHz. Using the new prediction lines of propynethial, as well as the related propynal, a variety of astronomical sources were searched, including star-forming regions and dark clouds. Conclusions. A total of 3288 transitions were newly assigned and fit together with those from previous studies, reaching quantum numbers up to J = 107 and Ka = 24. Watson’s symmetric top Hamiltonian in the Ir representation was used for the analysis, because the molecule is very close to the prolate limit. The search for propynethial resulted in a non-detection; upper limits to the column density were derived in each source.
Published: 2020
Full Text: View/download PDF

14. Millimeter- and submillimeter-wave spectroscopy of thioformamide and interstellar search toward Sgr B2(N)

Author: Laurent Margulès, Robin T. Garrod, Holger S. P. Müller, Arnaud Belloche, Roman A. Motiyenko, Karl M. Menten, Jean-Claude Guillemin, Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS), Physique Moléculaire aux Interfaces (PMI), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Max-Planck-Institut für Radioastronomie (MPIFR), University of Virginia, Université de Genève = University of Geneva (UNIGE), University of Applied Sciences of Western Switzerland, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), University of Virginia [Charlottesville], University of Geneva [Switzerland], Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: Astrochemistry, FOS: Physical sciences, Rotational transition, ISM: individual objects: Sagittarius B2(N), Context (language use), Astrophysics, 01 natural sciences, 7. Clean energy, Molecular physics, Spectral line, 0103 physical sciences, Spectroscopy, 010303 astronomy & astrophysics, Physics, radio lines: ISM, 010304 chemical physics, astrochemistry, Astronomy and Astrophysics, Astrophysics - Astrophysics of Galaxies, ISM: molecules, Interstellar medium, 13. Climate action, Space and Planetary Science, Astrophysics of Galaxies (astro-ph.GA), Excited state, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Ground state, [PHYS.ASTR]Physics [physics]/Astrophysics [astro-ph], line: identification
Abstract: Context. Thioformamide NH2CHS is a sulfur-bearing analog of formamide NH2CHO. The latter was detected in the interstellar medium back in the 1970s. Most of the sulfur-containing molecules detected in the interstellar medium are analogs of corresponding oxygen-containing compounds. Therefore, thioformamide is an interesting candidate for a search in the interstellar medium. Aims. A previous study of the rotational spectrum of thioformamide was limited to frequencies below 70 GHz and to transitions with J ≤ 3. The aim of this study is to provide accurate spectroscopic parameters and rotational transition frequencies for thioformamide to enable astronomical searches for this molecule using radio telescope arrays at millimeter wavelengths. Methods. The rotational spectrum of thioformamide was measured and analyzed in the frequency range 150−660 GHz using the Lille spectrometer. We searched for thioformamide toward the high-mass star-forming region Sagittarius (Sgr) B2(N) using the ReMoCA spectral line survey carried out with the Atacama Large Millimeter/submillimeter Array. Results. Accurate rigid rotor and centrifugal distortion constants were obtained from the analysis of the ground state of parent, 34S, 13C, and 15N singly substituted isotopic species of thioformamide. In addition, for the parent isotopolog, the lowest two excited vibrational states, v12 = 1 and v9 = 1, were analyzed using a model that takes Coriolis coupling into account. Thioformamide was not detected toward the hot cores Sgr B2(N1S) and Sgr B2(N2). The sensitive upper limits indicate that thioformamide is nearly three orders of magnitude at least less abundant than formamide. This is markedly different from methanethiol, which is only about two orders of magnitude less abundant than methanol in both sources. Conclusions. The different behavior shown by methanethiol versus thioformamide may be caused by the preferential formation of the latter (on grains) at late times and low temperatures, when CS abundances are depressed. This reduces the thioformamide-to-formamide ratio, because the HCS radical is not as readily available under these conditions.
Published: 2020
Full Text: View/download PDF

15. Phosphorescence excitation mapping and vibrational spectroscopy of HC9N and HC11N cyanopolyynes in organic solvents

Author: Yuma Ohnishi, Claudine Crépin, Kaito Tanaka, Yusuke Morisawa, Tomonari Wakabayashi, Robert Kołos, Hal Suzuki, Urszula Szczepaniak, Jean-Claude Guillemin, Yoriko Wada, Kazunori Ozaki, Polish Academy of Sciences (PAN), Kindai University, Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), SYSIPHE, Institut des Sciences Moléculaires d'Orsay (ISMO), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS)-Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS), The MEXT-Supported Program for the Strategic Research Foundation at Private Universities for Establishing a Best-Energy-Mix Research Center to Promote the Use of Solar Energy, S1411036, subsidized from the Ministry of Education, Culture, Sports, Science and Technology of Japan (MEXT) and Kindai University is greatly acknowledged. US is supported by the Mobility Contest Internship Program, Institute of Physical Chemistry, Polish Academy of Sciences for collaboration performed at Kindai University., Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Infrared absorption, Analytical chemistry, chemistry.chemical_element, Infrared spectroscopy, Shpolsky effect, 010402 general chemistry, 01 natural sciences, Matrix isolation, Resonance, Analytical Chemistry, Inorganic Chemistry, chemistry.chemical_compound, symbols.namesake, Raman, Spectroscopy, Cyanopolyyne, 010405 organic chemistry, Phosphorescence, Organic Chemistry, Krypton, [PHYS.PHYS.PHYS-ATM-PH]Physics [physics]/Physics [physics]/Atomic and Molecular Clusters [physics.atm-clus], 0104 chemical sciences, chemistry, Atomic electron transition, symbols, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Raman spectroscopy
Abstract: Cyanopolyyne molecules, HC9N and HC11N, were isolated in solutions and UV, IR, and resonance Raman spectra were measured for the study of their electronic and vibrational properties. Strong signals were observed both in the IR and resonance Raman spectra for the stretching vibrational mode of the sp-hybridized linear carbon chain in the electronic ground state, i.e., σ4 at 2141 cm−1 for HC9N and σ6 at 2105 cm−1 for HC11N. Trapped in cryogenic solid acetonitrile matrix hosts at 20 K, transitions in phosphorescence, a ˜ 3Σ+ → X ˜ 1Σ+, were observed for HC9N at 582.3 nm (0–0) and longer wavelengths and for HC11N at 643.7 nm (0–0) and longer wavelengths. Electronic transitions in the UV, 1Σ+ ← X ˜ 1Σ+, were elucidated by phosphorescence excitation mapping to observe asymmetric patterns with sharp emission-absorption features explainable by Shpolsky effects. For HC9N, three distinct trapping sites were discernible in solid acetonitrile, while the phosphorescence spectra were blurred in solid n-hexane. The observed phosphorescence lifetime of HC9N was longer than that of HC11N, comparable to the trend reported for the series of cyanopolyyne molecules in solid krypton matrix hosts.
Published: 2020
Full Text: View/download PDF

16. Relative thermodynamic stability of the [C,N,O] linkages as an indication of the most abundant structures in the ISM

Author: Jean-Claude Guillemin, O. Matz, Isabelle Fourré, Y. Ellinger, Laboratoire de chimie théorique (LCT), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: Physics, Astronomy and Astrophysics, Context (language use), Astrophysics, 010402 general chemistry, 01 natural sciences, Chemical formula, Quantum chemistry, ISM: molecules, ISM: abundances, 0104 chemical sciences, Ion, Coupled cluster, Space and Planetary Science, Computational chemistry, 0103 physical sciences, Density functional theory, Chemical stability, [PHYS.ASTR]Physics [physics]/Astrophysics [astro-ph], 010303 astronomy & astrophysics, Order of magnitude
Abstract: Context. Most of the compounds detected in the interstellar medium (ISM) that possess isomers correspond to the thermodynamically most stable isomer of a given chemical formula. Using the minimun energy principle (MEP) as a pragmatic tool is particularly efficient for less than six atoms, but for larger systems combinatorial analysis gives an intractable numbers of isomers. Aims. To make the MEP more applicable, we look for a chemical sieve to filter the thermodynamic data needed to determine which isomers of complex organic molecules (COMs) have higher chances of being present in the ISM. To do so, we investigate whether the nature of the [C,N,O] elementary fragment can be determinant for the stabilization of COMs, taking C2H3NO as a case study. Methods. We employed standard quantum chemistry methods to determine the ordering of fragments and derivatives on the energy scale. Density functional theory treatments were systematically performed, together with high-level coupled cluster calculations to refine relative energies. Results. For C2H3NO we find methylisocyanate CH3NCO, which is a compound that was very recently detected in the ISM, to be the most stable isomer in a corpus of 40 isomers of lowest energy. In neutral form we find the stability ordering of NCO > ONC; the same is true for the negative ion. Attachments of R=H, CH3, C2H5, HC2, H2CCH, and C6H5 and metals Al and Mg to the nitrogen atom of the NCO fragment provide the most stable isomers. The energy differences between the successive isomers on the energy scale R-NCO, R-OCN, R-CNO, and R-ONC are of the same order of magnitude for all carbonaceous R. Conclusions. Combining the criterion of most stable linkage with the MEP concept should greatly reduce the window of potential targets to be searched for in the ISM. Compounds containing the NCO linkage should be preferential targets of future research.
Published: 2020
Full Text: View/download PDF

17. VUV photoionization of the CH 2 NC radical: adiabatic ionization energy and cationic vibrational mode wavenumber determinations

Author: Oliver J. Harper, Sebastian Hartweg, Séverine Boyé-Péronne, Gustavo A. Garcia, Jean-Claude Guillemin, Bérenger Gans, Jean-Christophe Loison, Université de Bordeaux, ISM, UMR CNRS 5255, Talence, 33405, France, Institut des Sciences Moléculaires d'Orsay (ISMO), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS), European Synchrotron Radiation Facility (ESRF), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), This work was performed on the DESIRS beamline under proposal number 20181133. We acknowledge SOLEIL for provisionof synchrotron radiation facilities and the DESIRS beamline staff for their assistance. This work received financial support fromthe French Agence Nationale de la Recherche (ANR) under grant ANR-12-BS08-0020-02 (project SYNCHROKIN). This work wassupported by the Programme National Physique et Chimie du Milieu Interstellaire (PCMI) of CNRS/INSU with INC/INP co-fundedby CEA and CNES. J.-C.G. thanks the CNES for a grant., ANR-12-BS08-0020,SynchroKin,Mise en place d'une technique expérimentale pour la mesure de données cinétiques et mécanistiques utilisant la radiation synchrotron SOLEIL(2012), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Physics, [SDU.ASTR]Sciences of the Universe [physics]/Astrophysics [astro-ph], General Physics and Astronomy, 02 engineering and technology, Photoionization, Electron, 021001 nanoscience & nanotechnology, 01 natural sciences, 7. Clean energy, Spectral line, Ion, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Ab initio quantum chemistry methods, Molecular vibration, 0103 physical sciences, Physics::Atomic and Molecular Clusters, Physical and Theoretical Chemistry, Atomic physics, Ionization energy, Physics::Chemical Physics, 0210 nano-technology, 010303 astronomy & astrophysics, Excitation, ComputingMilieux_MISCELLANEOUS
Abstract: The photoelectron spectroscopy of CH2NC (isocyanomethyl) radical species is investigated for the first time between 9.3 and 11.2 eV in the vicinity of the first photoionizing transition X+1A1 ← X 2B1. The experiment combines a microwave discharge flow-tube reactor to produce the radicals through the CH3NC + F → CH2NC + HF reaction, a VUV synchrotron radiation excitation, and a double imaging electron/ion coincidence spectrometer which allows the recording of mass-selected threshold photoelectron spectra. Assignment of the observed vibrational structure of the CH2NC+ cation is guided by ab initio calculations and Franck-Condon simulations. From the experimental spectrum, the first adiabatic ionization energy of the CH2NC radical is measured as 9.439(6) eV. Fundamental wavenumbers are determined for several vibrational modes of the cation [small nu, Greek, tilde]1+(CH2 symmetric stretch) = 2999(80) cm-1, [small nu, Greek, tilde]2+(NC stretch) = 1925(40) cm-1, [small nu, Greek, tilde]4+(H2C-N stretch) = 1193(40) cm-1, [small nu, Greek, tilde]6+(CNC out-of-plane bend) = 237(50) cm-1, and [small nu, Greek, tilde]8+(CH2 rock) = 1185(60) cm-1.
Published: 2020
Full Text: View/download PDF

18. Spectroscopy of methylcyanodiacetylene revisited. Solid parahydrogen and solid neon matrix studies

Author: Robert Kołos, Michał Turowski, Claudine Crépin, Jean-Claude Guillemin, Urszula Szczepaniak, Alejandro Gutiérrez-Quintanilla, Thomas Custer, Institut des Sciences Moléculaires d'Orsay (ISMO), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS), Polish Academy of Sciences (PAN), Universidad de La Habana [Cuba], Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), This study was supported with the funds of the Polish National Science Centre, project No. 2011/03/B/ST4/02763, the French-Polish PICS project (2014–2016) and the RTRA Triangle de la Physique (2013-0436T REACMAQ)., Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Physics::General Physics, Polyyne, Analytical chemistry, chemistry.chemical_element, Infrared spectroscopy, 010402 general chemistry, Spin isomers of hydrogen, 01 natural sciences, Matrix isolation, Spectral line, Analytical Chemistry, Inorganic Chemistry, Neon, Ultraviolet visible spectroscopy, [CHIM]Chemical Sciences, UV/Vis spectroscopy, Spectroscopy, 010405 organic chemistry, Chemistry, Phosphorescence, Organic Chemistry, 0104 chemical sciences, IR spectroscopy
Abstract: International audience; Electronic phosphorescence and infrared absorption spectra of methylcyanodiacetylene (CH3C5N) are revisited using matrix isolation in solid parahydrogen and neon. Band assignments previously found for Ar, Kr, Xe, and N2 low-temperature host media were updated, with certain ambiguous attributions being resolved. A combined analysis of both dispersed phosphorescence and phosphorescence excitation spectra observed in different environments provides a means to estimate the singlet-triplet separation for the gas-phase and pure solid compound, where phosphorescence could not be observed.
Published: 2020
Full Text: View/download PDF

19. Photoisomerization of IC3N — An experimental and theoretical study

Author: Robert Kołos, A. Guzik, Marcin Gronowski, M. Turowski, Jean-Claude Guillemin, Cardinal Stefan Wyszyński University, Polska Akademia Nauk = Polish Academy of Sciences (PAN), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Centre National d'Etudes Spatiales, CNES, Cardinal Stefan Wyszyński University (UKSW), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Computational chemistry, Photoisomerization, Photochemistry, General Chemical Engineering, General Physics and Astronomy, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Matrix isolation, Ion, Ionization, [CHIM]Chemical Sciences, Physics::Chemical Physics, Quantum chemical, Argon, Chemistry, Photodissociation, General Chemistry, 021001 nanoscience & nanotechnology, Potential energy, 0104 chemical sciences, IR spectroscopy, Cyanoacetylenes, 0210 nano-technology, Electronic energy
Abstract: International audience; Here we present the results of a joint spectroscopic and quantum chemical study on the photochemistry of 3-iodo-2-propynenitrile (iodocyanoacetylene, IC3N). Vacuum-UV photolysis of the compound isolated in solid argon was explored. Calculations, carried out at the DFT and/or coupled-cluster level of theory, provided essential data concerning the thermodynamic stabilities, vibrational and electronic energy levels, ionization potentials, and electron affinities of IC3N-stoichiometry isomers and ions. The photochemical formation of thus far unknown species IC2NC and ICNC2 has been evidenced by the experiment and rationalized based on a detailed theoretical approach, involving the excited-state potential energy surfaces.
Published: 2020
Full Text: View/download PDF

20. Solid-state formation of CO and H2CO via the CHOCHO + H reaction

Author: Killian Leroux, Jean-Claude Guillemin, Lahouari Krim, De la Molécule aux Nanos-objets : Réactivité, Interactions et Spectroscopies (MONARIS), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Astrochemistry, Formaldehyde, chemistry.chemical_element, Reaction intermediate, 010402 general chemistry, Photochemistry, 01 natural sciences, 7. Clean energy, chemistry.chemical_compound, Neon, 0103 physical sciences, 010303 astronomy & astrophysics, Physics, Glycolaldehyde, [SDU.ASTR]Sciences of the Universe [physics]/Astrophysics [astro-ph], astrochemistry, Matrix isolation, Astronomy and Astrophysics, ISM: molecules, 0104 chemical sciences, chemistry, 13. Climate action, Space and Planetary Science, methods: laboratory: solid state, Glyoxal, [CHIM.OTHE]Chemical Sciences/Other, Ethylene glycol, techniques: spectroscopic
Abstract: Glycolaldehyde (CHOCH2OH) and ethylene glycol (HOCH2CH2OH) are among many complex organic molecules detected in the interstellar medium (ISM). Astrophysical models proposed very often that the formation of these compounds would be directly linked to the hydrogenation of glyoxal (CHOCHO), a potential precursor which is not yet detected in the ISM. We have performed, in this work, surface and bulk hydrogenations of solid CHOCHO under ISM conditions in order to confirm or invalidate the astrophysical modelling of glyoxal transformation. Our results show that the hydrogenation of glyoxal does not lead to the formation of detectable amounts of heavier organic molecules such as glycolaldehyde and ethylene glycol but rather to lighter CO-bearing species such as CO, H2CO, and CO–H2CO, a reaction intermediate resulting from an H-addition–elimination process on CHOCHO and where CO is linked to H2CO. The solid phase formation of such a reaction intermediate has been confirmed through the neon matrix isolation of CO–H2CO species. Additionally, the CHOCHO + H solid-state reaction might also lead to the production of CH3OH formed under our experimental conditions as a secondary product resulting from the hydrogenation of formaldehyde.
Published: 2020
Full Text: View/download PDF

21. The quest of chirality in the interstellar medium I. Lessons of propylene oxide detection

Author: Alexis Markovits, F. Pauzat, A. Allaire, Y. Ellinger, Jean-Claude Guillemin, Laboratoire de chimie théorique (LCT), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Hydrogen, astrobiology, chemistry.chemical_element, Context (language use), 02 engineering and technology, Astrophysics, 01 natural sciences, Spectral line, chemistry.chemical_compound, 0103 physical sciences, Molecule, solid state: volatile, Propylene oxide, 010303 astronomy & astrophysics, Physics, [SDU.ASTR]Sciences of the Universe [physics]/Astrophysics [astro-ph], SM: abundances, Astronomy and Astrophysics, 021001 nanoscience & nanotechnology, Interstellar medium, chemistry, 13. Climate action, Space and Planetary Science, Chemical physics, Density functional theory, 0210 nano-technology, Chirality (chemistry)
Abstract: Context. All but one complex organic molecule (COM) detected so far in the interstellar medium (ISM) are achiral; propylene oxide (c-C2H3O)-CH3 is the only exception to this. Finding other chiral species is a priority for astrobiology to progress in the understanding of the emergence of life. Whatever the conditions of their formation, i.e., gas phase or grain chemistry, the detection relies on rotational spectra. This means that, if adsorbed after formation in the gas phase or directly formed on the icy grains, these COMs must escape in the gas phase as free flyers to be detectable. Aims. Learning the lesson drawn from the only observation of a chiral compound and considering the structural constraints imposed to a molecule to be chiral, we look at what species could satisfy these conditions and be potential targets for a radio astronomy search in the ISM gas phase. Methods. This question was addressed by combining two complementary approaches that rely on density functional theory. The structure, energetics, and spectroscopic parameters of each potential candidate were determined using molecular calculations. The propensity for a molecule to remain trapped on the ice coating of the grains was evaluated by numerical simulations making use of a solid state periodic model. Results. Replacing the -CH3 group on rigid propylene oxide by -CN, -CCH, -NH2, -OH, or -HCO gives oxirane daughter molecules whose adsorption energies divide into two classes: below and above the adsorption energy of H2O on solid water-ice ~13.5 kcal mol−1. Conclusions. The best chiral candidate would be a rigid molecule for an easier determination of its radio spectra. This molecule would be composed of a central carbon linked to one hydrogen and three different chemical groups as simple as possible. If not the most stable isomer, this candidate should be as close as possible on the energy scale, possess a significant dipole moment, and be less strongly attached to the ice than H2O itself.
Published: 2020
Full Text: View/download PDF

22. Quasi-symmetry effects in the threshold photoelectron spectrum of methyl isocyanate

Author: Gustavo García, Laurent H. Coudert, Oliver J. Harper, Stéphane Douin, Jean-Christophe Loison, Bérenger Gans, Jean-Claude Guillemin, Séverine Boyé-Péronne, Coudert, Laurent, Institut des Sciences Moléculaires d'Orsay (ISMO), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires (ISM), Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1 (UB)-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut National des Sciences de l'Univers, Centre National de la Recherche Scientifique, Centre National d’Etudes Spatiales, Institut de Physique du CNRS, Institut de Chimie du CNRS, Université Montesquieu - Bordeaux 4-Université Sciences et Technologies - Bordeaux 1-École Nationale Supérieure de Chimie et de Physique de Bordeaux (ENSCPB)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), and ANR-17-CE30-0031,PRIMA,Processus de Relaxation Induits dans les Milieux Astrophysiques par photoexcitation VUV(2017)
Subjects: [PHYS]Physics [physics], Materials science, 010304 chemical physics, Photoemission spectroscopy, General Physics and Astronomy, Synchrotron radiation, 010402 general chemistry, 01 natural sciences, 7. Clean energy, 0104 chemical sciences, [PHYS] Physics [physics], chemistry.chemical_compound, Amplitude, chemistry, Ab initio quantum chemistry methods, Molecular vibration, 0103 physical sciences, Molecule, Physical and Theoretical Chemistry, Ionization energy, Atomic physics, Methyl group
Abstract: International audience; The vacuum-ultraviolet threshold photoelectron spectrum of methyl isocyanate CH3NCO has been recorded from 10.4 eV to 12 eV using synchrotron radiation and a coincidence technique allowing for a mass-discrimination of the photoelectron signal. A significant improvement is achieved over previous investigations as this experimental setup leads to a much more resolved spectrum. Ten sharp peaks and a broad feature spanning 1.2 eV were recorded. This spectrum consists of X̃+ 2A″←X̃ 1A' and Ã+ 2A'←X̃ 1A' ionizing transitions. For the former, the adiabatic ionization energy was determined experimentally to be 10.596(6) eV; for the latter, its value was estimated to be 10.759(50) eV. Seven sharp peaks could be assigned to vibrational modes of the cation X̃+ 2A″ and neutral X̃ 1A' ground electronic states involving only the NCO group atoms. Theoretical modeling of the threshold photoelectron spectrum has proven difficult as methyl isocyanate is a non-rigid molecule displaying large amplitude internal rotation of the methyl group and ∠CNC bending mode, leading to the quasi-symmetry. With the help of ab initio calculations, a theoretical model in which these two large amplitude motions are included in addition to the five small amplitude vibrational modes involving NCO group atoms is proposed. Comparison with the experimental spectrum shows that the broad feature and the strongest peak line positions are well accounted for; their intensities are also fairly well reproduced after adjusting a few parameters.
Published: 2020
Full Text: View/download PDF

23. The rotational spectrum of Methylarsine

Author: Jean Demaison, Natalja Vogt, Harald Møllendal, Roman A. Motiyenko, Laurent Margulès, Jean-Claude Guillemin, Vadim V. Ilyushin, Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS), Physique Moléculaire aux Interfaces (PMI), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), V.N. Karazin Kharkiv National University (KhNU), Lomonosov Moscow State University (MSU), University of Oslo (UiO), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National d'Etudes Spatiales, CNESDr. Barbara Mez-Starck-Stiftung, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: media_common.quotation_subject, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Asymmetry, Analytical Chemistry, Inorganic Chemistry, Ab initio quantum chemistry methods, [CHIM]Chemical Sciences, Hyperfine structure, Torsional large amplitude motion, Spectroscopy, media_common, Coupling, Quadrupole hyperfine structure, Spectrometer, Microwave spectrum, 010405 organic chemistry, Chemistry, Organic Chemistry, Methylarsine, 0104 chemical sciences, Amplitude, Excited state, Quadrupole, Atomic physics
Abstract: The rotational spectrum of an organoarsenic compound, methylarsine, CH 3 AsH 2 , was studied in the frequency range 10–80 GHz using the Stark-modulated spectrometer in Oslo, and in the frequency range 150–660 GHz using the Lille spectrometer. The experimental work was augmented by high-level ab initio calculations. The analysis of large amplitude torsional motion in CH 3 AsH 2 was performed using the rho axis method and the RAM36 code modified to take into account the nuclear quadrupole hyperfine structure. The final fit used 48 parameters (including 3 parameters of quadrupole coupling) to give an overall unitless root-mean-square deviation of 0.92 for the dataset consisting of 2753, 991, and 414 transitions belonging, respectively, to the ground, first, and second excited torsional states. Compact grouping of rotational transitions due to the small asymmetry ( κ = - 0.9986 ), torsional splittings due to internal rotation of the CH 3 group, and relatively large hyperfine splittings due to a rather large value of the arsenic nuclear quadrupole moment ( χ a a = 35.4 MHz, χ c c = − 117.2 MHz, χ a c = 115.7 MHz) represent an interesting case of interplay of different splittings in a molecule with a rather strong coupling between internal and overall rotations ( ρ = 0.413 ).
Published: 2020
Full Text: View/download PDF

24. Vibronic structure of the cyanobutadiyne cation: I-VUV photoionization study of HC 5 N

Author: Bérenger Gans, Christian Alcaraz, Stéphane Douin, Jacques Liévin, Nicolas Lamarre, Jean-Claude Guillemin, Gustavo A. Garcia, Séverine Boyé-Péronne, Claire Romanzin, Laboratoire de Photophysique Moléculaire (PPM), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Moléculaires d'Orsay (ISMO), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire pour l'utilisation du rayonnement électromagnétique (LURE), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-MENRT-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Chimie Physique D'Orsay (LCPO), Université Paris-Sud - Paris 11 (UP11)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Faculté des Sciences, Université libre de Bruxelles (ULB), ANR-17-CE30-0031, Agence Nationale de la Recherche, IISN-4.4504.10, Fonds De La Recherche Scientifique - FNRS, ANR-17-CE30-0031,PRIMA,Processus de Relaxation Induits dans les Milieux Astrophysiques par photoexcitation VUV(2017), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), and Centre National de la Recherche Scientifique (CNRS)-Université Paris-Sud - Paris 11 (UP11)
Subjects: Materials science, General Physics and Astronomy, Photoionization, 010402 general chemistry, 01 natural sciences, 7. Clean energy, Molecular physics, Spectral line, Physico-chimie générale, Ab initio quantum chemistry methods, 0103 physical sciences, Physics::Atomic and Molecular Clusters, Physical and Theoretical Chemistry, Spectral resolution, Adiabatic process, 010304 chemical physics, Physique, Chimie théorique, Astronomie, Triple bond, 0104 chemical sciences, 3. Good health, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph], Ionization energy, Ground state
Abstract: We report the vacuum-ultraviolet threshold-photoelectron spectrum of HC5N recorded over a wide spectral range, from 84 000 to 120 000 cm-1, with a 120 cm-1 spectral resolution, better than what was achieved in previous photoelectron studies, and with mass selectivity. The adiabatic ionization potential of cyanobutadiyne is measured at 85 366 (±40) cm-1. Assignment of the vibrational bands of the four lowest electronic states X+2Π, A+2Π, B+2ς+, and C+2Π are performed, supported by high level ab initio calculations which are fully detailed in Paper II [B. Gans et al. J. Chem. Phys. 150, 244303 (2019)] and by Franck-Condon simulations. Only vibrational stretching modes are observed in the threshold-photoelectron spectra. The ground state of HC5N+ exhibits a vibrational progression in the ν2 stretching mode involving mainly the elongation of the CC triple bonds, whereas the A+ and C+ excited electronic states show a progression in the stretching mode mainly associated with the elongation of the CN bond, i.e. ν4 and ν3, respectively. The B+ state appears almost as a vibrationless structure in close vicinity to the A+ state., SCOPUS: ar.j, info:eu-repo/semantics/published
Published: 2019
Full Text: View/download PDF

25. Isomerization of cyanopropyne in solid argon

Author: Urszula Szczepaniak, Michał Turowski, Thomas Custer, Jean-Claude Guillemin, Isabelle Couturier-Tamburelli, Nathalie Piétri, Marcin Gronowski, Robert Kołos, Polish Academy of Sciences (PAN), Institut des Sciences Moléculaires d'Orsay (ISMO), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS), Physique des interactions ioniques et moléculaires (PIIM), Aix Marseille Université (AMU)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Polish National Science Centre [2011/03/B/ST4/02763, 2015/17/B/ST4/03875], French-Polish Polonium project (2015-2016) [33570RK], European Social Fund, Polish Government, COST STSM action [39577], Program PCMI (INSU-CNRS), Centre National d'Etudes Spatiales (CNES), Podlaskie Voivodeship, Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: Argon, Nitrile, Isocyanide, Cyanide, Photodissociation, General Physics and Astronomy, chemistry.chemical_element, Infrared spectroscopy, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Photochemistry, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Propargyl, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, 0210 nano-technology, Isomerization
Abstract: International audience; Cyanopropyne, CH3-C[triple bond, length as m-dash]C-CN, is a simple molecule whose photochemistry is still unexplored. Here we investigate the UV photolysis of this astrophysically significant nitrile trapped in solid argon. The FTIR study was assisted with 15N-isotopic substitution data and with DFT-level computations including the analyses of ground- and excited-state potential energy surfaces. Cyanopropyne was found to decay mainly via a two-step isomerization process. Infrared absorption spectra evolved to show signals from allenyl cyanide, CH2[double bond, length as m-dash]C[double bond, length as m-dash]CH-CN, which then further convert into propargyl cyanide, H-C[triple bond, length as m-dash]C-CH2-CN. Some evidence for the presence of allenyl isocyanide, propargyl isocyanide, 3-cyanocyclopropene, and 1,2,3-butatrien-1-imine under particular experimental conditions was also observed. Although cyano/isocyano interconversion has been observed during photolysis of other closely related species in solid argon matrices, including H-C[triple bond, length as m-dash]C-CN, no evidence could be found for production of 1-isocyano-1-propyne, CH3-C[triple bond, length as m-dash]C-NC for these experiments.
Published: 2019
Full Text: View/download PDF

26. Formation of methyl ketenimine (CH 3 CH=C=NH) and ethylcyanide (CH 3 CH 2 C≡N) isomers through successive hydrogenations of acrylonitrile (CH 2 =CH−C≡N) under interstellar conditions: The role of CH 3 C°H−C≡N radical in the activation of the cyano group chemistry

Author: Lahouari Krim, David E. Woon, Jean-Claude Guillemin, De la Molécule aux Nanos-objets : Réactivité, Interactions et Spectroscopies (MONARIS), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), University of Illinois at Urbana-Champaign [Urbana], University of Illinois System, ANR-11-IDEX-0004–02, LabEx MiChem French state funds, ANR-11-IDEX-0004,SUPER,Sorbonne Universités à Paris pour l'Enseignement et la Recherche(2011), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: Astrochemistry, [SDU.ASTR]Sciences of the Universe [physics]/Astrophysics [astro-ph], astrochemistry, Astronomy and Astrophysics, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, ISM: molecules, 3. Good health, 0104 chemical sciences, Ketenimine, chemistry.chemical_compound, chemistry, 13. Climate action, Space and Planetary Science, Group (periodic table), 0103 physical sciences, methods: laboratory: solid state, Acrylonitrile, [CHIM.OTHE]Chemical Sciences/Other, 010303 astronomy & astrophysics, techniques: spectroscopic
Abstract: International audience; Possible formation routes of interstellar amino acids have been proposed where the first step consists in the transformation of organic nitriles (RCH2 − C≡N) into ketenimines (RCH = C = NH). Such a transformation shows high-energy barriers and needs energetic processing to occur. We show in this study that the CN bond could be activated through H-addition reactions to form ketenimines when starting from organic α, β-unsaturated nitriles (C≡N). Consequently, both methyl ketenimine CH3CH = C = NH and ethylcyanide CH3CH2C≡N might have their origin from H2C = CH − C≡N + 2H reaction occurring on the interstellar icy grains. During the hydrogenation of H2C = CH − C≡N ice under interstellar conditions, CH3CH2C≡N has been formed with an abundance 10 times higher than that of CH3CH = C = NH. Our measurements lead us to conclude that such a distribution would be directly linked to the π-electrons delocalization H3C − C°H − C≡N ↔ H3C − CH = C = N° occurring during the reduction of the CC double bond of acrylonitrile.
Published: 2019
Full Text: View/download PDF

27. Photochemistry of XCH2CN (X = -Cl, -SH) in Argon Matrices

Author: Joanna Zapala, Thomas Custer, Jean-Claude Guillemin, Marcin Gronowski, Polish Academy of Sciences (PAN), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), NCN Grant [2015/17/B/ST4/03875], PHC Polonium (Campus France) [33570RK], Centre National d'Etudes Spatiales (CNES), French Programme National 'Physique et Chimie du Milieu Interstellaire', Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Argon, 010304 chemical physics, Annealing (metallurgy), Photodissociation, chemistry.chemical_element, Infrared spectroscopy, 010402 general chemistry, Photochemistry, 01 natural sciences, Sulfur, Dissociation (chemistry), 3. Good health, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry, 13. Climate action, 0103 physical sciences, CN-group, Emission spectrum, Physical and Theoretical Chemistry
Abstract: International audience; We report infrared spectra and photochemical behavior of the potentially astrochemically significant species, mercaptoacetonitrile (HS-CHC≡N) and, for comparison purposes, chloroacetonitrile (Cl-CHC≡N), both suspended in an argon matrix at 6 K. Photolytic formation of the isocyano products HS-CH-NC and Cl-CH-NC were observed as well as CHNSC and CHSCN (in HS-CHCN photolysis). While no dissociation products were observed for Cl-CH-CN, photolysis of HS-CH-CN produced compounds necessitating the loss of the CN group to form CH═S, the SH group to form HC-CN and HC-CN, or both CN and SH to form CH and CH. Observation of emission spectra upon annealing indicates the presence of free sulfur atom in matrices of photolyzed HS-CH-CN.
Published: 2019
Full Text: View/download PDF

28. Fourier transform microwave spectroscopy of Criegee intermediates: The conformational behaviour of butyraldehyde oxide

Author: Yasuki Endo, Carlos Cabezas, Jean-Claude Guillemin, National Chiao Tung University (NCTU), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), MOST 105-2811-M-009-026, Ministry of Science and Technology, Taiwan, Centre National d’Etudes Spatiales, Ministry of Science and Technology (Taiwan), Centre National D'Etudes Spatiales (France), Centre National de la Recherche Scientifique (France), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Fourier transform microwave spectroscopy, Methyl ethyl ketones, Pulsed electric discharges, Oxide, General Physics and Astronomy, 010402 general chemistry, Photochemistry, 01 natural sciences, Isomers, chemistry.chemical_compound, Criegee intermediate, 0103 physical sciences, Structural isomer, Criegee intermediates, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Butyraldehyde, Conformational isomerism, Transient species, Ozonolysis, 010304 chemical physics, Ketones, 3. Good health, 0104 chemical sciences, chemistry, Microwave spectroscopy, Isobutyraldehyde, N-butyraldehyde, Rotational spectroscopy, Electric discharges, Gases, Structural isomers
Abstract: Four conformers of the n-propyl-substituted Criegee intermediate, CH CH CH CHOO, also named n-butyraldehyde oxide, have been observed by Fourier transform microwave spectroscopy. The transient species was produced using a pulsed electric discharge of a gas mixture of 1,1-diiodobutane/O diluted in Ar or Ne. The observation of only syn species is in contrast to the results of other previous studies of alkyl-substituted Criegee intermediates, in particular, those for the structural isomers, isobutyraldehyde oxide ((CH ) CHCHOO), and methyl-ethyl-ketone oxide (C H C(CH )OO), for which syn and anti species have been observed coexisting in the gas phase., This research was supported by the Ministry of Science and Technology of Taiwan under Grant Nos MOST 104-2113-M-009-020 (Y.E.) and MOST 105-2811-M-009-026 and MOST 105- 2811-M-009-026 (C.C.). J.-C.G. thanks the Centre National d’Etudes Spatiales (CNES) and the Program PCMI (INSU-CNRS) for financial support.
Published: 2019
Full Text: View/download PDF

29. Rotational spectroscopy of malononitrile and its corresponding monoisocyanide isomer, isocyanoacetonitrile

Author: Laurent Margulès, E. A. Alekseev, Jean-Claude Guillemin, I. Armieieva, Roman A. Motiyenko, Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS), Physique Moléculaire aux Interfaces (PMI), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Institute of Radio Astronomy of NASU [Kharkiv] (IRA), National Academy of Sciences of Ukraine (NASU), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), French Programme National 'Physique et Chimie du Milieu Interstellaire', French Agence Nationale de la Recherche [ANR-13-BS05-0008 IMOLABS], Centre National d'Etudes Spatiales (CNES), ANR-13-BS05-0008,IMOLABS,Molecules interstellaires : spectroscopie et synthèse en laboratoire(2013), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: Astrochemistry, 010504 meteorology & atmospheric sciences, Context (language use), Astrophysics, 01 natural sciences, Molecular physics, Spectral line, chemistry.chemical_compound, ISM molecules, 0103 physical sciences, Molecule, 010303 astronomy & astrophysics, 0105 earth and related environmental sciences, Malononitrile, Physics, Spectrometer, [SDU.ASTR]Sciences of the Universe [physics]/Astrophysics [astro-ph], astrochemistry, astronomical databases miscellaneous, Astronomy and Astrophysics, submillimeter ISM, Interstellar medium, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry, Space and Planetary Science, Rotational spectroscopy, line identification, [CHIM.OTHE]Chemical Sciences/Other
Abstract: Context. Nitriles constitute almost 20% of the molecules observed in the interstellar medium, whereas only one dinitrile and one isocyanonitrile compound have been detected up to now. The lack of detections of such compounds may be partially explained by the lack of accurate spectroscopic data on their rotational spectra.Aims. Two small seven-atom dinitriles, malononitrile NCCH2CN and isocyanoacetonitrile NCCH2NC, were chosen as target species for this study. For malononitrile the goal of the study is to systematize all the previous measurements, and to extend the measurements to the sub-millimeter wavelength range. The spectrum of isocyanoacetonitrile has not been studied before.Methods. The rotational spectra of the two molecules were measured in the frequency range 150–660 GHz using the Lille fast-scan spectrometer. The spectroscopic study was supported by high-level theoretical calculations on the structure of these molecules and their harmonic force field.Results. Accurate frequency predictions for malononitrile and isocyanoacetonitrile were calculated on the basis of the analysis of their rotational spectra. The influence of the spin statistics on the intensities of the lines of malononitrile was taken into account. The provided line lists and sets of molecular parameters meet the needs of astrophysical searches for the two molecules.
Published: 2019
Full Text: View/download PDF

30. Alkylation of uracil and thymine in the gas phase through interaction with alkylmercury compounds

Author: M. Merced Montero-Campillo, Emmanuelle Léon, Manuel Yáñez, Jean-Claude Guillemin, Jeanine Tortajada, Jean-Yves Salpin, Violette Haldys, Latifa Latrous, Otilia Mó, Laboratoire Analyse et Modélisation pour la Biologie et l'Environnement (LAMBE), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Cergy Pontoise (UCP), Université Paris-Seine-Université Paris-Seine-Université d'Évry-Val-d'Essonne (UEVE)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Saclay (COmUE), Université de Tunis El Manar (UTM), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Universidad Autónoma de Madrid (UAM), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Universidad Autonoma de Madrid (UAM), Ministerio de Economía y Competitividad (España), and Comunidad de Madrid
Subjects: Alkylation, Electrospray ionization, Gas phase, Alkylmercury compounds, 010402 general chemistry, DFT calculations, 01 natural sciences, Dissociation (chemistry), Nucleobase, chemistry.chemical_compound, IRMPD, MS/MS, Infrared multiphoton dissociation, Physical and Theoretical Chemistry, Uracil, Instrumentation, Spectroscopy, Alkyl, chemistry.chemical_classification, 010401 analytical chemistry, Condensed Matter Physics, 0104 chemical sciences, Thymine, Crystallography, chemistry, [PHYS.PHYS.PHYS-CHEM-PH]Physics [physics]/Physics [physics]/Chemical Physics [physics.chem-ph]
Abstract: The gas-phase interactions of uracil and thymine with alkylmercury cations, in particular [CHHg], n-BuHg and t-BuHg, were studied through the use of electrospray ionization coupled to tandem mass spectrometry. We observed that the interaction of akylmercury compounds with the nucleobases (NB) gives rise to a single type of complex of general formula [RHg(NB)], except for t-butyl-mercury (no interaction). The subsequent MS/MS experiments show that the [RHg] ions (R = Me, n-Bu) exhibit a peculiar reactivity characterized by the transfer of the alkyl group to the nucleobases. Indeed, the main fragmentation process observed leads to the loss of neutral Hg, producing [(NB)R] ions. Only when the length of the alkyl chain increases, as in the case of reactions with [n-BuHg], a new fragmentation path is opened, yielding the protonated nucleobase, [(NB)H], with the concomitant elimination of 2 CH + Hg. A thorough analysis of the mechanisms behind both dominant processes was carried out through the use of Infrared Multiple Photon Dissociation (IRMPD) in the fingerprint region, combined with an analysis of the corresponding potential energy surfaces by using high-level density functional theory (DFT) calculations., The CLIO team (J. M. Ortega, G. Perilhous, J. P. Berthet) as well asP. Maître, D. Scuderi and V. Steinmetz are warmly acknowledgedfor their support during the FEL experiments. This work has beenalso partially supported by the “Fonds pour le Rayonnement dela Recherche (FRR, Université d’Evry Val d’Essonne) and by theProjects CTQ2015-63997-C2 and CTQ2016-76061-P of the Minis-terio de Economía y Competitividad of Spain, FOTOCARBON-CMS2013/MIT-2841 of the Comunidad Autónoma de Madrid and bythe COST Action CM1204 of the EU Framework Programme. Hori-zon 2020. Computational time at Centro de Computación Científica(CCC) of Universidad Autónoma de Madrid is also acknowledged.
Published: 2019
Full Text: View/download PDF

31. Astrophysical detections and databases for the mono deuterated species of acetaldehyde CH2DCOH and CH3COD

Author: Roman A. Motiyenko, L. H. Coudert, Charlotte Vastel, Jean-Claude Guillemin, L. Margulès, Emmanuel Caux, Institut des Sciences Moléculaires d'Orsay (ISMO), Université Paris-Sud - Paris 11 (UP11)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS), Physique Moléculaire aux Interfaces (PMI), Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Université de Lille, Institut de recherche en astrophysique et planétologie (IRAP), Institut national des sciences de l'Univers (INSU - CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Observatoire Midi-Pyrénées (OMP), Météo France-Centre National d'Études Spatiales [Toulouse] (CNES)-Université Fédérale Toulouse Midi-Pyrénées-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Météo France-Centre National d'Études Spatiales [Toulouse] (CNES)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche pour le Développement (IRD)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire Midi-Pyrénées (OMP), Institut de Recherche pour le Développement (IRD)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National d'Études Spatiales [Toulouse] (CNES)-Centre National de la Recherche Scientifique (CNRS)-Météo-France -Institut de Recherche pour le Développement (IRD)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National d'Études Spatiales [Toulouse] (CNES)-Centre National de la Recherche Scientifique (CNRS)-Météo-France -Centre National de la Recherche Scientifique (CNRS), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Astrochemistry, computer.software_genre, 01 natural sciences, chemistry.chemical_compound, ISM molecules, 0103 physical sciences, Molecule, Binary system, 010303 astronomy & astrophysics, ISM abundances, Physics, 010304 chemical physics, Database, [SDU.ASTR]Sciences of the Universe [physics]/Astrophysics [astro-ph], astrochemistry, Acetaldehyde, Astronomy and Astrophysics, Amplitude, chemistry, Deuterium, Space and Planetary Science, Ophiuchus, line identification, [CHIM.OTHE]Chemical Sciences/Other, computer, Methyl group
Abstract: Context. Detection of deuterated species may provide information on the evolving chemistry in the earliest phases of star-forming regions. For molecules with two isomeric forms of the same isotopic variant, gas-phase and solid-state formation pathways can be differentiated using their abundance ratio. Aims. Spectroscopic databases for astrophysical purposes are built for the two mono deuterated isomeric species CH2DCOH and CH3COD of the complex organic molecule acetaldehyde. These databases can be used to search and detect these two species in astrophysical surveys, retrieving their column density and therefore abundances. Methods. Submillimeter wave and terahertz transitions were measured for mono deuterated acetaldehyde CH2DCOH which is a non-rigid species displaying internal rotation of its asymmetrical CH2D methyl group. An analysis of a dataset consisting of previously measured microwave data and the newly measured transition was carried out with a model accounting for the large amplitude torsion. Results. The frequencies of 2556 transitions are reproduced with a unitless standard deviation of 2.3 yielding various spectroscopic constants. Spectroscopic databases for astrophysical purposes were built for CH2DCOH using the results of the present analysis and for CH3COD using the results of a previous spectroscopic investigation. These two species were both searched for and are detected toward a low-mass star-forming region. Conclusions. We report the first detection of CH2DCOH (93 transitions) and the detection of CH3COD (43 transitions) species in source B of the IRAS 16293−2422 young stellar binary system located in the ρ Ophiuchus cloud region, using the publicly available ALMA Protostellar Interferometric Line Survey.
Published: 2019
Full Text: View/download PDF

32. Photoionization and dissociative photoionization of propynal in the gas phase: theory and experiment

Author: Zied Gouid, Jean-Claude Guillemin, Mohammad Esmaïl Alikhani, Imene Derbali, Marie-Claire Gazeau, Majdi Hochlaf, Helgi Rafn Hrodmarsson, Emilie-Laure Zins, Martin Schwell, De la Molécule aux Nanos-objets : Réactivité, Interactions et Spectroscopies (MONARIS), Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Laboratoire de Modélisation et Simulation Multi Echelle (MSME), Université Paris-Est Marne-la-Vallée (UPEM)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA (UMR_7583)), Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris Diderot - Paris 7 (UPD7)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Rennes-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES), This work was supported by the Programme National 'Physique et Chimie du Milieu Interstellaire' (PCMI) of CNRS/INSU with INC/INP co-funded by CEA and CNES. We thank the COST ACTION CM 1401 'Our Astro-chemical history' and COST ACTION CM 1405 'Molecules in Motions' for support., Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris Diderot - Paris 7 (UPD7)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)-Université Paris Cité (UPCité), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Instrumentation, Simulation et Informatique Scientifique (COSYS-LISIS), Université Gustave Eiffel, Centre National de la Recherche Scientifique (CNRS)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Université Paris-Est Marne-la-Vallée (UPEM), Centre National de la Recherche Scientifique (CNRS)-Université Paris Diderot - Paris 7 (UPD7)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Institut national des sciences de l'Univers (INSU - CNRS), and zins, émilie-laure
Subjects: Population, General Physics and Astronomy, Zero-point energy, 02 engineering and technology, Photoionization, 010402 general chemistry, 01 natural sciences, chemistry.chemical_compound, Ionization, [CHIM] Chemical Sciences, Physics::Atomic and Molecular Clusters, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Physics::Chemical Physics, education, Physics, education.field_of_study, 021001 nanoscience & nanotechnology, Propynal, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Coupled cluster, chemistry, 13. Climate action, Excited state, Atomic physics, Ionization energy, 0210 nano-technology
Abstract: International audience; Propynal (HCCCHO) is a complex organic compound (COM) of astrochemical and astrobiological interest. We present a combined theoretical and experimental investigation on the single photon ionization of gas-phase propynal, in the 10 to 15.75 eV energy range. Fragmentation pathways of the resulting cation were investigated both theoretically and experimentally. The adiabatic ionization energy (AIE) has been measured to be AIEexp = 10.715 ± 0.005 eV using tunable VUV synchrotron radiation coupled with a double imaging photoelectron photoion coincidence (i2PEPICO) spectrometer. In the energy range under study, three fragments formed by dissociative photoionization were identified experimentally: HC3O+, HCO+ and C2H2+, and their respective appearance energies (AE) were found to be AE = 11.26 ± 0.03, 13.4 ± 0.3 and 11.15 ± 0.03 eV, respectively. Using explicitly correlated coupled cluster calculations and after inclusion of the zero point vibrational energy, core–valence and scalar relativistic effects, the AIE is calculated to be AIEcalc = 10.717 eV, in excellent agreement with the experimental finding. The appearance energies of the fragments were calculated using a similar methodological approach. To further interpret the observed vibrational structure, anharmonic frequencies were calculated for the fundamental electronic state of the propynal cation. Moreover, MRCI calculations were carried out to understand the population of excited states of the cationic species. This combined experimental and theoretical study will help to understand the presence and chemical evolution of propynal in the external parts of interstellar clouds where it has been observed.
Published: 2019
Full Text: View/download PDF

33. A Comprehensive Spectral Rotational Analysis of the Interstellar Methyl Isocyanate CH3NCO

Author: Zbigniew Kisiel, Ivan R. Medvedev, Manfred Winnewisser, JoséL. Alonso, Jean-Claude Guillemin, Elena R. Alonso, Lucie Kolesniková, Spanish National Research Council (CSIC), Polish Academy of Sciences (PAN), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Wright State University, Ohio State University [Columbus] (OSU), Ministerio de Ciencia e InnovacionInstituto de Salud Carlos IIISpanish Government [CSD2009-00038, CTQ2013-40717-P, CTQ2016-76393-P, BES-2014-067776], Junta de Castilla y LeonJunta de Castilla y Leon [VA077U16], European Research Council under the European Union's Seventh Framework Programme (FP/2007-2013)/ERC-2013-SyG [610256], Program PCMI (INSU-CNRS), Centre National d'Etudes Spatiales (CNES)Centre National D'etudes Spatiales, Czech Science Foundation (GACR)Grant Agency of the Czech Republic [19-25116Y], Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Physics, Laboratory astrophysics, Spectral line lists, Experimental techniques, Astronomy and Astrophysics, Interstellar molecules, Molecular spectroscopy, Methyl isocyanate, Interstellar medium, chemistry.chemical_compound, chemistry, Space and Planetary Science, High resolution spectroscopy, Physical chemistry, [CHIM]Chemical Sciences
Abstract: International audience; Methyl isocyanate (CH3NCO) is a recently identified interstellar molecule giving rise to many detected lines. Interestingly, its delayed identification was due not to weak lines but to a very complex rotational spectrum. To date, the only published laboratory transitions for this molecule are those between rotational energy levels with K
Published: 2019
Full Text: View/download PDF

34. Single photon ionization of methyl isocyanide and the subsequent unimolecular decomposition of its cation experiment and theory

Author: Martin Schwell, Marie-Claire Gazeau, A. Bellili, Yves Bénilan, Zied Gouid, Jean-Claude Guillemin, Nicolas Fray, Majdi Hochlaf, Laboratoire de Modélisation et Simulation Multi Echelle (MSME), Université Paris-Est Marne-la-Vallée (UPEM)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA (UMR_7583)), Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris Diderot - Paris 7 (UPD7)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Institut National des Sciences de l'Univers, Centre National de la Recherche Scientifique, Commissariat à l'Énergie Atomique et aux Énergies Alternatives, Centre National d’Etudes Spatiales, CM 1405, European Cooperation in Science and Technology, Centre National de la Recherche Scientifique (CNRS)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Université Paris-Est Marne-la-Vallée (UPEM), Centre National de la Recherche Scientifique (CNRS)-Université Paris Diderot - Paris 7 (UPD7)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Institut national des sciences de l'Univers (INSU - CNRS), Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Chimie de Rennes-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Institut national des sciences de l'Univers (INSU - CNRS)-Université Paris Diderot - Paris 7 (UPD7)-Centre National de la Recherche Scientifique (CNRS)
Subjects: education.field_of_study, Materials science, Methyl isocyanide, Population, Analytical chemistry, General Physics and Astronomy, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Spectral line, 0104 chemical sciences, 3. Good health, Ion, chemistry.chemical_compound, chemistry, Fragmentation (mass spectrometry), 13. Climate action, Ionization, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Ionization energy, 0210 nano-technology, Ground state, education
Abstract: International audience; Methyl isocyanide, CH3NC, is a key compound in astrochemistry and astrobiology. A combined theoretical and experimental investigation of the single photon ionization of gas phase methyl isocyanide and its fragmentation pathways is presented. Vacuum ultraviolet (VUV) synchrotron radiation based experiments are used to measure the threshold photoelectron photoion coincidence (TPEPICO) spectra between 10.6 and 15.5 eV. This allowed us to experimentally determine the adiabatic ionization energy (AIE) and fragment ion appearance energies (AE) of gas-phase methyl isocyanide. Its AIE has been measured with a precision never achieved before. It is found to be AIEexp = 11.263 ± 0.005 eV. We observe a vibrational progression upon ionization corresponding to the population of vibrational levels of the ground state of the methyl isocyanide cation. In addition, four fragment ion appearance energies (AEs) were measured to be AE (m/z 40) = 12.80 ± 0.05 eV, AE (m/z 39) = 13.70 ± 0.05, AE (m/z 15) = 13.90 ± 0.05 eV, AE (m/z 14) 13.85 ± 0.05 eV, respectively. In order to interpret the experimental data, we performed state-of-the-art computations using the explicitly correlated coupled cluster approach. We also considered the zero-point vibrational energy (ZPVE), core-valence (CV) and scalar relativistic (SR) effects. The results of theoretical calculations of the AIE and AEs are in excellent agreement with the experimental findings allowing for assignment of the fragmentations to the loss of neutral H, H2, CN and HCN upon ionization of CH3NC. The computations show that in addition to the obvious bond breakings, some of the corresponding ionic fragments result from rearrangements - upon photon absorption - either before or after electron ejection.
Published: 2019
Full Text: View/download PDF

35. Formation of amines hydrogenation of nitrile and isonitrile as selective routes in the interstellar medium

Author: S. Baouche, François Dulieu, Isabelle Fourré, Jean-Claude Guillemin, T. Nguyen, E. Congiu, Y. Ellinger, Cécile Favre, C. Barois, Laboratoire d'Etude du Rayonnement et de la Matière en Astrophysique (LERMA (UMR_8112)), Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Cergy Pontoise (UCP), Université Paris-Seine-Université Paris-Seine-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Hokkaido University [Sapporo, Japan], Laboratoire de chimie théorique (LCT), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut de Planétologie et d'Astrophysique de Grenoble (IPAG), Institut national des sciences de l'Univers (INSU - CNRS)-Centre National d'Études Spatiales [Toulouse] (CNES)-Centre National de la Recherche Scientifique (CNRS)-Observatoire des Sciences de l'Univers de Grenoble (OSUG ), Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut national des sciences de l'Univers (INSU - CNRS)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019]), LERMA Cergy (LERMA), Université Paris-Seine-Université Paris-Seine-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Programme National 'Physique et Chimie du Milieu Interstellaire' (PCMI) of CNRS/INSU, CNES, DIM ACAV+, a funding program of the Region Ile de France, LabEx MICHEM, French National Research Agency [ANR-15-IDEX-02], European Research Council (ERC) under the European Union [741002], INC/INP, CEA, ANR-15-IDEX-0002,UGA,IDEX UGA(2015), PSL Research University (PSL)-PSL Research University (PSL)-Université de Cergy Pontoise (UCP), Hokkaido University, Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Centre National d'Études Spatiales [Toulouse] (CNES)-Université Grenoble Alpes (UGA)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire des Sciences de l'Univers de Grenoble (OSUG), Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Joseph Fourier - Grenoble 1 (UJF)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Joseph Fourier - Grenoble 1 (UJF)-Centre National de la Recherche Scientifique (CNRS), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes-Centre National de la Recherche Scientifique (CNRS), Sorbonne Université (SU)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université de Cergy Pontoise (UCP), Université Paris-Seine-Université Paris-Seine-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Sorbonne Université (SU)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université de Cergy Pontoise (UCP), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: Astrochemistry, 010504 meteorology & atmospheric sciences, Nitrile, Infrared spectroscopy, Context (language use), Astrophysics, Photochemistry, Mass spectrometry, 01 natural sciences, chemistry.chemical_compound, ISM molecules, 0103 physical sciences, 010303 astronomy & astrophysics, Quantum tunnelling, 0105 earth and related environmental sciences, Physics, [SDU.ASTR]Sciences of the Universe [physics]/Astrophysics [astro-ph], astrochemistry, Substrate (chemistry), Astronomy and Astrophysics, ISM: molecules, Interstellar medium, chemistry, 13. Climate action, Space and Planetary Science, [CHIM.OTHE]Chemical Sciences/Other, [PHYS.ASTR]Physics [physics]/Astrophysics [astro-ph]
Abstract: Context. Beyond NH3, only one primary alkylamine, CH3NH2, has been identified in the interstellar medium and the reason why is still not understood: its formation could occur in the gas phase or in icy environments. Aims. To consider any possible difference between the formation of primary and secondary amines, we studied the hydrogenation processes of CH3CN and CH3NC, which would lead to the simple primary CH3CH2NH2 and secondary CH3NHCH3 amines, respectively. Methods. Experimentally, the hydrogenation of CH3CN and CH3NC was carried out under ultra-high vacuum, using two beamlines to inject the nitrile/isonitrile and H onto substrate surfaces of gold or water ice. The reactions were monitored using infrared spectroscopy and the products were followed by mass spectrometry. Theoretically, the energetics of the hydrogenation paths were determined using the M06-2X functional after benchmarking against post Hartree–Fock procedures. Meanwhile, a survey of the high-mass star forming region W51/e2 has been performed. Results. Following co-deposition of CH3CN and H, we show that these species do not react together between 10 and 60 K. For CH3NC we found that the hydrogenation process works all the way through the CH3NHCH3 end product; we also identified the CH3NCH2 intermediate together with side products, CH4 and HCN, showing that the isonitrile backbone is breaking. These results are consistent with the calculations of a high barrier on the first hydrogenation step for CH3CN and a lower barrier for CH3NC. Conclusions. The formation of CH3CH2NH2 by hydrogenation of CH3CN appears rather unlikely in both the gas phase and ice environment whereas that of CH3NHCH3 is a clear possibility. The limiting factor appears to be the efficiency of the tunneling effect through the first activation barrier on the reaction paths. More surveys are required for further insight into the search for amines.
Published: 2019
Full Text: View/download PDF

36. The Laboratory Millimeter and Submillimeter Rotational Spectrum of Lactaldehyde and an Astronomical Search in Sgr B2(N), Orion-KL, and NGC 6334I

Author: Lucie Kolesniková, Elena R. Alonso, Iker León, Brett A. McGuire, Crystal L. Brogan, José L. Alonso, Jean-Claude Guillemin, P. Brandon Carroll, Todd R. Hunter, Spanish National Research Council (CSIC), Universidad de Valladolid [Valladolid] (UVa), University of the Basque Country/Euskal Herriko Unibertsitatea (UPV/EHU), National Radio Astronomy Observatory (NRAO), Harvard-Smithsonian Center for Astrophysics (CfA), Smithsonian Institution-Harvard University [Cambridge], Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), European Research Council under the European UnionEuropean Research Council (ERC) [610256 NANOCOSMOS], Ministerio de Ciencia e InnovacionMinistry of Science and Innovation, Spain (MICINN) [CTQ201340717-P, CTQ2016-76393-P, BES-2014-067776], Junta de Castilla y LeonJunta de Castilla y Leon [VA175U13, VA077U16], NASA through Hubble Fellowship - Space Telescope Science Institute [HST-HF2-51396], NASANational Aeronautics and Space Administration (NASA) [NAS5-26555], Centre National d'Etudes Spatiales (CNES)Centre National D'etudes Spatiales, French Programme National 'Physique et Chimie du Milieu Interstellaire, Harvard University-Smithsonian Institution, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Physics, Astrochemistry, astrochemistry, Astronomy, Astronomy and Astrophysics, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, chemistry.chemical_compound, ISM molecules, chemistry, Space and Planetary Science, 0103 physical sciences, Rotational spectrum, [CHIM]Chemical Sciences, Millimeter, Lactaldehyde, 010303 astronomy & astrophysics
Abstract: International audience; We present a laboratory rotational study of, and astronomical search for, lactaldehyde (CH3CH(OH)CH(O)), one of the simplest chiral molecules that could reasonably be seen in the interstellar medium (ISM), in the millimeter and submillimeter wave regions from 80 to 460 GHz. More than 5000 transitions were assigned to the most stable conformer, and a set of spectroscopic constants was accurately determined. Lactaldehyde is involved in numerous metabolic pathways used by life on Earth, and is a logical step up in complexity from glycolaldehyde (CH(O)CH2OH) which is being detected with increasing regularity in the ISM. We present an accompanying radio astronomical search for lactaldehyde in three high-mass star-forming regions (NGC 6334I, Sgr B2(N), and Orion-KL) as well as in the publicly available data from the ASAI Large Project. Neither molecule is detected in these sources, and we report corresponding upper limits to the column densities. We discuss the potential utility of lactaldehyde in combination with other members of the [C-3,H-6,O-2] isomeric family in probing pathways of chemical evolution in the ISM.
Published: 2019
Full Text: View/download PDF

37. Internal Rotation of OH Group in 4-Hydroxy-2-butynenitrile Studied by Millimeter-Wave Spectroscopy

Author: Laurent Margulès, María Luisa Senent, Roman A. Motiyenko, Jean-Claude Guillemin, Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Centre National d’Etudes Spatiales, ANR-13-BS05-0008, Agence Nationale de la Recherche, Institut National des Sciences de l'Univers, Centre National de la Recherche Scientifique, FIS2013-40626-P, Ministerio de Economía y Competitividad, Commissariat à l'Énergie Atomique et aux Énergies Alternatives, Institut de chimie, Centre National de la Recherche Scientifique, Institut de physique, Centre National de la Recherche Scientifique, ANR-13-BS05-0008,IMOLABS,Molecules interstellaires : spectroscopie et synthèse en laboratoire(2013), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: [PHYS]Physics [physics], Chemistry, Internal rotation, Formaldehyde, 010402 general chemistry, 01 natural sciences, Molecular physics, 0104 chemical sciences, Adduct, chemistry.chemical_compound, 0103 physical sciences, Extremely high frequency, Molecule, Cyanoacetylene, [CHIM]Chemical Sciences, Rotational spectroscopy, Physical and Theoretical Chemistry, Spectroscopy, 010303 astronomy & astrophysics
Abstract: International audience; Cyanoacetylene, HCC-CN is a ubiquitous molecule in the Universe. However, its interstellar chemistry is not well understood and its understanding requires laboratory data including rotational spectroscopy of possible products coming from a reaction with another compounds. In this study we present the first spectroscopic characterization of gauche conformation of 4-hydroxy-2-butynenitrile (HOCHCCCN), a formal adduct of cyanoacetylene on formaldehyde, in the frequency range up to 500 GHz. The analysis of the rotational spectrum was complicated by internal rotation of the OH group that connects two equivalent gauche configurations. The spectral assignment was aided by high-level quantum chemical calculations that were particularly useful in the interpretation of torsional-rotational part of the problem. The applied reduced-axis-system (RAS) formalism allowed fitting within experimental accuracy the lines with K < 18. We also present the method of search for initial global solution of torsional-rotational problem within RAS formalism. Accurate spectroscopic parameters obtained in this study provide a reliable basis for the detection of 4-hydroxy-2-butynenitrile in the interstellar medium.
Published: 2018
Full Text: View/download PDF

38. Laboratory spectroscopy of methoxymethanol in the millimeter-wave range

Author: Jean-Claude Guillemin, Laurent Margulès, Roman A. Motiyenko, D. Despois, Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS), FORMATION STELLAIRE 2018, Laboratoire d'Astrophysique de Bordeaux [Pessac] (LAB), Université de Bordeaux (UB)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université de Bordeaux (UB)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), This work was supported by the French Programme National 'Physique et Chimie du Milieu Interstellaire', and by the ANR-13-BS05-0008 IMOLABS of the French Agence Nationale de la Recherche., ANR-13-BS05-0008,IMOLABS,Molecules interstellaires : spectroscopie et synthèse en laboratoire(2013), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: Range (particle radiation), [SDU.ASTR]Sciences of the Universe [physics]/Astrophysics [astro-ph], Radical, Formaldehyde, General Physics and Astronomy, 010402 general chemistry, Rotation, 01 natural sciences, 0104 chemical sciences, Characterization (materials science), Interstellar medium, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, Amplitude, chemistry, Computational chemistry, 0103 physical sciences, Physical chemistry, [SDU.ASTR.GA]Sciences of the Universe [physics]/Astrophysics [astro-ph]/Galactic Astrophysics [astro-ph.GA], Physical and Theoretical Chemistry, Spectroscopy, 010303 astronomy & astrophysics
Abstract: International audience; Methoxymethanol, CHOCHOH is a very interesting candidate for detection in the interstellar medium since it can be formed in the recombination reaction between two radicals considered as intermediates in methanol formation: CHO (already detected in the ISM) and CHOH. It could also be formed by the addition of CHO to formaldehyde (another abundant compound in the ISM) followed by abstraction of a hydrogen radical. In this study, we present the first spectroscopic characterization of methoxymethanol in the millimeter-wave range augmented by high level quantum chemical calculations. The analysis revealed three stable conformations all exhibiting different large amplitude motions (LAMs). For the analysis of the most stable conformation (I) we applied a model that accounts for hindered internal rotation of the methyl top. The analysis of conformation III was performed taking the interaction between the overall rotation and OH torsional motion into account. Conformation II was only tentatively assigned, as it exhibits several LAMs that significantly complicate the theoretical description. Accurate spectroscopic parameters obtained in this study provide a reliable basis for the detection of methoxymethanol in the ISM.
Published: 2018
Full Text: View/download PDF

39. Reduction of CO functional groups through H addition reactions a comparative study between H2CO + H, CH3CH2CHO + H and CH3OCHO + H under interstellar conditions

Author: Lahouari Krim, Al Mokhtar Lamsabhi, Manuel Yáñez, Jean-Claude Guillemin, Mindaugas Jonusas, De la Molécule aux Nanos-objets : Réactivité, Interactions et Spectroscopies (MONARIS), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Universidad Autonoma de Madrid (UAM), CTQ2015-63997-C2, MADRISOLAR2, CNES, Centre National d’Etudes Spatiales, ANR-11-IDEX-0004-02, Labex, CSC2007-00010, Comunidad de Madrid, ANR-11-IDEX-0004,SUPER,Sorbonne Universités à Paris pour l'Enseignement et la Recherche(2011), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Universidad Autónoma de Madrid (UAM)
Subjects: chemistry.chemical_classification, Addition reaction, Interstellar ice, Photodissociation, Formaldehyde, General Physics and Astronomy, 02 engineering and technology, 021001 nanoscience & nanotechnology, Photochemistry, 01 natural sciences, Aldehyde, chemistry.chemical_compound, chemistry, 13. Climate action, 0103 physical sciences, Functional group, [CHIM]Chemical Sciences, Methanol, Physical and Theoretical Chemistry, 0210 nano-technology, Saturation (chemistry), 010303 astronomy & astrophysics
Abstract: International audience; H-addition reactions on the icy interstellar grains may play an important role in the formation of complex organic molecules. In the present work we propose a comparative study of H2CO + H, CH3CH2CHO + H and CH3OCHO + H solid state reactions at 10 K under interstellar conditions in order to characterize the main reaction pathways involved in the hydrogenation of a CHO functional group. We show that the most probable mechanism for the formation of alcohols under non-energetic conditions through the saturation of the CHO group corresponds to the attachment of the H atom to the CH group with noticeable variations of the energy barriers for each studied reaction. These energy barriers have been calculated to be 8.3, 14.6 and 32.7 kJ mol-1 for H2CO + H, CH3CH2CHO + H and CH3OCHO + H, respectively. The coupling of the experimental and theoretical analysis proves that while the simplest aldehyde, formaldehyde, is easily reduced to methanol, methylformate and propanal behave differently under H-bombardments but they cannot be a source of alcohol formation through H-addition reactions. Consequently, for the formation of alcohols larger than CH3OH, other chemical pathways should be taken into account, probably energetic processing such as the photolysis of interstellar ice analogues containing C-, H- and O-bearing compounds or the coupling of the H-addition reaction and photon-irradiation on species with a CHO functional group. © 2018 the Owner Societies.
Published: 2018
Full Text: View/download PDF

40. Glycinamide, a Glycine Precursor, Caught in the Gas Phase A Laser-ablation Jet-cooled Rotational Study

Author: José L. Alonso, Elena R. Alonso, Jean-Claude Guillemin, E. Białkowska-Jaworska, Lucie Kolesniková, Iker León, Zbigniew Kisiel, Spanish National Research Council (CSIC), Polish Academy of Sciences (PAN), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Ministerio de Ciencia e Innovacion [2010 CSD2009-00038, CTQ2013-40717-P, CTQ2016-76393-P, BES-2014-067776], Junta de Castilla y Leon [VA077U16], European Research Council under European Union/ERC-2013-SyG [610256], Junta de Castilla y Leon, Program PCMI (INSU-CNRS), Centre National d'Etudes Spatiales (CNES), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Physics, Jet (fluid), Laser ablation, molecular data, techniques spectroscopic, Astronomy and Astrophysics, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Gas phase, ISM molecules, Space and Planetary Science, 0103 physical sciences, Glycine, [CHIM]Chemical Sciences, Atomic physics, 010303 astronomy & astrophysics, catalogs
Abstract: International audience; Glycinamide, a glycine precursor, has been successfully generated in the gas phase by laser ablation of its hydrochloride salt, and its microwave spectrum, recorded from 6 to 16 GHz using a Chirped Pulse Fourier Transform Microwave (LA-CP-FTMW) spectrometer, is reported for the first time. The existence of a single structure stabilized by a N-a-H center dot center dot center dot NtH2 hydrogen bond has been revealed in the supersonic expansion. The complex nuclear quadrupole coupling hyperfine structure due to the two N-14 nuclei has been completely resolved and analyzed using a Molecular Beam Fourier Transform Microwave spectrometer in combination with laser ablation (LA-MB-FTMW spectrometer). The first precise data obtained on this glycine precursor could be of great importance for possible future identifications in the interstellar medium.
Published: 2018
Full Text: View/download PDF

41. Rotational spectrum of methoxyamine up to 480 GHz: a laboratory study and astronomical search

Author: Lucie Kolesniková, Elena R. Alonso, José Cernicharo, Jean-Claude Guillemin, Belén Tercero, José L. Alonso, Spanish National Research Council (CSIC), Instituto de Ciencia de Materiales de Madrid (ICMM), Consejo Superior de Investigaciones Científicas [Madrid] (CSIC), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), INSU/CNRS (France), MPG (Germany), Program PCMI (INSU-CNRS), Centre National d'Etudes Spatiales (CNES), Ministerio de Ciencia e Innovacion for FPI grant [BES-2014-067776], [ANR-13-BS05-0008 IMOLABS], IGN (Spain), European Research Council under the European Union's Seventh Framework Programme/ERC-SyG [610256 NANOCOSMOS], Ministerio de Ciencia e Innovacion [CTQ2013-40717-P, AYA2012-32032], Ministerio de Ciencia e Innovacion (program 'ASTROMOL') [Consolider-Ingenio 2010 CSD2009-00038], Junta de Castilla y Leon [VA070A08, VA175U13], ANR-13-BS05-0008,IMOLABS,Molecules interstellaires : spectroscopie et synthèse en laboratoire(2013), European Project: 610256,EC:FP7:ERC,ERC-2013-SyG,NANOCOSMOS(2014), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Astrochemistry, Astrophysics, astronomical databases: miscellaneous, 010402 general chemistry, 01 natural sciences, Molecular physics, Article, chemistry.chemical_compound, Optics, Methoxyamine, 0103 physical sciences, Molecule, [CHIM]Chemical Sciences, 010303 astronomy & astrophysics, Conformational isomerism, Astrophysics::Galaxy Astrophysics, Physics, Spectrometer, [SDU.ASTR]Sciences of the Universe [physics]/Astrophysics [astro-ph], business.industry, astrochemistry, Molecular cloud, Astronomy and Astrophysics, ISM: molecules, 0104 chemical sciences, chemistry, Space and Planetary Science, Millimeter, business, line: identification, Methyl group
Abstract: Aims.Methoxyamine is a potential interstellar amine that has been predicted by gas-grain chemical models for the formation of complex molecules. The aim of this work is to provide direct experimental frequencies of its ground-vibrational state in the millimeter- and submillimeter-wave regions to achieve its detection in the interstellar medium.Methods.Methoxyamine was chemically liberated from its hydrochloride salt, and its rotational spectrum was recorded at room temperature from 75 to 480 GHz using the millimeter-wave spectrometer in Valladolid. Many observed transitions revealedA−Esplitting caused by the internal rotation of the methyl group, which had to be treated with specific internal rotation codes.Results.Over 400 lines were newly assigned for the most stable conformer of methoxyamine, and a precise set of spectroscopic constants was obtained. Spectral features of methoxyamine were then searched for in the Orion KL, Sgr B2, B1-b, and TMC-1 molecular clouds. Upper limits to the column density of methoxyamine were derived.
Published: 2018
Full Text: View/download PDF

42. Submillimeter wave spectroscopy of ethyl isocyanide and its searches in Orion

Author: Jean-Claude Guillemin, Roman A. Motiyenko, Laurent Margulès, José Cernicharo, B. Tercero, Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS), Instituto de Ciencia de Materiales de Madrid (ICMM), Consejo Superior de Investigaciones Científicas [Madrid] (CSIC), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), CNES, CNRS program 'Physique et Chimie du Milieu Interstellaire' (PCMI), INSU/CNRS (France), MPG (Germany), IGN (Spain), MINECO [CSD 2009-00038, AYA2012-32032, CTQ 2013-40717 P, CTQ 2010-19008], ERC [ERC-2013-Syg-610256-NANOCOSMOS], Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Physics, molecular data, Terahertz radiation, Isocyanide, Extrapolation, Astronomy and Astrophysics, Astrophysics, submillimeter ISM, 010402 general chemistry, Quantum number, 01 natural sciences, Spectral line, 0104 chemical sciences, Interstellar medium, methods laboratory molecular, chemistry.chemical_compound, ISM molecules, chemistry, Space and Planetary Science, 0103 physical sciences, Extremely high frequency, [CHIM]Chemical Sciences, line identification, Spectroscopy, 010303 astronomy & astrophysics
Abstract: Context. About 40 cyanide compounds have been detected in the interstellar medium, but only 3 examples of organic isocyanide compounds were observed in this medium. Ethyl isocyanide is one of the best candidates for possible detection. Aim. To date, measurements of rotational spectra are limited to 40 GHz. The extrapolation of the prediction in the millimeter wave domain is inaccurate and does not permit an unambiguous detection. Methods. The rotational spectra were reinvestigated from 0.15 to 1 THz. Using the new prediction, we searched for the compound ethyl isocyanide in Orion KL and Sgr B2. Results. We newly assigned 2906 transitions and fitted these new data with those from previous studies, reaching quantum numbers up to J = 103 and Ka = 30. The asymmetric top Hamiltonian proposed by Watson in the Ir representation was used for the analysis, and both reductions A and S were tested. The search for CH3CH2NC in Sgr B2 (IRAM 30m) and Orion KL (IRAM 30m, ALMA Science Verification) result in a non-detection; upper limits to the column density were derived.
Published: 2018
Full Text: View/download PDF

43. Stability of CH3NCO in Astronomical Ices under Energetic Processing: A Laboratory Study

Author: Ramón J. Peláez, Belén Maté, Jean-Claude Guillemin, José Cernicharo, Víctor J. Herrero, Isabel Tanarro, Germán Molpeceres, Spanish National Research Council (CSIC), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Spanish MINECO [FIS2013-48087-C2-1P, FIS2016-C3-1P, AYA2016-75066-C2-1-P], Program PCMI (INSU-CNRS), Centre National d'Etudes Spatiales (CNES), European Union [ERC-2013-Syg 610256], European Project: 610256,EC:FP7:ERC,ERC-2013-SyG,NANOCOSMOS(2014), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Ministerio de Economía y Competitividad (España), Agence Nationale de la Recherche (France), Centre National D'Etudes Spatiales (France), Institut national des sciences de l'Univers (France), Centre National de la Recherche Scientifique (France), and European Commission
Subjects: Kuiper Belt general, molecular data, Library science, interstellar medium (ISM), general [Kuiper Belt], 010402 general chemistry, 7. Clean energy, 01 natural sciences, 0103 physical sciences, solid state volatile, media_common.cataloged_instance, [CHIM]Chemical Sciences, European union, Solid state: volatile, 010303 astronomy & astrophysics, Interstellar medium (ISM), Astrochemistry, media_common, Physics, Molecular data, astrochemistry, volatile [Solid state], Astronomy and Astrophysics, 0104 chemical sciences, Work (electrical), 13. Climate action, Space and Planetary Science, Kuiper Belt: general
Abstract: Methyl isocyanate (CH3NCO) was recently found in hot cores and suggested to exist on comet 67P/CG. The incorporation of this molecule into astrochemical networks requires data on its formation and destruction. In this work, ices of pure CH3NCO and of CH3NCO(4%–5%)/H2O mixtures deposited at 20 K were irradiated with a UV D2 lamp (120–400 nm) and bombarded by 5 keV electrons to mimic the secondary electrons produced by cosmic rays (CRs). The destruction of CH3NCO was studied using IR spectroscopy. After processing, the νa–NCO band of CH3NCO disappeared and IR bands corresponding to CO, CO2, OCN−, and HCN/CN− appeared instead. The products of photon and electron processing were very similar. Destruction cross sections and half-life doses were derived from the measurements. Water ice provides a good shield against UV irradiation (half-life dose of ∼64 eV molecule−1 for CH3NCO in water ice), but is not so good against high-energy electrons (half-life dose ∼18 eV molecule−1). It was also found that CH3NCO does not react with H2O over the temperature range 20–200 K. These results indicate that hypothetical CH3NCO in the ices of dense clouds should be stable against UV photons and relatively stable against CRs over the lifetime of a cloud (∼107 yr), and could sublime in the hot core phase. On the surface of a Kuiper Belt object (the original location of comet 67P/CG) the molecule would be swiftly destroyed, by both photons and CRs, but embedded below just 10 μm of water ice, the molecule could survive for ∼109 yr., This work has been funded by the Spanish MINECO under grants FIS2013-48087-C2-1P, FIS2016-C3-1P, and AYA2016- 75066-C2-1-P. J.-C.G. and J.C. also thank the ANR-13-BS05- 0008 IMOLABS and J.-C.G. thanks the Program PCMI (INSU-CNRS) and the Centre National d’Etudes Spatiales (CNES) for funding support. European Union funding under grant ERC-2013-Syg 610256 (NANOCOSMOS) is also acknowledged.
Published: 2018
Full Text: View/download PDF

44. Isoselenocyanates versus Isothiocyanates and Isocyanates

Author: Jean-Claude Guillemin, Clovis Darrigan, Alain Dargelos, Anna Chrostowska, Alain Graciaa, Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux (IPREM), Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire des Fluides Complexes et leurs Réservoirs (LFCR), TOTAL FINA ELF-Université de Pau et des Pays de l'Adour (UPPA)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Centre National d’Etudes Spatiales, Institut National des Sciences de l'Univers, Centre National de la Recherche Scientifique, Commissariat à l'Énergie Atomique et aux Énergies Alternatives, Institut de chimie, Centre National de la Recherche Scientifique, Institut de Physique, Centre National de la Recherche Scientifique, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: chemistry.chemical_classification, Allylic rearrangement, 010304 chemical physics, Aryl, Substituent, chemistry.chemical_element, 010402 general chemistry, 01 natural sciences, Medicinal chemistry, 3. Good health, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, Organoselenium Compound, chemistry, Group (periodic table), 0103 physical sciences, Physical and Theoretical Chemistry, Conformational isomerism, Selenium, Alkyl
Abstract: International audience; Alkyl and aryl isoselenocyanates are well known intermediates in the synthesis of various organoselenium compounds, but the knowledge of the physicochemical properties of simple unsaturated derivatives is still fragmentary. Vinyl-, 2-propenyl-, and cyclopropyl isoselenocyanates have been prepared by reaction of selenium in powder with the corresponding isocyanides. The isoselenocyanates of this series, with a variable distance between the N═C═Se group and the unsaturated or pseudounsaturated group, have been studied by UV-photoelectron spectroscopy and quantum-chemical calculations. For each of these three isoselenocyanates, the exploration of conformers and geometrical optimization always converge toward only one local minimum. The vinyl and cyclopropyl derivatives are characterized by similar order of magnitude of interactions between the NCSe group and the substituent, while for allylic compound two noninteracting moieties should be considered. The same conclusions were obtained for vinylic and cyclopropylic sulfur and oxygen derivatives. Thus the type and extent of interactions between the N═C═X (X = O, S, Se) group and an unsaturated (vinyl, allyl, or cyclopropyl) moiety are now clarified.
Published: 2018
Full Text: View/download PDF

45. Nitrile versus isonitrile adsorption at interstellar grain surfaces: II. Carbonaceous aromatic surfaces

Author: Xavier Michaut, Alexis Markovits, M. Doronin, Françoise Pauzat, Yves Ellinger, Laurent Philippe, Mathieu Bertin, Jean-Claude Guillemin, Jean-Hugues Fillion, Laboratoire d'Etude du Rayonnement et de la Matière en Astrophysique (LERMA), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université de Cergy Pontoise (UCP), Université Paris-Seine-Université Paris-Seine-Centre National de la Recherche Scientifique (CNRS), Laboratoire de chimie théorique (LCT), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), PCMI, ANR-11-10EX-0004-02, Labex MiChem, École normale supérieure - Paris (ENS Paris), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Astrochemistry, Nitrile, FOS: Physical sciences, Context (language use), Astrophysics, 01 natural sciences, ISM: abundances, law.invention, chemistry.chemical_compound, Adsorption, law, Desorption, Physics - Chemical Physics, 0103 physical sciences, Molecule, 010303 astronomy & astrophysics, Physics, Chemical Physics (physics.chem-ph), 010304 chemical physics, Graphene, astrochemistry, Astronomy and Astrophysics, Triple bond, Astrophysics - Astrophysics of Galaxies, ISM: molecules, chemistry, Space and Planetary Science, Astrophysics of Galaxies (astro-ph.GA), Physical chemistry, [PHYS.ASTR]Physics [physics]/Astrophysics [astro-ph]
Abstract: Context. Almost 20% of the ~200 different species detected in the interstellar and circumstellar media present a carbon atom linked to nitrogen by a triple bond. Of these 37 molecules, 30 are nitrile R-CN compounds, the remaining 7 belonging to the isonitrile R-NC family. How these species behave in their interactions with the grain surfaces is still an open question. Aims. In a previous work, we have investigated whether the difference between nitrile and isonitrile functional groups may induce differences in the adsorption energies of the related isomers at the surfaces of interstellar grains of various nature and morphologies. This study is a follow up of this work, where we focus on the adsorption on carbonaceous aromatic surfaces. Methods. The question is addressed by means of a concerted experimental and theoretical approach of the adsorption energies of CH3CN and CH3NC on the surface of graphite (with and without surface defects). The experimental determination of the molecule and surface interaction energies is carried out using temperature-programmed desorption in an ultra-high vacuum between 70 and 160 K. Theoretically, the question is addressed using first-principle periodic density functional theory to represent the organised solid support. Results. The adsorption energy of each compound is found to be very sensitive to the structural defects of the aromatic carbonaceous surface: these defects, expected to be present in a large numbers and great diversity on a realistic surface, significantly increase the average adsorption energies to more than 50% as compared to adsorption on perfect graphene planes. The most stable isomer (CH3CN) interacts more efficiently with the carbonaceous solid support than the higher energy isomer (CH3NC), however.
Published: 2017
Full Text: View/download PDF

46. Laboratory study of methyl isocyanate ices under astrophysical conditions

Author: Belén Maté, Germán Molpeceres, Víctor J. Herrero, Isabel Tanarro, José Cernicharo, Jean-Claude Guillemin, Vicente Timón, Rafael Escribano, Instituto de Estructura de la Materia (IEM), Consejo Superior de Investigaciones Científicas [Madrid] (CSIC), Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Instituto de Ciencia de Materiales de Madrid (ICMM), European Union [ERC-2013-Syg 610256 (NANOCOSMOS)], Spanish MINECO [CSD2009-00038 (ASTROMOL)], MINECO [FIS2013-48087-C2-1P, FIS2016-C3-1P, AYA2012-32032, AYA2016-75066-C2-1-P, BES-2014-0693], IMOLABS [ANR-13-BS05-0008], PCMI (INSU-CNRS), Centre National d'Etudes Spatiales (CNES), ANR-13-BS05-0008,IMOLABS,Molecules interstellaires : spectroscopie et synthèse en laboratoire(2013), European Project: 610256,EC:FP7:ERC,ERC-2013-SyG,NANOCOSMOS(2014), European Commission, Ministerio de Economía y Competitividad (España), Agence Nationale de la Recherche (France), Centre National D'Etudes Spatiales (France), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Comet, Infrared spectroscopy, Methyl isocyanate, 010402 general chemistry, 01 natural sciences, ISM: clouds, Spectral line, Article, spectroscopic [Techniques], Crystal, chemistry.chemical_compound, 0103 physical sciences, [CHIM]Chemical Sciences, 010303 astronomy & astrophysics, Physics, infrared: ISM, Astronomy and Astrophysics, Isocyanic acid, 0104 chemical sciences, chemistry, Deuterium, laboratory: solid state [Methods], 13. Climate action, Space and Planetary Science, methods: laboratory: solid state, Physical chemistry, Density functional theory, clouds [ISM], techniques: spectroscopic
Abstract: 9 pags., 5 figs., 6 tabs., Methyl isocyanate has been recently detected in comet 67P/Churyumov–Gerasimenko (67P/CG) and in the interstellar medium. New physicochemical studies on this species are now necessary as tools for subsequent studies in astrophysics. In this work, infrared spectra of solid CH3NCO have been obtained at temperatures of relevance for astronomical environments. The spectra are dominated by a strong, characteristic multiplet feature at 2350–2250 cm−1, which can be attributed to the asymmetric stretching of the NCO group. A phase transition from amorphous to crystalline methyl isocyanate is observed at ∼90 K. The band strengths for the absorptions of CH3NCO in ice at 20 K have been measured. Deuterated methyl isocyanate is used to help with the spectral assignment. No X-ray structure has been reported for crystalline CH3NCO. Here we advance a tentative theoretical structure, based on density functional theory (DFT) calculations, derived taking the crystal of isocyanic acid as a starting point. A harmonic theoretical spectrum is then calculated for the proposed structure and compared with the experimental data. A mixed ice of H2O and CH3NCO was formed by simultaneous deposition of water and methyl isocyanate at 20 K. The absence of new spectral features indicates that methyl isocyanate and water do not react appreciably at 20 K, but form a stable mixture. The high CH3NCO/H2O ratio reported for comet 67P/CG, and the characteristic structure of the 2350–2250 cm−1 band, makes it a very good candidate for future astronomical searches., This work was funded by the European Union under grant ERC-2013-Syg 610256 (NANOCOSMOS) and by the Spanish MINECO CSD2009-00038 (ASTROMOL) within the Consolider–Ingenio Program. MINECO funding from grants FIS2013-48087-C2-1P, FIS2016-C3-1P, AYA2012- 32032 and AYA2016-75066-C2-1-P is also acknowledged. G. M. acknowledges MINECO PhD grant BES-2014-0693. JCG and JC also thank the ANR-13-BS05-0008 IMOLABS and JCG thanks the Program PCMI (INSU-CNRS) and the Centre National d’Etudes Spatiales (CNES) for funding support
Published: 2017
Full Text: View/download PDF

47. Probing the conformational behavior of the doubly substituted methyl-ethyl Criegee intermediate by FTMW spectroscopy

Author: Yasuki Endo, Carlos Cabezas, Jean-Claude Guillemin, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Ministry of Science and Technology of Taiwan [MOST 104-2113-M-009-020, MOST 105-2811-M-009-026], Centre National d'Etudes Spatiales (CNES), Program PCMI (INSU-CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: 010304 chemical physics, Internal rotation, General Physics and Astronomy, 010402 general chemistry, Photochemistry, 01 natural sciences, Spectral line, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Criegee intermediate, 0103 physical sciences, [CHIM]Chemical Sciences, Electric discharge, Rotational spectroscopy, Physical and Theoretical Chemistry, Spectroscopy, Conformational isomerism, Methyl group
Abstract: International audience; Four conformers of the doubly substituted methyl-ethyl Criegee intermediate, C2H5C(CH3) OO, have been observed by Fourier-transform microwave spectroscopy. The transient species was produced using a pulsed electric discharge of a gas mixture of 2,2-diiodobutane/O-2. The conformational preferences differ from those observed previously for related alkyl-substituted Criegee intermediates. The observation of small splittings in the spectra due to the internal rotation of only one methyl group enabled us to determine the barrier heights of the hindered methyl rotation for the four conformers, which have been compared with those reported for other methyl-substituted Criegee intermediates. Published by AIP Publishing.
Published: 2017
Full Text: View/download PDF

48. Luminescent probing of the simplest chiral α-amino acid-alanine in an enantiopure and racemic state

Author: Valeriy N. Snytnikov, Alexander Rastorguev, Mark G. Baronskiy, Anton I. Kostyukov, Arkadii V. Tarasevych, Jean-Claude Guillemin, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique, 16-33-00369, Russian Foundation for Basic Research, Centre National d'Etudes Spatiales, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)
Subjects: Actinoid Series Elements, Stereochemistry, chemistry.chemical_element, Terbium, Gadolinium, luminescent probing, 010402 general chemistry, 01 natural sciences, Lanthanoid Series Elements, Catalysis, Analytical Chemistry, chemistry.chemical_compound, Europium, uranyl, Drug Discovery, [CHIM]Chemical Sciences, Spectroscopy, Pharmacology, Alanine, chemistry.chemical_classification, rare earths, luminescent spectroscopy, Luminescent Agents, 010405 organic chemistry, Chemistry, terbium, Organic Chemistry, α-amino acid, Stereoisomerism, Uranyl, enantiopure, 0104 chemical sciences, Amino acid, DL-Alanine, Enantiopure drug, Luminescent Measurements, racemate, Enantiomer
Abstract: International audience; Luminescent spectroscopy combined with the technique of luminescent probing with rare earth ions (europium, gadolinium, terbium) and an actinide ion (uranyl) was used to differentiate enantiopure and racemic alanine, the simplest chiral proteinogenic amino acid. Using the achiral luminescent probes, small differences between pure L and DL alanine in the solid state were strongly amplified. Based on the observed electronic transitions of the probes, the position of the triplet level of the coordinated alanine was estimated. Formation of homo- and heterochiral complexes between enantiomers of alanine and the metal ions is discussed as a possible mechanism of chiral self-discrimination.
Published: 2017
Full Text: View/download PDF

49. One-step synthesis of conjugated enynenitriles from bromocyanoacetylene

Author: Yann Trolez, Romain Ligny, Etienne S. Gauthier, Thierry Roisnel, Jean-Claude Guillemin, Manuel Yáñez, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Departemento de Química C-9, Universidad Autónoma de Madrid (UAM), Agence Nationale pour la Recherche [ANR-13-BS05-0008 IMOLABS], CNES (Centre National d'Etudes Spatiales), Programme National Physique et Chimie du Milieu Interstellaire (PCMI) of CNRS/INSU, INC/INP - CEA, INC/INP - CNES, ANR-13-BS05-0008,IMOLABS,Molecules interstellaires : spectroscopie et synthèse en laboratoire(2013), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Universidad Autonoma de Madrid (UAM)
Subjects: inorganic chemicals, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Organic Chemistry, chemistry.chemical_element, One-Step, Conjugated system, 010402 general chemistry, 01 natural sciences, Biochemistry, Combinatorial chemistry, 0104 chemical sciences, chemistry.chemical_compound, chemistry, Organic chemistry, Physical and Theoretical Chemistry, Triphenylphosphine, Palladium, Copper iodide
Abstract: International audience; The chemical reactivity of bromocyanoacetylene has been evaluated for the first time by making it react with terminal alkynes and secondary amines in the presence of bis( triphenylphosphine) palladium dichloride and copper iodide as co-catalysts. This reaction provides new conjugated enynenitriles stereoselectively in one step in variable yields.
Published: 2017
Full Text: View/download PDF

50. The millimeter and sub-millimeter rotational spectrum of triple 13C-substituted ethyl cyanide

Author: Laurent Margulès, Jean-Claude Guillemin, Holger S. P. Müller, A. Pienkina, Roman A. Motiyenko, Laboratoire de Physique des Lasers, Atomes et Molécules - UMR 8523 (PhLAM), Université de Lille-Centre National de la Recherche Scientifique (CNRS), I. Physikalisches Institut [Köln], Universität zu Köln, Institut des Sciences Chimiques de Rennes (ISCR), Université de Rennes 1 (UR1), Université de Rennes (UNIV-RENNES)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), Institut National des Sciences Appliquées (INSA)-Université de Rennes (UNIV-RENNES)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), ANR, Agence Nationale de la Recherche, CNRS, Conseil National de la Recherche Scientifique, Universität zu Köln = University of Cologne, Université de Rennes (UR)-Institut National des Sciences Appliquées - Rennes (INSA Rennes), and Institut National des Sciences Appliquées (INSA)-Institut National des Sciences Appliquées (INSA)-Ecole Nationale Supérieure de Chimie de Rennes (ENSCR)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: 010504 meteorology & atmospheric sciences, molecular data, methods: laboratory: molecular, Astrophysics, 01 natural sciences, Spectral line, symbols.namesake, Nuclear magnetic resonance, 0103 physical sciences, Molecule, Sagittarius B2, 010303 astronomy & astrophysics, 0105 earth and related environmental sciences, Physics, Spectrometer, [SDU.ASTR]Sciences of the Universe [physics]/Astrophysics [astro-ph], Galactic Center, Astronomy and Astrophysics, Quantum number, ISM: molecules, Space and Planetary Science, symbols, submillimeter: ISM, Millimeter, Atomic physics, Hamiltonian (quantum mechanics), [CHIM.OTHE]Chemical Sciences/Other, line: identification, techniques: spectroscopic
Abstract: Context. A recently published astronomical detection of all three doubly 13C-substituted ethyl cyanides toward Sgr B2(N2) motivated us to investigate triple 13C isotopic species that are expected to be also present in the ISM. Aims. We aim to present an experimental study of the rotational spectrum of triple 13C-substituted ethyl cyanide, 13CH313CH213CN, in the frequency range 150–990 GHz. We want to use the determined spectroscopic parameters for searching for 13CH313CH213CN in ALMA data. The main objective of this work is to provide accurate frequency predictions to search for this molecule in the Galactic center source Sagittarius B2(N) and to facilitate its detection in space. Methods. The laboratory rotational spectrum of 13CH313CH213CN has been recorded with the Lille’s fast DDS solid-state spectrometer between 150 GHz and 990 GHz. Results. More than 4000 rotational transitions were identified in the laboratory. The quantum numbers reach J = 115 and Ka = 39. Watson’s Hamiltonian in the A and S reductions were used to analyze the spectra. Accurate spectroscopic parameters were determined. The rotational spectra of the 13C containing species CH3CH2CN have been assigned, thus allowing the determination of the rotational and centrifugal distortion constants
Published: 2017
Full Text: View/download PDF

Catalog

Books, media, physical & digital resources

See catalog results

Searchworks

Select search scope, currently: Articles Catalog books, media & more in Jio Institute collections Articles journal articles & other e-resources

Search

Search Constraints

Refine your results

Search Limiters

Topic

Publication Year Range

Language

Database

144 results on '"Jean-Claude Guillemin"'

Search Results

Catalog

Select search scope, currently: Articles

Catalog

books, media & more in Jio Institute collections

Articles

journal articles & other e-resources