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Internal Rotation of OH Group in 4-Hydroxy-2-Butynenitrile Studied

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Internal Rotation of OH Group in 4-Hydroxy-2-Butynenitrile Studied Internal Rotation of OH Group in 4-Hydroxy-2-butynenitrile Studied by Millimeter-Wave Spectroscopy Roman A Motiyenko, Laurent Margulès, Maria L Senent, Jean-Claude Guillemin To cite this version: Roman A Motiyenko, Laurent Margulès, Maria L Senent, Jean-Claude Guillemin. Internal Rotation of OH Group in 4-Hydroxy-2-butynenitrile Studied by Millimeter-Wave Spectroscopy. Journal of Physical Chemistry A, American Chemical Society, 2018, 122 (12), pp.3163-3169. 10.1021/acs.jpca.7b12051. hal-01771512 HAL Id: hal-01771512 https://hal-univ-rennes1.archives-ouvertes.fr/hal-01771512 Submitted on 3 May 2018 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. Page 1 of 23 The Journal of Physical Chemistry 1 2 3 4 5 6 7 8 Internal rotation of OH group in 9 10 11 4-hydroxy-2-butynenitrile studied by 12 13 14 15 millimeter-wave spectroscopy 16 17 18 ∗,y y z 19 Roman A. Motiyenko, Laurent Margulès, Maria L. Senent, and Jean-Claude 20 ∗,{ 21 Guillemin 22 23 24 yLaboratoire de Physique des Lasers, Atomes et Molécules, UMR 8523, CNRS - Université 25 26 de Lille, F-59655 Villeneuve d’Ascq Cedex, France 27 28 zDepartamento de Química y Física Teóricas, Instituto de Estructura de la Materia, 29 30 IEM-C.S.I.C., Serrano 121, Madrid 28006, Spain 31 32 {Univ Rennes, École Nationale Supérieure de Chimie de Rennes, CNRS, ISCR - 33 manuscritpt 34 UMR6226, F-35000 Rennes, France 35 36 37 E-mail: [email protected]; [email protected] 38 39 Phone: +33(0)320434490. Fax: +33(0)320337020 40 41 42 43 44 45 46 47 48 49 50 51 Accepted 52 53 54 55 56 57 58 59 1 60 ACS Paragon Plus Environment The Journal of Physical Chemistry Page 2 of 23 1 2 3 Abstract 4 5 6 Cyanoacetylene, HCC−CN is a ubiquitous molecule in the Universe. However, 7 8 its interstellar chemistry is not well understood and its understanding re- 9 quires laboratory data including rotational spectroscopy of possible products 10 11 coming from a reaction with another compounds. In this study we present the 12 13 first spectroscopic characterization of gauche conformation of 4-hydroxy-2-butynenitrile 14 15 (HOCH2CCCN), a formal adduct of cyanoacetylene on formaldehyde, in the fre- 16 17 quency range up to 500 GHz. The analysis of the rotational spectrum was complicated 18 19 by internal rotation of OH group that connects two equivalent gauche configurations. 20 21 The spectral assignment was aided by high level quantum chemical calculations that 22 23 were particularly useful in the interpretation of torsion-rotational part of the problem. 24 The applied reduced-axis-system (RAS) formalism allowed fitting within experimental 25 26 accuracy the lines with Ka < 18. We also present the method of search for initial 27 28 global solution of torsion-rotational problem within RAS formalism. Accurate spectro- 29 30 scopic parameters obtained in this study provide a reliable basis for the detection of 31 32 4-hydroxy-2-butynenitrile in the interstellar medium. 33 manuscritpt 34 35 36 37 Introduction 38 39 Cyanoacetylene is a ubiquitous molecule in the Universe since it has been observed in in- 40 41 terstellar clouds1–5, Hale-Bopp comet6 and in the atmosphere of Titan, the largest moon of 42 43 Saturn7,8. Cyanoacetylene is probably the precursor of many cyanopolyynes by photolysis 44 45 in the presence of acetylene or polyynes.9–12 Besides two methyl derivatives, MeC N and 46 3 47 MeC N, which could be formed by a similar approach but with propyne or 1,3-pentadiyne13,14 48 5 49 instead of acetylene or unsubstituted polyynes, no other derivative containing the C N moiety 50 3 51 hasAccepted been detected in the interstellar medium (ISM). For many compounds, this could be ex- 52 53 plained by the lack of rotational spectra recorded in laboratory. However, the formal addition 54 55 of ammonia, hydrogen sulfide or water which respectively gives 3-amino-2-propenenitrile,15 3- 56 57 58 59 2 60 ACS Paragon Plus Environment Page 3 of 23 The Journal of Physical Chemistry 1 2 3 mercapto-2-propenitrile16 and 3-hydroxy-2-propenenitrile (the latter rearranges in cyanoac- 4 5 etaldehyde)17 was studied and the rotational spectra of these adducts were recorded. At 6 7 present, none of them has yet been detected to date in the ISM. Another approach of in- 8 9 terstellar formation of C N derivatives involves the reaction of the C N radical, a species 10 3 3 11 detected in the ISM,18 with another compound, and this is much more comparable to the 12 13 formation of cyanopolyynes than the Michael addition of nucleophiles on cyanoacetylene. In 14 15 TMC-1, for example, the C N radical and formaldehyde have been detected.19 The addi- 16 3 17 tion of this radical on the carbonyl could produce 4-hydroxy-2-butynenitrile (HOCH CCCN, 18 2 19 HBN) after abstraction of one hydrogen from another compound (Scheme 1). 20 21 22 23 24 25 26 27 Scheme 1 28 29 30 Thus, as a first target species based on the hypothesis of interstellar compounds coming 31 32 from the cyanoethynyl radical addition on an unsaturated compound, we investigated the 33 manuscritpt 34 rotational spectrum of HBN. The spectral studies were augmented by high-level quantum 35 36 chemical calculations performed to aid in the interpretation of the observed spectra. 37 38 39 40 41 Experiment 42 43 20 44 4-Hydroxy-2-butynenitrile has been prepared as previously reported starting from a pro- 45 46 tected propargyl alcohol and phenyl cyanate. We recorded the rotational spectrum of HBN 47 48 using fast-scan terahertz spectrometer. The details of the spectrometer except of the fast- 49 21 50 scan feature are described by Zakharenko et al. In the present study, the spectrum was 51 recordedAccepted in the frequency ranges 50 - 110 GHz, 150 - 195 GHz, 225 - 330 GHz and 400 - 52 53 54 500 GHz. As a radiation source in the spectrometer, we use commercially available frequency 55 56 multiplication chains that are driven by home-made fast sweep frequency synthesizer. In the 57 58 59 3 60 ACS Paragon Plus Environment The Journal of Physical Chemistry Page 4 of 23 1 2 3 frequency range 50 - 75 GHz we use active frequency multiplier x4 from Millitech. In the 4 5 frequency range 75 - 110 GHz the source is active multiplier x6 from VDI. At higher fre- 6 7 quencies, we use passive frequency multiplication of the VDI source by factors 2, 3, 5, etc. 8 9 The fast sweep system is based on the up-conversion of AD9915 direct digital synthesizer 10 11 (DDS) operating between 320 and 420 MHz into Ku band by mixing the signals from AD9915 12 13 and Agilent E8257 synthesizers with subsequent sideband filtering. The DDS provides rapid 14 15 frequency scan with up to 50 µs/point frequency switching rate. Because of the HBN line 16 17 weakness the spectrum was scanned with slower rate of 5 ms/point or 10 ms/point depend- 18 19 ing on the frequency range. As an absorption cell in the spectrometer we used a stainless 20 21 steel tube of 10 cm in diameter, and 2 m long. Owing to good stability of the synthesized 22 23 sample of HBN under room temperature, the measurements were performed in a static mode 24 25 with practically constant amount of the sample and consequently constant gas 26 27 pressure in the absorption cell. Nevertheless, to minimize observations of decomposition 28 29 products in the spectra, the absorption cell was pumped out and refilled with new sample 30 31 of HBN at optimum pressure of about 20 Pa every 3-4 hours. 32 33 manuscritpt 34 35 36 Ab initio calculations 37 38 39 Highly correlated ab initio calculations were used to determine the geometries of the two con- 40 41 formers, gauche and trans, and to compute low-energy torsional levels. Electronic structure 42 22 23 43 calculations were performed using both the MOLPRO and GAUSSIAN packages . 44 45 The equilibrium structures, gauche and trans, of HOCH2CCCN, as well as the most rel- 46 47 evant spectroscopic parameters (equilibrium rotational constants and the one-dimensional 48 49 potential energy surface, 1D-PES, for the hydroxyl torsion) were computed using explic- 50 51 itlyAccepted correlated coupled cluster theory with single and double substitutions augmented by 52 24,25 53 a perturbative treatment of triple excitations (CCSD(T)-F12b) with an aug-cc-pVTZ 54 26 55 basis set . For this purpose, we employed the MOLPRO default options. Second-order 56 57 58 59 4 60 ACS Paragon Plus Environment Page 5 of 23 The Journal of Physical Chemistry 1 2 3 Möller-Plesset theory (MP2) was employed to determine vibrational corrections for the po- 4 5 tential energy surface and the αr vibration-rotation constants. For the explicitly correlated 6 j 7 calculations, the MOLPRO default options were selected. 8 9 The torsional energy levels were determined by variational calculations using 10 11 the procedure previously employed for other non-rigid species27.
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