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Title: Spectroscopy of cyanodiacetylene in solid argon and the photochemical generation of isocyanodiacetylene

Abstract

Following the measurements of UV and mid-IR spectra of cyanodiacetylene, H-(CC){sub 2}-CN, isolated in low temperature Ar matrices, the first photochemical study on this compound and on its {sup 2}H isotopomer was carried out with the laser light tuned to 267 nm and with far-UV discharge lamps. Evidence for the formation of isocyanodiacetylene, H-(CC){sub 2}-NC, was found in infrared absorption spectra interpreted with the aid of available theoretical predictions.

Authors:
; ; ; ; ; ;  [1];  [2];  [3];  [2];  [3]
  1. UMR CNRS 6633, Physique des Interactions Ioniques et Moleculaires, Equipe de Spectrometries et Dynamique Moleculaires, Universite de Provence, Case 252, Centre de St. Jerome, 13397 Marseille Cedex 20 (France)
  2. (Poland)
  3. (France)
Publication Date:
OSTI Identifier:
20991255
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 126; Journal Issue: 16; Other Information: DOI: 10.1063/1.2720842; (c) 2007 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION SPECTRA; ARGON; DENSITY FUNCTIONAL METHOD; DEUTERIUM; INFRARED SPECTRA; ORGANIC NITROGEN COMPOUNDS; PHOTOCHEMISTRY; REACTION KINETICS; SPECTROSCOPY; ULTRAVIOLET SPECTRA

Citation Formats

Coupeaud, Anne, Turowski, Michal, Gronowski, Marcin, Pietri, Nathalie, Couturier-Tamburelli, Isabelle, Kolos, Robert, Aycard, Jean-Pierre, Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44, 01-224 Warsaw, UMR CNRS 6633, Physique des Interactions Ioniques et Moleculaires, Equipe de Spectrometries et Dynamique Moleculaires, Universite de Provence, Case 252, Centre de St. Jerome, 13397 Marseille Cedex 20, Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44, 01-224 Warsaw, and UMR CNRS 6633, Physique des Interactions Ioniques et Moleculaires, Equipe de Spectrometries et Dynamique Moleculaires, Universite de Provence, Case 252, Centre de St. Jerome, 13397 Marseille Cedex 20. Spectroscopy of cyanodiacetylene in solid argon and the photochemical generation of isocyanodiacetylene. United States: N. p., 2007. Web. doi:10.1063/1.2720842.
Coupeaud, Anne, Turowski, Michal, Gronowski, Marcin, Pietri, Nathalie, Couturier-Tamburelli, Isabelle, Kolos, Robert, Aycard, Jean-Pierre, Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44, 01-224 Warsaw, UMR CNRS 6633, Physique des Interactions Ioniques et Moleculaires, Equipe de Spectrometries et Dynamique Moleculaires, Universite de Provence, Case 252, Centre de St. Jerome, 13397 Marseille Cedex 20, Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44, 01-224 Warsaw, & UMR CNRS 6633, Physique des Interactions Ioniques et Moleculaires, Equipe de Spectrometries et Dynamique Moleculaires, Universite de Provence, Case 252, Centre de St. Jerome, 13397 Marseille Cedex 20. Spectroscopy of cyanodiacetylene in solid argon and the photochemical generation of isocyanodiacetylene. United States. doi:10.1063/1.2720842.
Coupeaud, Anne, Turowski, Michal, Gronowski, Marcin, Pietri, Nathalie, Couturier-Tamburelli, Isabelle, Kolos, Robert, Aycard, Jean-Pierre, Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44, 01-224 Warsaw, UMR CNRS 6633, Physique des Interactions Ioniques et Moleculaires, Equipe de Spectrometries et Dynamique Moleculaires, Universite de Provence, Case 252, Centre de St. Jerome, 13397 Marseille Cedex 20, Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44, 01-224 Warsaw, and UMR CNRS 6633, Physique des Interactions Ioniques et Moleculaires, Equipe de Spectrometries et Dynamique Moleculaires, Universite de Provence, Case 252, Centre de St. Jerome, 13397 Marseille Cedex 20. Sat . "Spectroscopy of cyanodiacetylene in solid argon and the photochemical generation of isocyanodiacetylene". United States. doi:10.1063/1.2720842.
@article{osti_20991255,
title = {Spectroscopy of cyanodiacetylene in solid argon and the photochemical generation of isocyanodiacetylene},
author = {Coupeaud, Anne and Turowski, Michal and Gronowski, Marcin and Pietri, Nathalie and Couturier-Tamburelli, Isabelle and Kolos, Robert and Aycard, Jean-Pierre and Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44, 01-224 Warsaw and UMR CNRS 6633, Physique des Interactions Ioniques et Moleculaires, Equipe de Spectrometries et Dynamique Moleculaires, Universite de Provence, Case 252, Centre de St. Jerome, 13397 Marseille Cedex 20 and Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44, 01-224 Warsaw and UMR CNRS 6633, Physique des Interactions Ioniques et Moleculaires, Equipe de Spectrometries et Dynamique Moleculaires, Universite de Provence, Case 252, Centre de St. Jerome, 13397 Marseille Cedex 20},
abstractNote = {Following the measurements of UV and mid-IR spectra of cyanodiacetylene, H-(CC){sub 2}-CN, isolated in low temperature Ar matrices, the first photochemical study on this compound and on its {sup 2}H isotopomer was carried out with the laser light tuned to 267 nm and with far-UV discharge lamps. Evidence for the formation of isocyanodiacetylene, H-(CC){sub 2}-NC, was found in infrared absorption spectra interpreted with the aid of available theoretical predictions.},
doi = {10.1063/1.2720842},
journal = {Journal of Chemical Physics},
number = 16,
volume = 126,
place = {United States},
year = {Sat Apr 28 00:00:00 EDT 2007},
month = {Sat Apr 28 00:00:00 EDT 2007}
}
  • The wavelength dependence of the photochemistry of C[sub 2]H[sub 4]NO[sub 2] and C[sub 2]D[sub 2]NO[sub 2] paris, isolated in solid Ar, in the range 555-355 nm is reported. Continuous-wave and pulsed dye lasers were used to excite the reactants, and the products were monitored by FT infrared spectroscopy. Acetaldehyde, ethylene oxide, NO, and ethyl nitrite radical were the products observed at wavelengths longer than the 398-nm dissociation threshold of NO[sub 2]. D isotope effects on the branching among these species derived from kinetic analysis of growth curves support our conclusion in previous work that the mechanism involves large-amplitude O transfermore » from NO[sub 2] to the carbon-to-carbon double bond to yield a transient oxirane biradical. The latter acts as a common precursor of the observed products. A new species, ketene, appears at excitation energies just above the NO[sub 2] dissociation limit (385 and 355 nm). 55 refs., 8 figs., 1 tab.« less
  • Matrix photoionization experiments with bicyclooctadiene and cyclooctatriene gave sharp new bands between 400 and 500 nm. Selective photolysis with visible light decreased the longer wavelength absorptions and increased a band system beginning at 447 nm; irradiation at 420-470 nm essentially restored the original spectrum. Photoionization of all-trans-octatetraene directly produced a strong 447-nm band system and a sharp weaker 756-nm band system; the latter origin and vibrational structure are in excellent agreement with the emission spectrum of the gaseous cation. Cyclooctatriene and bicyclooctadiene cations experienced a series of photochemical rearrangements, which initially gave a mixture of trans- and cis-octatetraene cations thatmore » were converted to all-trans-octatetraene cation by selective irradiation in the solid argon matrix. 23 references, 4 figures, 3 tables.« less
  • UV laser irradiations of cryogenic solid argon matrices doped with a mixture of acetylene and cyanodiacetylene (HC{sub 5}N) resulted in the formation of a longer carbon–nitrogen chain, cyanotriacetylene (HC{sub 7}N). The identification of this species was accomplished based on IR vibrational spectroscopy (including the study of isotopically labeled compounds), on electronic luminescence spectroscopy, and on theoretical predictions. Additionally, IR absorption bands recognized as due to HC{sub 7}N were detected in photolysed Ar matrices doped with a cyanoacetylene/diacetylene mixture; this assignment was confirmed with the mass spectrometry of gases released upon the warm-up of the sample.
  • Four consecutive HC/sub 5/N transitions J = 7--6, 8--7, 9--8, and 10--9 have been recorded for each of the three sources Sgr B2, TMC 1, and IRC +10216. The observed line brightness temperatures have been used to derive HC/sub 5/N rotational temperatures: 28 K for Sgr B2, 5.5 K for TMC-1, and 13 K for IRC +10216. These are consistent with temperatures previously estimated for these molecular clouds. The J = 55--54 transition of HC/sub 11/N was searched in TMC-1 but was not found.
  • Deuterated cyanodiacetylene (DC/sub 5/N) has been observed for the first time in an interstellar cloud. The J = 10..-->..9 and J = 9..-->..8 transitions have been detected in emission in TMC 1. The abundance ratio DC/sub 5/N/HC/sub 5/N is found to lie in the range 0.006--0.016 overlapping the range 0.013--0.017 observed for DCO/sup +//HCO/sup +/, but somewhat less than the range 0.02--0.08 determined for DC/sub 3/N/HC/sub 3/N. From these observations, it is not possible to rule out the formation of HC/sub 5/N on grain surfaces or by dissociation of larger molecules.