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UV Photolysis of Pyrazine and the Production of Hydrogen Isocyanide.
Wilhelm, Michael J; Petersson, George A; Smith, Jonathan M; Behrendt, Drew; Ma, Jianqiang; Letendre, Laura; Dai, Hai-Lung.
Afiliación
  • Wilhelm MJ; Department of Chemistry , Temple University , 1901 North 13th Street , Philadelphia , Pennsylvania 19122 , United States.
  • Petersson GA; Institute for Computational Molecular Science , Temple University , 1925 North 12th Street , Philadelphia , Pennsylvania 19122 , United States.
  • Smith JM; Department of Chemistry , Temple University , 1901 North 13th Street , Philadelphia , Pennsylvania 19122 , United States.
  • Behrendt D; Department of Chemistry , Temple University , 1901 North 13th Street , Philadelphia , Pennsylvania 19122 , United States.
  • Ma J; Department of Chemistry , Temple University , 1901 North 13th Street , Philadelphia , Pennsylvania 19122 , United States.
  • Letendre L; Department of Chemistry , University of Pennsylvania , 231 South 34th Street , Philadelphia , Pennsylvania 19104 , United States.
  • Dai HL; Department of Chemistry , Temple University , 1901 North 13th Street , Philadelphia , Pennsylvania 19122 , United States.
J Phys Chem A ; 122(46): 9001-9013, 2018 Nov 21.
Article en En | MEDLINE | ID: mdl-30373368
Photolysis of the diazine heterocycle, pyrazine, following irradiation at 308, 248, and 193 nm was examined using nanosecond time-resolved Fourier transform infrared emission spectroscopy. The resulting time-resolved IR emission spectra reveal that for 308 and 248 nm vibrationally highly excited pyrazine is produced, but no photolysis products were detected. However, at 193 nm excitation, the measured IR emission spectra consist solely of resonances originating from rovibrationally excited photofragments, including acetylene (HCCH), hydrogen cyanide (HCN), and hydrogen isocyanide (HNC), indicating that photofragmentation proceeds from vibrationally highly excited pyrazine on the ground electronic state. Spectral fit analysis of the time-resolved HCN and HNC IR emission band shapes and intensities allowed an estimate of the nascent product population distributions, from which a lower bound estimate of the HNC/HCN branching ratio was deduced as Φ ≥ 0.07. Additionally, ab initio calculations were performed in order to examine the propensity of photoinduced reactions on the ground- and lowest-energy excited-state surfaces. The calculations provide a basis for understanding the wavelength dependence of the UV photolysis of pyrazine, the photolytic production of HNC, and also explain previous experimental observations in the literature.
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: J Phys Chem A Asunto de la revista: QUIMICA Año: 2018 Tipo del documento: Article País de afiliación: Estados Unidos Pais de publicación: Estados Unidos
Texto completo
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Imprimir
XML
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: J Phys Chem A Asunto de la revista: QUIMICA Año: 2018 Tipo del documento: Article País de afiliación: Estados Unidos Pais de publicación: Estados Unidos