Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Photodissocaition Dynamics of Propiolic Acid at 212 nm: The OH Production Channel

  • Shin, Myeong Suk (Department of Chemistry, Institute for Molecular Science and Fusion Technology, Kangwon National University) ;
  • Lee, Ji Hye (Department of Chemistry, Institute for Molecular Science and Fusion Technology, Kangwon National University) ;
  • Hwang, Hyonseok (Department of Chemistry, Institute for Molecular Science and Fusion Technology, Kangwon National University) ;
  • Kwon, Chan Ho (Department of Chemistry, Institute for Molecular Science and Fusion Technology, Kangwon National University) ;
  • Kim, Hong Lae (Department of Chemistry, Institute for Molecular Science and Fusion Technology, Kangwon National University)
  • Received : 2012.06.27
  • Accepted : 2012.08.07
  • Published : 2012.11.20
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Abstract

Photodissociation dynamics of propiolic acid ($HC{\equiv}C-COOH$) at 212 nm in the gas phase was investigated by measuring rotationally resolved laser-induced fluorescence spectra of OH ($^2{\Pi}$) radicals exclusively produced in the ground electronic state. From the spectra, internal energies of OH and total translational energy of products were determined. The electronic transition at 212 nm responsible for OH dissociation was assigned as the ${\pi}_{C{\equiv}C}{\rightarrow}{\pi}^*{_{C=O}}$ transition by time-dependent density functional theory calculations. Potential energy surfaces of both the ground and electronically excited states were obtained employing quantum chemical calculations. It was suggested that the dissociation of OH from propiolic acid excited at 212 nm should take place along the $S_1/T_1$ potential energy surfaces after internal conversion and/or intersystem crossing from the initially populated $S_2$ state based upon the potential energy calculations and model calculations for energy partitioning of the available energy among products.

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