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Photodissociation dynamics of HNCO at 248 nm

✍ Scribed by R.A. Brownsword; T. Laurent; R.K. Vatsa; H.-R. Volpp; J. Wolfrum

Publisher: Elsevier Science
Year: 1996
Tongue: English
Weight: 520 KB
Volume: 258
Category: Article
ISSN: 0009-2614
DOI: 10.1016/0009-2614(96)00626-4

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✦ Synopsis

Using the laser photolysis/laser-induced fluorescence (LP/LIF) pump-probe technique, the gas-phase photodissociation dynamics of room temperature HNCO was studied at a photolysis wavelength of 248 nm. H atoms produced via HNCO + hv ~ H(2S)+ NCO(X 2H) were detected by vacuum-UV laser-induced fluorescence (VUV-LIF) at the Lyman-a transition. By means of a calibration method -using H2S photolysis as a source of well defined H atom concentrationsthe absolute cross section for direct photolytic H atom formation was determined to be tr H = (1.2 + 0.3)× 10 -2~ cm 2 molecule-~. From the H atom Doppler profiles, measured under single-collision conditions, the fraction of the available energy released as product translational energy was determined to be fT(H + NCO) = (0.55 + 0.02). In addition, the second energetically accessible 'spin-forbidden' dissociation channel, HNCO + h v ~ NH(X 3E-) + CO(X ~E ÷ ), was investigated. Our results show that at a wavelength of 248 nm, direct H atom formation is the dominant dissociation channel in the HNCO photolysis.

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