標題: Photodissociation dynamics of ClOOCl at 248.4 and 308.4 nm
作者: Huang, Wen-Tsung
Chen, Andrew F.
Chen, I-Cheng
Tsai, Chen-Hsun
Lin, Jim Jr-Min
應用化學系
Department of Applied Chemistry
公開日期: 2011
摘要: The dynamics of ClOOCl photodissociation at 248.4 and 308.4 nm was studied with photofragment translational spectroscopy. At 248.4 nm photoexcitation, the observed products are Cl, O(2), ClO and O. Product translational energy distributions P(E) and anisotropy parameters beta were deduced from the measured time-of-flight spectra of the Cl, O(2), and ClO photoproducts. The photodissociation mechanisms have been discussed and compared with available theoretical results. Synchronous and fast sequential breaking of the two Cl-O bonds may both contribute to the dissociation. The relative product yields for [ClO] : [Cl] was measured to be 0.15 +/- 0.04 : 1. The relative amounts of [O] : [O(2)] products were estimated to be 0.12 : 1. The branching ratios among the Cl + O(2) + Cl : ClO + ClO : ClO + Cl + O product channels were estimated to be 0.82 : 0.08 : 0.10. At 308.4 nm excitation, time-of-flight spectra of the O(2) and ClO photoproducts were recorded while there was interference from Cl(2) impurity in detecting the Cl product. Nonetheless, the observed ClO yield relative to the O(2) yield at 308.4 nm is 1.5 times that at 248.4 nm. The branching ratio between the Cl + O(2) + Cl : ClO + ClO product channels was estimated to be 0.81 : 0.19 at 308.4 nm. This result suggests that the ClO product may contribute a noticeable yield in the photolysis of ClOOCl at the atmospherically important wavelengths above 300 nm.
URI: http://hdl.handle.net/11536/26004
http://dx.doi.org/10.1039/c0cp02453h
ISSN: 1463-9076
DOI: 10.1039/c0cp02453h
期刊: PHYSICAL CHEMISTRY CHEMICAL PHYSICS
Volume: 13
Issue: 18
起始頁: 8195
結束頁: 8203
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