Photodissociation dynamics of ClOOCl at 248.4 and 308.4 nm
Identifieur interne : 006833 ( Main/Exploration ); précédent : 006832; suivant : 006834Photodissociation dynamics of ClOOCl at 248.4 and 308.4 nm
Auteurs : Wen-Tsung Huang [Taïwan] ; Andrew F. Chen [Taïwan] ; I-Cheng Chen [Taïwan] ; Chen-Hsun Tsai [Taïwan] ; Jim Jr-Min Lin [Taïwan]Source :
- PCCP. Physical chemistry chemical physics : (Print) [ 1463-9076 ] ; 2011.
Descripteurs français
- Pascal (Inist)
English descriptors
- KwdEn :
Abstract
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, O2, ClO and O. Product translational energy distributions P(E) and anisotropy parameters β were deduced from the measured time-of-flight spectra of the Cl, O2, 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]: [O2] products were estimated to be 0.12: 1. The branching ratios among the Cl + O2 + Cl: ClO + CIO: CIO + 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 O2 and ClO photoproducts were recorded while there was interference from Cl2 impurity in detecting the Cl product. Nonetheless, the observed ClO yield relative to the O2 yield at 308.4 nm is 1.5 times that at 248.4 nm. The branching ratio between the Cl + O2 + 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.
Affiliations:
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<profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>Anisotropy</term>
<term>Branching ratio</term>
<term>Dissociation</term>
<term>Dynamics</term>
<term>Energy distribution</term>
<term>Excitation</term>
<term>Impurity</term>
<term>Mechanism</term>
<term>Photodissociation</term>
<term>Photolysis</term>
<term>Sequential</term>
<term>Translational energy</term>
<term>Wavelength</term>
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<keywords scheme="Pascal" xml:lang="fr"><term>Photodissociation</term>
<term>Dynamique</term>
<term>Energie translationnelle</term>
<term>Distribution énergie</term>
<term>Anisotropie</term>
<term>Mécanisme</term>
<term>Séquentiel</term>
<term>Dissociation</term>
<term>Rapport branchement</term>
<term>Excitation</term>
<term>Impureté</term>
<term>Photolyse</term>
<term>Longueur onde</term>
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<front><div type="abstract" xml:lang="en">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<sub>2</sub>
, ClO and O. Product translational energy distributions P(E) and anisotropy parameters β were deduced from the measured time-of-flight spectra of the Cl, O<sub>2</sub>
, 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<sub>2</sub>
] products were estimated to be 0.12: 1. The branching ratios among the Cl + O<sub>2</sub>
+ Cl: ClO + CIO: CIO + 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<sub>2</sub>
and ClO photoproducts were recorded while there was interference from Cl<sub>2</sub>
impurity in detecting the Cl product. Nonetheless, the observed ClO yield relative to the O<sub>2</sub>
yield at 308.4 nm is 1.5 times that at 248.4 nm. The branching ratio between the Cl + O<sub>2</sub>
+ 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.</div>
</front>
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<name sortKey="Chen, Andrew F" sort="Chen, Andrew F" uniqKey="Chen A" first="Andrew F." last="Chen">Andrew F. Chen</name>
<name sortKey="Chen, I Cheng" sort="Chen, I Cheng" uniqKey="Chen I" first="I-Cheng" last="Chen">I-Cheng Chen</name>
<name sortKey="Huang, Wen Tsung" sort="Huang, Wen Tsung" uniqKey="Huang W" first="Wen-Tsung" last="Huang">Wen-Tsung Huang</name>
<name sortKey="Jr Min Lin, Jim" sort="Jr Min Lin, Jim" uniqKey="Jr Min Lin J" first="Jim" last="Jr-Min Lin">Jim Jr-Min Lin</name>
<name sortKey="Jr Min Lin, Jim" sort="Jr Min Lin, Jim" uniqKey="Jr Min Lin J" first="Jim" last="Jr-Min Lin">Jim Jr-Min Lin</name>
<name sortKey="Jr Min Lin, Jim" sort="Jr Min Lin, Jim" uniqKey="Jr Min Lin J" first="Jim" last="Jr-Min Lin">Jim Jr-Min Lin</name>
<name sortKey="Tsai, Chen Hsun" sort="Tsai, Chen Hsun" uniqKey="Tsai C" first="Chen-Hsun" last="Tsai">Chen-Hsun Tsai</name>
</country>
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