OH production in the collision-free UV photolysis of aliphatic nitro compounds

The low-pressure gas phase photolysis of some simple nitroalkanes (C nH 2n+ 1NO 2) at ≈ 282 nm leads to OH radical formation for n > 1. The results indicate a transition state involving a five-membered ring, as suggested previously for the thermal dissociation of these compounds. This result is s...

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Bibliographic Details
Published in:Chemical physics letters 1987-03, Vol.134 (6), p.593-599
Main Authors: Greenblatt, G.D., Zuckermann, H., Haas, Y.
Format: Article
Language:English
Subjects:
Chemistry
Exact sciences and technology
General and physical chemistry
Photochemistry
Physical chemistry of induced reactions (with radiations, particles and ultrasonics)
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Summary:The low-pressure gas phase photolysis of some simple nitroalkanes (C nH 2n+ 1NO 2) at ≈ 282 nm leads to OH radical formation for n > 1. The results indicate a transition state involving a five-membered ring, as suggested previously for the thermal dissociation of these compounds. This result is supported by isotopic substitution studies, and by the fact that the rotational distribution of nascent OH radicals is essentially independent of the parent molecule. The low quantum yield (0.5–2%) and the absence of parent fluorescence show that another dissociation channel (or radiationless process) is the major route of electronic energy dissipation.
ISSN:0009-2614
1873-4448
DOI:10.1016/0009-2614(87)87200-7