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Red‐Light‐Induced Decomposition of an Organic Peroxy Radical: A New Source of the HO 2 Radical
Author(s) -
Kumar Manoj,
Francisco Joseph S.
Publication year - 2015
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201509311
Subject(s) - radical , chemistry , decomposition , troposphere , photochemistry , photodissociation , hydroxyl radical , atmospheric chemistry , autocatalysis , methyl radical , organic chemistry , catalysis , meteorology , ozone , physics
Abstract The gas‐phase decomposition of the α ‐hydroxy methylperoxy radical has been theoretically examined, and the results provide insight into a new source of the hydroperoxy radical (HO 2 ) in the troposphere. Bimolecular peroxy decomposition is promoted by the red‐light or near‐IR radiation excitation. The calculations suggest for the first time, an important chemical role for the H 2 O⋅HO 2 radical complex that exist in significant abundance in the troposphere. In particular, the reaction of organic peroxy radicals with the HO 2 radical and the H 2 O⋅HO 2 radical complex represent an autocatalytic source of atmospheric HO 2 . This reaction is a new example of red‐light‐initiated atmospheric chemistry that may help in understanding the discrepancy between the observed and measured levels of the HO x at sunrise.