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Published on: November 3, 2016
Dihalogenated Methylperoxy Radicals: Spectroscopic Characterization and Photodecomposition by Release of HO.
1College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, P. R. China.
Abstract:
Two atmospherically relevant dihalogenated methylperoxy radicals CHX2 OO. (X=F and Cl) have been generated through O2 -oxidation of the corresponding alkyl radicals CHX2 . in the gas phase. The IR spectroscopic characterization of both radicals in cryogenic Ar- and N2 -matrices (15 K) is supported by 18 O-labeling and ab initio calculations at the UCCSD(T)/aug-cc-pVTZ level. Upon 266 nm laser irradiation, both radicals decompose mainly by releasing hydroxyl radicals (→HO. +X2 CO) via the intermediacy of intriguing α-hydroperoxyalkyl radicals (. CX2 OOH), implying that the photooxidation of dihalogenated hydrocarbons might serve as important sources of HO. radicals in the atmosphere.
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