Red-Light-Induced Decomposition of an Organic Peroxy Radical: A New Source of the HO2 Radical.

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 (HO2 ) 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 H2 O⋅HO2 radical complex that exist in significant abundance in the troposphere. In particular, the reaction of organic peroxy radicals with the HO2 radical and the H2 O⋅HO2 radical complex represent an autocatalytic source of atmospheric HO2 . 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 HOx at sunrise.

DOI: 10.1002/anie.201509311

Cite this paper

@article{Kumar2015RedLightInducedDO, title={Red-Light-Induced Decomposition of an Organic Peroxy Radical: A New Source of the HO2 Radical.}, author={Manoj Kumar and Joseph S Francisco}, journal={Angewandte Chemie}, year={2015}, volume={54 52}, pages={15711-4} }