Computational studies on the reactions of the peroxy radical CF3OCH2O2 .with HO2.and NO

Publication date: Available online 27 June 2019Source: Computational and Theoretical ChemistryAuthor(s): Zoi Salta, Stavroula Liaska, Demetrios K. Papayannis, Antonija Lesar, Agnie M. KosmasAbstractComputational studies on the reactions of the peroxy radical, CF3OCH2O2., with the species HO2. and NO. in the gas-phase are carried out , using ab initio and density functional theory methods. Formation of CF3OCH2OOH, through the attractive triplet state, is shown to be the dominant pathway in the reaction with HO2 . . The coupling with NO. leads primarily to CF3OCH2O. and NO2. through the decomposition of the association nitrite minimum CF3OCH2OONO. The nitrate adduct CF3OCH2ONO2 , a sink byproduct, may be produced in a two-step mechanism by the partial recombination of CF3OCH2O. and NO2. . The results are discussed in comparison with the general mechanism of the reactions of the organic peroxy radicals ROO with HO2 and NO. Also the present systems are shown to exhibit interesting correlations with regard to the reactivity of the peroxy radical, CH3OCH2O2. , reflecting the inductive effect of the fluorine atoms in the methoxy methyl group.Graphical abstract

Source: Computational and Theoretical Chemistry - June 28, 2019 Category: Chemistry Source Type: research