Computational study on mechanisms of C₂H₅O₂+OH reaction and properties of C₂H₅O₃H complex

Abstract

A comprehensive theoretical study on the bimolecular reaction of C₂H₅O₂ with OH radicals was performed at the CCSD(T)/6-311++G(2df,2p)//B3LYP/6-311+G(d,p) level of theory. The calculation results show that C₂H₅O₂ + OH reaction proceeds on both the singlet and the triplet potential energy surfaces(PESs). On the singlet PES, the favorable pathway is the addition of OH radical to the terminal oxygen atom of C₂H₅O₂ radical, leading to the formation of trioxide C₂H₅O₃H with a barrierless process. Then, the trioxide directly decomposes to the products C₂H₅O and HO₂ radicals. On the triplet PES, the predominant pathways are α and β hydrogen atom abstractions of C₂H₅O₂ radical by OH radical-forming products ³CH₃CHO₂+H₂O and ³CH₂CH₂O₂+H₂O, and the corresponding barriers are 12.02(³TS8) and 19.19 kJ/mol(³TS9), respectively. In addition, the comprehensive properties of trioxide C₂H₅O₃H were investigated for the first time. The results indicate that the trioxide complex RC1 can exist stably in the atmosphere owing to a significantly large and negative enthalpy of formation(‒118.44 kJ/mol) as well as a high first excitation energy(5.94 eV).

Keywords

C₂H₅O₂ radical / Trioxide C₂H₅O₃H complex / Reaction mechanism / Enthalpy of formation / First excited energy

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