Computational Study on Mechanisms of C2H5O2+OH Reaction and Properties of C2H5O3H Complex

作者：Liu Yanli; Chen Long; Chen Dongping; Wang Weina; Liu Fengyi; Wang Wenliang^*

来源：Chemical Research in Chinese Universities, 2017, 33(4): 623-630.

DOI：10.1007/s40242-017-7055-4

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

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 alpha and beta hydrogen atom abstractions of C2H5O2 radical by OH radical-forming products (CH3CHO2)-C-3+H2O and (CH2CH2O2)-C-3+H2O, and the corresponding barriers are 12.02((3)TS8) and 19.19 kJ/mol((3)TS9), respectively. In addition, the comprehensive properties of trioxide C2H5O3H were investigated for the first time. The results indicate that the trioxide complex RC 1 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).

• 出版日期2017-8
• 单位陕西师范大学