A computational study on the reaction mechanism of C₂H₅S with HO₂

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• 作者：Yue Zhang ; Wei Zhang ; Tianlei Zhang ; Wenxin Tian ; Wenliang Wang
• 关键词：C2H5S ; HO2 ; Reaction mechanism ; Hydrogen abstraction reaction ; Addition&ndash ; elimination reaction
• 刊名：Computational and Theoretical Chemistry
• 出版年：2012
• 出版时间：15 August, 2012
• 年：2012
• 卷：994
• 期：Complete
• 页码：65-72
• 全文大小：916 K

文摘

The mechanism of the reaction of the radical C₂H₅S with the radical HO₂ has been investigated theoretically by means of the density functional theory (DFT) and coupled cluster theory (CC). The geometries of all the stationary points and the selected points along the potential energy surfaces for the reaction of C₂H₅S with HO₂ were optimized at the B3LYP/6-311G(2d,p) level of theory. The harmonic vibrational frequencies of all the stationary points were calculated at the above same level of theory. The single point energies were further refined at the CCSD(T)/aug-cc-pVDZ level of theory based on the B3LYP/6-311G(2d,p) optimized geometries. Eight possible reaction pathways including eleven reaction channels on both the singlet and triplet potential energy profiles for the title reaction were explored. The calculated results indicated that Path R4, the formation of the products C₂H₅SO + OH on the singlet potential energy profile, is likely to be the most favorable channel among Path R1¡«4, and Path R5, hydrogen abstraction of HO₂ by the S atom of CH₃CH₂S, is the most favorable among Path R5¡«8 on the triplet potential energy profile. The major products of the reaction may be C₂H₅SH, ³O₂, C₂H₅SO and OH.