文献类型：期刊文献

英文题名：Theoretical and kinetic study of the reaction of C2H3 + HO2 on the C2H3O2H potential energy surface

作者：Guo, Junjiang Tang, Shiyun Tan, Ningxin

第一作者：郭俊江

通信作者：Guo, JJ[1];Tan, NX[2]

机构：[1]Guizhou Inst Technol, Sch Chem Engn, Guiyang 550003, Guizhou, Peoples R China;[2]Sichuan Univ, Sch Chem Engn, Chengdu 610064, Sichuan, Peoples R China

第一机构：贵州理工学院化学工程学院

通信机构：corresponding author), Guizhou Inst Technol, Sch Chem Engn, Guiyang 550003, Guizhou, Peoples R China;corresponding author), Sichuan Univ, Sch Chem Engn, Chengdu 610064, Sichuan, Peoples R China.|贵州理工学院化学工程学院;贵州理工学院;

年份：2017

卷号：7

期号：71

起止页码：44809-44819

外文期刊名：RSC ADVANCES

收录：;EI(收录号：20174104256541);Scopus(收录号：2-s2.0-85030712113);WOS:【SCI-EXPANDED(收录号:WOS:000411662100025)】；

基金：We would like to thank Dr Long Li with China University of Mining and Technology for his help. We are also thankful to Shenzhen Cloud Computing Center, for providing us computational resources. This work is supported by the National Natural Science Foundation of China (No. 91441132) and S& T Plan Project Approving in Guizhou (No. Guizhou branch in LH word [2016] 7104).

语种：英文

外文关键词：Ethylene - Ignition - Molecular physics - Potential energy - Potential energy surfaces - Quantum chemistry - Shock tubes

摘要：The potential energy surface (PES) for reaction of C2H3 + HO2 was examined by using high-level quantum chemical methods. Conventional transition state theory (TST) was used to determine the rates where the reaction has a tight transition state; variable reaction coordinate transition-state theory (VRC-TST) was used for rate constant calculations corresponding to the barrierless reactions. And Rice-RamsbergerKassel- Marcus/Master-Equation (RRKM/ME) theory was used to calculate the pressure-dependent rate constants of these channels. The major product channel of the reaction C2H3 + HO2 is the formation of C2H3O2H via a highly vibrationally excited product. Thermochemical properties of the species involved in the reactions were determined using the QCISD(T)/CBS//M062X/6-311++G(d, p) method and enthalpies of formation of species were compared with literature values. The calculated rate constants are in good agreement with limited data from the literature and are given in modified Arrhenius equation form, which are useful in combustion modeling of hydrocarbons. Finally, in order to investigate the effect of the calculated parameters on ignition delay, they were used to simulate ignition delay with the current mainstream mechanism. It is shown that these parameters have improved the mechanism and that the simulation results for ethylene ignition in a shock tube are similar to the observed values.