丙烯基自由基(·C_3H_5)与O_2反应机理的理论研究
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- 英文论文题名：Theoretical Calculation of Reaction Mechanisms for ·C_3H_5 + O_2
- 论文作者：曹晓梅 ; 李泽荣 ; 李象远
- 英文论文作者：Xiao-Mei Cao ; Ze-Rong Li ; Xiang-Yuan Li ; Department of Aeronautics & Astronautics ; Sichuan University ; Department of Chemistry ; Sichuan University ; Department of Chemical Engineering ; Sichuan University
- 年：2016
- 作者机构：四川大学空天科学与工程学院;四川大学化学学院;四川大学化学工程学院;
- 论文关键词：丙烯基自由基 ; 氧气 ; 低温
- 英文论文关键词：allyl radical ; oxygen ; low temperature
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第四十六分会：燃烧化学
- 语种：中文
- 分类号：O643.12
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第四十六分会 ; 燃烧化学
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：179k
- 原文格式：D
- 会议级别：全国
摘要
丙烯在碳氢燃料的燃烧中起着非常重要的作用,近年来,与燃烧化学相关的自由基-分子反应备受关注,丙烯基自由基对于预测丙烯的燃烧特性至关重要。然而,不管是实验还是理论计算方面,丙烯基自由基低温氧化的研究都十分缺乏。我们用量子化学计算方法对C_3H_5两步加氧的反应机理进行了理论研究,在B3LYP/6-31G(2df,p)水平下优化稳定分子结构和过渡态,并在此构型的基础上,采用高精度组合方法G4得到各驻点的高级单点能量。采用TST,VTST结合RRKM/ME方法计算了压力相关反应的速率常数。并与C_2H_3等共轭体系进行了对比。本文的研究将为烷烃低温燃烧动力学模拟提供有力帮助。
Propene is a key intermediate in the combustion of large molecular alkanes. Recently, the reactions of free radicals and molecule associated with combustion chemistry have received great attention, what's more, the allyl radical is critical to predicting the combustion properties of propene. However, there are few experiments and theoretical researches on these reactions. The theoretical calculation on the mechanisms for C_3H_5 + O_2 reaction was carried out based on the quantum chemical calculating methods. The geometries of reactants, transition states, intermediates and products have been optimized by B3LYP/6-31G(2df, p) level. G4 has been used to calculate the energies. Variational transition state theory, Rice-Ramsperger-Kassel-Marcus/master equation simulations provided temperature-and pressure-dependent rate constants. This system was compared with some analogous such as C_2H_3. The results of this study provide insight into the combustion of allyl radical and will benefit the development of alkane kinetic mechanisms.
Propene is a key intermediate in the combustion of large molecular alkanes. Recently, the reactions of free radicals and molecule associated with combustion chemistry have received great attention, what's more, the allyl radical is critical to predicting the combustion properties of propene. However, there are few experiments and theoretical researches on these reactions. The theoretical calculation on the mechanisms for C_3H_5 + O_2 reaction was carried out based on the quantum chemical calculating methods. The geometries of reactants, transition states, intermediates and products have been optimized by B3LYP/6-31G(2df, p) level. G4 has been used to calculate the energies. Variational transition state theory, Rice-Ramsperger-Kassel-Marcus/master equation simulations provided temperature-and pressure-dependent rate constants. This system was compared with some analogous such as C_2H_3. The results of this study provide insight into the combustion of allyl radical and will benefit the development of alkane kinetic mechanisms.
引文
[1]Goldsmith C.F.;Harding L.B.;J.Phys.Chem.A 2015,119:7766-7779
[2]Lee J.;Bozzelli J.W.;Proc.Combust.Inst.2005,30:1015-1022
[2]Lee J.;Bozzelli J.W.;Proc.Combust.Inst.2005,30:1015-1022
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