关于CH_3OCH_3和CH_3OCH_2CH_3与NO_3自由基提氢反应的理论研究
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- 英文论文题名：Theoretical investigation of H-abstraction reactions CH_3OCH_3 and CH_3OCH_2CH_3 with NO_3 radicals
- 论文作者：叶近婷 ; 白凤杨 ; 潘秀梅
- 英文论文作者：Jinting Ye ; Fengyang Bai ; Xiumei Pan ; Faculty of Chemistry ; Northeast Normal University
- 年：2016
- 作者机构：东北师范大学化学学院;
- 论文关键词：过渡态 ; 速率常数 ; 分支比
- 英文论文关键词：Transition state ; Rate constants ; Branching ratio
- 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-第十八分会：电子结构理论方法的发展与应用
- 语种：中文
- 分类号：O621.25
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第十八分会 ; 电子结构理论方法的发展与应用
- 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：197k
- 原文格式：D
- 会议级别：全国
摘要
CH_3OCH_3和CH_3OCH_2CH_3作为典型的含氧挥发性有机化合物,由于含有醚键(–O–)促使在对流层有很强的反应活性~([1])。为了更好地指导实验和理论工作,我们采用密度泛函理论(DFT)及CCSD(T)方法计算了CH_3OCH_3和CH_3OCH_2CH_3与NO_3自由基详细的提氢反应机理。根据考虑小曲率隧道效应(SCT)校正的正则变分过渡态理论(CVT)得到的298K温度下的速率常数与实验值~([2])很好的吻合。在CCSD(T)//MP2/6-311G(d,p)理论水平上,我们给出了该反应在200-600K温度下的三参数表达式和分支比。
CH_3OCH_3 and CH_3OCH_2CH_3 are prototypical species of volatile oxygenated organic compounds(VOCs), since the introduction of ether linkage –O– may lead to an even greater reactivity in the troposphere.In order to guide the future of the experimental and theoretical work, detailed reaction mechanisms of title reactions have been investigated using density functional theory(DFT) and CCSD(T) methods.The total rate constants calculated by canonical variational transition state dynamic computations with the small-curvature tunneling correction are good agreement with the experimental values at 298 K.The three-parameter expressions and branching ratios over the temperature range of 200–600 K at CCSD(T)//MP2/6-311G(d,p) level are obtained.
CH_3OCH_3 and CH_3OCH_2CH_3 are prototypical species of volatile oxygenated organic compounds(VOCs), since the introduction of ether linkage –O– may lead to an even greater reactivity in the troposphere.In order to guide the future of the experimental and theoretical work, detailed reaction mechanisms of title reactions have been investigated using density functional theory(DFT) and CCSD(T) methods.The total rate constants calculated by canonical variational transition state dynamic computations with the small-curvature tunneling correction are good agreement with the experimental values at 298 K.The three-parameter expressions and branching ratios over the temperature range of 200–600 K at CCSD(T)//MP2/6-311G(d,p) level are obtained.
引文
[1]Atkinson,R.Atmos.Environ.2007,41,200.
[2]Chen,L.Uchimaru,T.Kutsuna,S.Tokuhashi,K.Sekiya,A.Okamoto,H.Int.J.Chem.Kinet.2009,41,490.
[2]Chen,L.Uchimaru,T.Kutsuna,S.Tokuhashi,K.Sekiya,A.Okamoto,H.Int.J.Chem.Kinet.2009,41,490.