| CH_3SO+HO_2气相反应机理与主通道速率常数 |
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| 引用本文： | 卢彦霞,王文亮,王渭娜,刘英英,张越.CH_3SO+HO_2气相反应机理与主通道速率常数[J].化学学报,2010,68(13). |
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| 作者姓名： | 卢彦霞 王文亮 王渭娜 刘英英 张越 |
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| 作者单位： | 陕西师范大学化学与材料科学学院,陕西省大分子科学重点实验室,西安,710062 |
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| 摘 要： | 在MPW1PW91/6-311G(d,p)水平上优化了标题反应各驻点物种的几何构型,并在相同水平上通过频率计算和内禀反应坐标(IRC)分析对过渡态结构及连接性进行了验证.采用QCISD(T)/6-311G(d,p)方法对所有驻点及反应路径的部分选择点进行单点能校正,分别构建了CH3SO+HO2反应体系的单、三重态反应势能剖面.研究结果表明,CH3SO+HO2反应体系存在6条反应通道7条路径,优势通道(1)R→3IM→P1(CH3SOH+3O2)发生在三重态势能面上,此通道包含两条路径,其表观活化能分别为12.01和-30.04kJ?mol-1,主路径(2)R→3IM→3TS2→P1(CH3SOH+3O2)是一个无势垒氢迁移过程.利用经典过渡态理论(TST)与变分过渡态理论(CVT)并结合小曲率隧道效应模型(SCT),分别计算了主路径(2)在200～2500K温度范围内的速率常数kTST,kCVT和kCVT/SCT,在此温度区间内的表观反应速率常数三参数表达式为kCVT/SCT=4.08×10-24T3.13exp(8012.2/T)cm3imolecule-1is-1,具有负温度系数效应.速率常数计算结果显示,变分效应在计算温度段内影响较小,而量子力学隧道效应在低温段有显著影响.
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| 关 键 词： | 单重态势能剖面 三重态势能剖面 反应机理 速率常数 |
Mechanistic Study of CH3SO+HO2 Reaction and Rate Constants of Major Channel in the Gas Phase |
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| Lu Yanxia,Wang Wenliang,Wang Weina,Liu Yingying,Zhang Yue.Mechanistic Study of CH3SO+HO2 Reaction and Rate Constants of Major Channel in the Gas Phase[J].Acta Chimica Sinica,2010,68(13). |
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| Authors: | Lu Yanxia Wang Wenliang Wang Weina Liu Yingying Zhang Yue |
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| Institution: | Lu,Yanxia Wang,Wenliang Wang,Weina Liu,Yingying Zhang,Yue (Key Laboratory for Macromolecular Science of Shaanxi Province,School of Chemistry and Materials Science,Shaanxi Normal University,Xi'an 710062) |
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| Abstract: | The geometries,vibrational frequencies of all stationary points involved in the title reaction were calculated at the MPW1PW91/6-311G(d,p) level.Relationships of reactants,intermediates,transition states and products are confirmed by the intrinsic reaction coordinate (IRC) calculations.The single-point energy and the selected points along the minimum energy potential were calculated at the QCISD(T)/6-311G(d,p),as well as the singlet and triplet potential energy surfaces were investigated.The results show th... |
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| Keywords: | CH3SO HO2 |
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