| 气相中二氧化铬与乙烯反应机理的理论研究 |
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| 引用本文： | 封雪松,陈晓霞. 气相中二氧化铬与乙烯反应机理的理论研究[J]. 四川理工学院学报(自然科学版), 2008, 21(6) |
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| 作者姓名： | 封雪松 陈晓霞 |
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| 作者单位： | 四川理工学院化学与制药工程学院,四川,自贡,643000;四川理工学院化学与制药工程学院,四川,自贡,643000 |
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| 基金项目： | 四川省教育厅科研基金项目 |
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| 摘 要： | 用密度泛函B3LYP/6-311++G(3df,3pd)//6-311G(2d,p)法研究了CrO2(+2A1/4A″)+C2H4生成P1[Cr(OCH2)(+2A"/4A")+CH2O]和P2[CrO(+2Σg/4Σg)+C2H4O]的气相反应,重点对影响反应机理和反应速率的势能面交叉现象进行了讨论,并运用Hammond假设和Yoshizawa等的内禀反应坐标单点垂直激发计算的方法大致确定了势能面交叉点(crossing point(CP))或势能面交叉缝(crossing seam)的位置。研究结果表明,CrO2+活化乙烯C-C键是一个[2+2]类型反应,整个反应经历了重排过程。
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| 关 键 词： | 密度泛函 势能面交叉现象 势能面交叉点 |
Theoretical Study on the Mechanism of the CrO_2~+ + C_2H_4 Reaction in Gas-phase |
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| FENG Xue-song,CHEN Xiao-xia. Theoretical Study on the Mechanism of the CrO_2~+ + C_2H_4 Reaction in Gas-phase[J]. Journal of Sichuan University of Science & Engineering(Natural Science Editton), 2008, 21(6) |
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| Authors: | FENG Xue-song CHEN Xiao-xia |
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| Affiliation: | FENG Xue-song,CHEN Xiao-xia(School of Chemistry , Pharmaceutical Engineering,Sichuan University of Science & Engineering,Zigong 643000,China) |
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| Abstract: | The gas-phase reaction of CrO2(+2A1/4A″)+ C2H4 to yield P1[Cr(OCH2)+(2A"/ 4A")+ CH2O] and P2[CrO+(2Σg /4Σg)+ C2H4O] has been investigated using density functional theory(DFT) at the B3LYP/6-311++G(3df,3pd)//6-311G(2d,p) level.The involving crossing between the potential energy surfaces is discussed.By means of the Hammond postulate and the intrinsic reaction coordinate(IRC) approach used by Yoshizawa et al,a crossing point(CP1) and a crossing seam between CP2 and CP3 are located.Our investigation indicates that activation C-C double bond of C2H4 by CrO2+ is [2+2] pathway,the whole reaction experiences rearranging process. |
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| Keywords: | DFT potential energy surfaces crossing potential energy surfaces crossing points |
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