高等学校化学学报

高等学校化学学报

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烯丙基自由基(·C3H5)与一氧化氮(NO)反应势能面的理论研究

张浩, 孙延波, 李泽生, 孙家锺   

  1. 吉林大学理论化学研究所, 理论化学计算国家重点实验室, 长春 130023
  • 收稿日期:2006-03-02 修回日期:1900-01-01 出版日期:2006-12-10 发布日期:2006-12-10
  • 通讯作者: 李泽生

A Theoretical Study on the Potential Energy Surface of the Reaction ·C3H5+NO

ZHANG Hao, SUN Yan-Bo, LI Ze-Sheng, SUN Chia-Chung   

  1. State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, China
  • Received:2006-03-02 Revised:1900-01-01 Online:2006-12-10 Published:2006-12-10
  • Contact: LI Ze-Sheng

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摘要： 在CCSD(T)/6-311G(d,p)//B3LYP/6-311G(d,p)+ZPE水平上对反应·CHCHCH3+NO进行了计算, 并建立了其单重态的反应势能面. 在该反应中, 分别找到生成P1(CH3CHO+HCN), P2(CH3CHO+HNC), P3(CH3CN+HCHO), P4(CH3CCH+HNO)的4条产物通道, 其中·CHCHCH3和NO中的氮原子直接连接形成m1(trans-CH3CHCHNO), m1经过顺反异构形成m2(cis-CH3CHCHNO), m2再经过CCNO四元环合, 然后发生环解离, 最后生成产物P1(CH3CHO+HCN)是最可行的产物通道, 其余三条通道为次要产物通道. 该体系中生成P1的反应路径与同类体系·C2H3+NO的主要反应路径相类似, 两者的差别是前者为动力学可行的反应, 而后者为动力学不可行反应, 这使得·CHCHCH3+NO反应比·C2H3+NO反应更具有实际意义.

关键词: 烯丙基自由基(·C3H5), 一氧化氮(NO), 势能面

Abstract: In this article, the singlet potential energy surface of the reaction ·C3H5+NO was studied at CCSD(T)/6-311G(d,p)//B3LYP/6-311G(d,p) levels. The most favorable pathway leading to the product P1(CH3CHO+HCN) is as follows: R(CH3CHC·H+NO)→m1(trans-CH3CHCHNO)→m2(cis-CH3CHCHNO)→m8(CCNO four-member ring)→P1(CH3CHO+HCN). In the title reaction, other products P2(CH3CHO+HNC), P3(H2CO+CH3CN) and P4(CH3CCH+HNO) have also lower energies than the reactant, but the pathways leading to these products are all unfeasible in dynamics so that they are minor product channels. The comparison with the analogous C2H3+NO reaction was discussed. The two systems were analogous in the channels leading to the most favorable products P1 except that the former is feasible in kinetics and the latter is opposite.

Key words: Allyl radical(·C3H5), Nitric oxide(NO), Potential energy surface

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