高等学校化学学报

高等学校化学学报 ›› 2002, Vol. 23 ›› Issue (6): 1147.

• 研究论文 • 上一篇    下一篇

乙烯基自由基(C2H3·)与羟基自由基(OH·)反应势能面的理论研究

刘桂霞, 丁益宏, 李泽生, 黄旭日, 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:2001-06-11 出版日期:2002-06-24 发布日期:2002-06-24
  • 通讯作者: 李泽生(1954年出生),男,博士,教授,博士生导师,从事理论化学研究.E-mail:zeshengli@mail.jlu.edu.cn E-mail:zeshengli@mail.jlu.edu.cn
  • 基金资助:

    国家自然科学基金(批准号:29892168;20073014);教育部博士学科点基金;教育部高校骨干教师基金;教育部科学技术重点项目基金资助

Theoretical Study on the Potential Energy Surface of the Reaction of Vinyl Radical (C2H3·) with Hydroxyl Radical(OH·)

LIU Gui-Xia, DING Yi-Hong, LI Ze-Sheng, HUANG Xu-Ri, SUN Chia-Chung   

  1. Institute of Theoretical Chemistry, State Key Laboratory of Theoretical and Computational Chemistry, Jilin University, Changchun 130023, China
  • Received:2001-06-11 Online:2002-06-24 Published:2002-06-24

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摘要： 在QCISD(T)/6-311G(2df,p)//B3LYP/6-311G(d,p)水平上对自由基反应C2H3·+OH·进行了计算,结果表明,经过缔合、多步H转移、CH3转移和离解等复杂过程,最终可得到8种产物(P1～P8),其中产物P2(H2CCO+H2)和P6(CH3CO·+H·)是主要产物.本文得到的CH2CHOH(1或1′),CH3CHO(2)和CH3COH(3)之间的过渡态TS1/2,TS1′/3和TS2/3的能量顺序与Wesdemiotis等的实验推测相反,而与Smith等的计算结果一致.

关键词: 乙烯基(C2H3·, ), 羟基(OH), 反应势能面

Abstract: The QCISD(T)/6-311G(2 df,p)//B3LYP/6-311G(d,p) calculations are performed on the mechanism of the radical reaction C2H3·+OH·. Eight products, P1-P8, may be obtained via the complex reaction channels, i.e. association, multi step Hshift, CH3 shift, dissociation, and so on. According to our calculated results, we predict that producets P2 and P6 may be the main products. In this paper, the energy ordering of the transition states TS1/2, TS1′/3 and TS2/3, which connect the C2H4O isomers CH2CHOH(1 or 1′), CH3CHO(2)and CH3COH(3), is TS2/3>TS1′/3>TS1/2, and it is the reverse of the ordering proposed by Wesdemiotis and McLafferty, but in good agreement with Smith et al.′s calculated result.

Key words: Vinyl radical, Hydroxyl radical, Potential energy surface

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