高等学校化学学报

高等学校化学学报 ›› 2005, Vol. 26 ›› Issue (4): 723.

• 研究论文 • 上一篇    下一篇

HCCO与CH(2Π)双自由基反应微观动力学的理论研究

刘朋军1,2, 常鹰飞2, 孙昊2, 苏忠民2, 王荣顺2   

  1. 1. 海南师范学院化学系, 海口 571158;
    2. 东北师范大学化学学院功能材料化学研究所, 长春 130024
  • 收稿日期:2004-05-12 出版日期:2005-04-10 发布日期:2005-04-10
  • 通讯作者: 王荣顺(1934年生),男,教授,博士生导师,从事量子化学和材料化学的研究.E-mail:wangrs@nenu.edu.cn E-mail:wangrs@nenu.edu.cn
  • 基金资助:

    教育部“跨世纪优秀人才培养计划”基金(批准号:教技函[2001]3);海南省教育厅科研基金(批准号:hjkj200312)资助.

Dynamics of Biradical Micro-reaction Between HCCO and CH(2Π)

LIU Peng-Jun1,2, CHANG Ying-Fei2, SUN Hao2, SU Zhong-Min2, WANG Rong-Shun2   

  1. 1. Department of Chemistry, Hainan Normal College, Haikou 571158, China;
    2. Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, China
  • Received:2004-05-12 Online:2005-04-10 Published:2005-04-10

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摘要： 用量子化学密度泛函理论的UB3LYP/6-311+G**方法和高级电子相关的UQCISD(T)/6-311+G**方法研究了HCCO与CH(2Π)自由基反应的微观机理.采用双水平直接动力学方法IVTST-M和正则变分过渡态理论研究了在1000～2500K温度范围内反应的速率常数.结果表明,HCCO与CH(2Π)双自由基反应过程中存在3个反应通道,生成产物为C2H2+CO.通道2为主要反应路径,通道1也占一定的比例.在所研究的温度范围内,速率常数计算的变分效果均较小,反应为放热反应.

关键词: 乙烯酮自由基(HCCO), 反应机理, 密度泛函理论(DFT), 变分过渡态

Abstract: The mechanism for the biradical reaction beween HCCO and CH(2Π) was investigated theoretically by using the DFT-UB3LYP/6-311+G** and the high-level electron-correlation UQCISD(T)/6-311+G** at single-point. The dual-level direct dynamics method was employed to gain the information of potential energy surface for the title reaction. The rate constants were calculated over the range of temperature 1 000-2 500 K by using variational transition-state theory. The results show that the reaction mechanism of the title reaction involves three channels, producing C2H2+CO product. Channels 2 and 1 are the favorable routes. It is found that the variational effect for the rate constant calculation is very small in the studied temperature range. The reaction is exothermic.

Key words: Ketenyl radical(HCCO), Reaction mechanism, Density functional theory(DFT), Variational transition state

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