高等学校化学学报

高等学校化学学报 ›› 2004, Vol. 25 ›› Issue (4): 685.

• 研究论文 • 上一篇    下一篇

NCS自由基与NO反应动力学的理论研究

刘朋军1,2, 潘秀梅1, 赵岷1, 孙昊1, 苏忠民1, 王荣顺1   

  1. 1. 东北师范大学化学学院功能材料化学研究所, 长春 130024;
    2. 海南师范学院化学系, 海口 571158
  • 收稿日期:2003-05-06 出版日期:2004-04-24 发布日期:2004-04-24
  • 通讯作者: 王荣顺(1934年出生),男,教授,博士生导师,从事量子化学和功能材料化学研究.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);东北师范大学青年教师基金(批准号:111382)资助

Theoretical Studies on Kinetics Reaction for the Reaction ofNCS Radical and NO

Liu Peng-Jun1,2, PAN Xiu-Mei1, ZHAO Min1, SUN Hao1, SU Zhong-Min1, WANG Rong-Shun1   

  1. 1. Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, China;
    2. Depattment of Chemistry, Hainan Normal University, Haikou 571158, China
  • Received:2003-05-06 Online:2004-04-24 Published:2004-04-24

PDF (PC)

被引次数

24

摘要： 用量子化学密度泛函理论B3LYP/6-31+G*和高级电子相关校正的偶合簇[CCSD(T)/6-311+G*]方法,对NCS自由基与NO反应的机理和动力学进行了理论研究,得到了体系的势能面信息和可能的反应机理.计算了反应的热力学参数及反应能垒.采用传统过渡态理论计算了各反应通道的速率常数.研究结果表明,NCS自由基与NO反应中存在4个反应通道,产物分别为OCS+N2,CS+N2O,ONS+CN和ONCNS.从能量变化和反应速率两方面考虑,NCS+NOOCS+N2应为主反应通道.

关键词: NCS自由基, NO, 反应机理, 动力学

Abstract: DFT-B3LYP was used to calculate the geometries of reactants, intermediates, transition states and products for NCS + NO reaction on the 6-31+G* level. The transition states and intermediates of the reaction were verified by frequency analysis. The intrinsic reaction coordinate(IRC) calculations at the same level were also carried out to check the connection between all the critical structures located on the potential energy surface. Single point energies were calculated on the CCSD(T)/6-311+G* level. The energy barriers, rate constants and thermodynamic quantities of the reaction were also calculated. The results show that the reaction system of the title reaction involves four paths, producing OCS+N2(1), CS+N2O(2), NS+OCN(3) and ONCNS(4) products, respectively. The NCS+NOOCS+N2 is the dominant reaction path.

Key words: NCS radical, NO, Reaction mechanism, Kinetics

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