高等学校化学学报 ›› 2001, Vol. 22 ›› Issue (12): 2077.

• 研究论文 • 上一篇    下一篇

O(3P)+O2H——OH+O2反应机理的密度泛函理论研究

潘秀梅1, 王荣顺1, 苏忠民1, James Tyrrell2   

  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. 南伊利诺斯大学化学与生物化学系, IL 62901, 美国
  • 收稿日期:2001-01-18 出版日期:2001-12-24 发布日期:2001-12-24
  • 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:

    2000年教育部“跨世纪优秀人才培养计划”基金(批准号:教技函[2001]3);东北师范大学年轻教师基金(批准号:111382)资助

DFT Study on the Reaction Mechanism of O(3P)+O2H——OH+O2

PAN XiuMei1, WANG RongShun1, SU ZhongMin1, James Tyrrell2   

  1. 1. Instituteof Functional Material Chemistry, Facultyof Chemistry, Northeast Normal University, Changchun 130024, China;
    2. Departmentof Chemistry and Biochemistry, Southern Illinois University, Carbondale, IL 62901, USA
  • Received:2001-01-18 Online:2001-12-24 Published:2001-12-24

摘要: 用密度泛函理论方法研究了O(3P)与O2H反应生成羟基和氧分子的反应机理.在PW91/6-31+G*水平上用梯度解析技术全自由度优化上述反应物、产物和反应路径上的中间体及过渡态几何构型,并通过频率振动分析加以确认,计算IRC反应路径及中间体异构化过程,确定了此反应的可能反应通道.结果表明:该反应是多通道多步骤的强放热反应.首先形成顺式或反式O3H富能中间体,此过程无能垒;然后跨过一个能垒分解成产物OH和O2.通道IM1→TS1比IM2→TS2克服的能垒要大,反应放热372.822kJ.mol-1.IM1TS3IM2可相互转化.

关键词: 密度泛函理论(DFT), O(3P), 反应机理, 过渡态

Abstract: The reaction mechanism of O(3P)+O2HOH+O2 has been studied by using Density Function Theory. The geometries of reactions, transition states, intermediates and products have been optimized by PW91/631+G* basis set and verified by frequency analysis. The reaction pathway and isomerized process were traced by Fukui's theory of intrinsic reaction coordinate(IRC). The reaction channels were verified. The results show that the reaction is a multistep and multichannel complex one followed by heat giving out strongly. Along the reaction path there are a little of transition state and two intermediates. The potential energy of IM1→TS1 is larger than that of IM2→TS2. The reaction heat is 372.822 kJ5mol-1. IM1TS3IM2 can isomerize each other.

Key words: Density functional theory, O(3P), Reaction mechanism, Transition state

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