高等学校化学学报

高等学校化学学报 ›› 2003, Vol. 24 ›› Issue (6): 1059.

• 论文 • 上一篇    下一篇

CH3O2·+NO气相反应的密度泛函理论研究

傅强1,2, 陈丽莉2, 潘秀梅2, 李泽生1, 孙家锺1   

  1. 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;
    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:2002-10-31 出版日期:2003-06-24 发布日期:2003-06-24
  • 通讯作者: 傅强(1956年出生),男,博士,教授,从事物理化学研究.E-mail:ifmc@nenu.edu.cn E-mail:ifmc@nenu.edu.cn
  • 基金资助:

    国家自然科学基金(批准号:29892168)资助

DFT Study of Reaction CH3O2·+NO→CH3O·+NO2 in Gas Phase

FU Qiang1,2, CHEN Li-Li2, PAN Xiu-Mei2, LI Ze-Sheng1, SUN Jia-Zhong1   

  1. 1. Institute of Theoretical Chemistry, State Key Laboratory of Theoretical and Computational Chemistry, Jilin University, Changchun, 130023, China;
    2. Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, China
  • Received:2002-10-31 Online:2003-06-24 Published:2003-06-24
  • Supported by:

    d:\PDF\.pdf

PDF (PC)

摘要： 用密度泛函方法分别研究了单态和三态CH3O 2·+NOCH3O·+NO2气相反应.结果表明,反应中NO进攻CH3O 2·经过了一个顺反异构化的过程,摘取CH3O 2·的端基氧.整个反应是吸热反应,理论计算吸热值为50.93kJ/mol,单态为多通道多步骤反应,决定速度步骤的能垒为190.61kJ/mol.而三态为单通道反应,其决定速度步骤的能垒为163.31kJ/mol.三态反应为最佳反应通道.该反应的研究将为保护臭氧层及大气环境提供重要的理论依据.

关键词: CH3O 2·, +NO, 密度泛函理论, 反应机理

Abstract: The mechanism of the reaction CH3O 2·+NO CH3O ·+NO2 in gas phase has been studied bYUsing density functional theory. The geometries of reactants, transition states, intermediates and products have been optimized by B3LYP/6-31G * and HF/6-31G* basis set. Transition states and intermediates have been verified by frequency analysis. The reaction path has been traced by Fukui′s theory of intrinsic reaction coordinate(IRC), with the change of geometry parameter being computed. In order to obtain credible energy, single points energy has been calculated by QCISD methods using the 6-311G** basis set with zero-point energy correction done by B3LYP method. The isomerizations of the intermediates and the charge densities have been analyzed. The results show that the whole reaction comes through many courses, and it is an endothermic reaction with 50.93 kJ/mol endothermic value calculated. Among the three reaction paths proposed, the triplet state reaction is the most probable one with the lowest activation energy of 163.31 kJ/mol. This work will provide the important theoretical foundation for protecting theozonosphere and atmosphere.

Key words: CH3O 2·+NO, Density functional theory, Reaction mechanism

中图分类号: 

TrendMD: