CH3O与ClO双自由基反应机理的量子化学研究.pdf

2005 年第 63 卷化学学报 Vol. 63, 2005 第 11 期, 1013 ~1017 ACTA CHIMICA SINICA No. 11, 1013 ~ 1017 * E-mail: ******@nenu. Received June 23, 2004; revised December 10, 2004; accepted January 28, 2005. 教育部“跨世纪优秀人才培养计划”( 教技函[2001]3) 资助项目. ·研究论文· CH 3 O 与 ClO 双自由基反应机理的量子化学研究赵岷 a , b 刘朋军 a 常鹰飞 a 孙昊 a 苏忠民 a 王荣顺* , a ( a 东北师范大学化学学院功能材料化学研究所长春 130024) ( b 渤海大学化学化工学院锦州 121000) 摘要在 QCISD(T)/6-311 + G(d,p)//B3LYP/6-311 + G(3df,3pd) 水平上, 对 CH 3 O 与 ClO 双自由基反应进行了理论研究. 结果表明, 该反应共有三个反应通道, 产物分别为 HOCl + CH 2 O, CH 2 O 2 + HCl 和 CH 3 Cl + O 2 ( 1 ?). 不论从动力学角度, 还是从热力学角度看, 形成产物 HOCl + CH 2 O 的通道均是最有利的, 因此为主要反应通道, 这与实验观察到的结果是一致的. 关键词 CH 3 O; ClO; 反应机理; 过渡态 Quantum Chemical Investigation of the Reaction Mechanism of CH 3 O with ClO ZHAO, Min a , b LIU, Peng-Jun a CHANG, Ying-Fei a SUN, Hao a SU, Zhong-Min a WANG, Rong-Shun * , a ( a Institute of Functional Material Chemistry , Faculty of Chemistry , Northeast Normal University , Changchun 130024 ) ( b College of Chemistry and Chemical Engineering , Bohai University , Jinzhou 121000 ) Abstract The mechanism for the double radicals reaction of CH 3 O with ClO has been investigated theo- retically at QCISD(T)/6-311 +G(d,p)//B3LYP/6-311 + G(3df,3pd) level. The results show that the reaction has three channels, yielding the products of HOCl + CH 2 O, CH 2 O 2 + HCl and CH 3 Cl + O 2 ( 1 ?), respectively. The