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Theoretical study on thermal decomposition of azoisobutyronitrile in ground state

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Science china {1. 2004年第5期47卷 373-380页

作者： sun chengke1,2, zhao hongmei1 & li zonghe1 1. department of chemistry, beijing normal university, beijing 100875, china 2. department of chemistry, Qujing normal College, Qujing 655000, china Dept. of Chem. Beijing Normal Univ. Beijing 100875 China Dept. of Chem. Qujing Normal Coll. Qujing 655000 China

The thermal decomposition mechanisms of azoisobutyronitrile (AIBN) in the ground state have been investigated systematically. Based on the potential energy surfaces (PES) of various possible dissociation paths obtained using the semiempirical AM1.method with partial optimization, the density function theory B3LYP/6-31.G* method was employed to optimize the geometric parameters of the reactants, the intermediates, the products and the transition states, which were further confirmed by the vibrational analysis. The obtained results show that the re- action process of the two-bond (three-body) simultaneous cleavage Me2(CN)C─ N=N─ C(CN)Me2? 2Me2(CN)C?+N2 is much more favorable than the reaction process of the two one- bond asynchronous cleavage Me2(CN)CN=N─C(CN)Me2 ? Me2(CN)CN=N?+ Me2(CN)C?? Me2(CN)C?+ N2. It was suggested that the electron shrinking effect of double bond (─N=N─) in AIBN and the stabilities of the Me2(CN)C?radical as well as N2 molecule are main factors of leading to the reaction proceeding in the former pathway. The calculation results were consistent with all the experimental facts.

关键词： azoisobutyronitrile, radicals, thermal decomposition, density function theory (DFT).

Theoretical study on the reaction mechanism of(CH_3)_3CO+CO

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Science china {1. 2005年第1期48卷 18-24页

作者： zhao hongmei1,2,3, sun chengke1,4, ZHANG Rongchang3, XI Hongmin3 & li zonghe1 1. department of chemistry, beijing normal university, beijing 100875, china 2. The Laboratory of Molecular Reaction Dynamics, Institute of chemistry, Chinese Academy of Sciences, beijing 100080, china 3. department of chemistry, Beihua university, Jilin 132013, china 4. department of chemistry, Qujing normal university, Yunnan 655000, china department of {1. Beijing Normal University Beijing China The Laboratory of Molecular Reaction Dynamics Institute of Chemistry Chinese Academy of Sciences Beijing China department of {1. Beihua University Jilin China department of {1. Qujing Normal University Yunnan China

The reaction mechanism of (CH3)3CO with CO has been theoretically investigated using density-functional theory (DFT) calculations at B3LYP/6-31.* level. In order to get more reliable energy values the single-point energy is evaluated at CCSD (T)/6-31.+G** level. The results show that the reaction is multi-channel and the reaction of (CH3)3CO radical with CO mostly produces (CH3)3C + CO2. The reaction could play a role in eliminating air pollution.

关键词： DFT, B3LYP, (CH3)3CO, radical.

气相中Fe^(2+)和H_2O_2作用生成OH自由基的理论研究

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化学学报 2003年第12期61卷 1934-1938页

作者：赵红梅孙成科刘鲲李宗和北京师范大学化学系

利用B3LYP方法 ,在 6 3 1.G 基组下研究了气相中Fe2 +与H2 O2 作用生成OH自由基的反应途径 ,探讨了铁离子对生成羟基自由基所起的作用 .结果表明反应的途径为 :Fe2 +与H2 O2 首先形成中间体 (FeO2 H2 ) 2 +,然后通过O—O键的断裂生成... 详细信息

利用B3LYP方法 ,在 6 3 1.G 基组下研究了气相中Fe2 +与H2 O2 作用生成OH自由基的反应途径 ,探讨了铁离子对生成羟基自由基所起的作用 .结果表明反应的途径为 :Fe2 +与H2 O2 首先形成中间体 (FeO2 H2 ) 2 +,然后通过O—O键的断裂生成中间体 (HOFeOH) 2 +,再断Fe—OH键生成羟基自由基 .Fe2 +和H2 O2 的电荷强烈相互作用以及Fe2 +的d轨道上的电子促进H2 O2 中的O—O键断裂。

关键词：过氧化氢 Fe^2+ OH自由基气相自由基反应铁离子羟基自由基