引用本文:
【打印本页】   【HTML】   【下载PDF全文】   View/Add Comment  【EndNote】   【RefMan】   【BibTex】
←前一篇|后一篇→ 过刊浏览    高级检索
本文已被:浏览 1883次   下载 868 本文二维码信息
码上扫一扫!
分享到: 微信 更多
Theoretical Study of Decomposition Mechanism of Azoisobutyronitrile
Xue-fei Lin,Cheng-ke Sun*,Si-ya Yang,Zong-he Li*
Author NameAffiliationE-mail
Xue-fei Lin Department of Chemistry, Qujing Normal University, Qujing 655000, China  
Cheng-ke Sun* Department of Chemistry, Qujing Normal University, Qujing 655000, China cksun99@126.com 
Si-ya Yang Department of Chemistry, Qujing Normal University, Qujing 655000, China  
Zong-he Li* Department of Chemistry, Beijing Normal University, Beijing 100875, China cksun99@126.com 
Abstract:
The decomposition mechanisms of azoisobutyronitrile were systematically investigated. Density function theory B3LYP/6-311G*, B3LYP/6-311+G* and BHandH/6-31+G** methods were employed to optimize the geometry parameters of the reactants, transition states, possible intermediates and products based on the detailed potential energy surfaces scanned with AM1. The reaction mechanisms were also analyzed theoretically. The results indicate that the decomposition of azoisobutyronitrile is a two-bond (three body) synchronouscleavage process in the ground state (CH3)2CNC-N=N-CCN(CH3)2→2(CH3)2CNC·+N2; and is a twobond asynchronous cleavage process while in the triple state (CH3)2CNCN=N-CCN(CH3)2→(CH3)2CN{CN=N· · ·CCN(CH3)2→2(CH3)2CNC·+N2. The calculations rationalize and verify all experimental facts.
Key words:  Azoisobutyronitrile, Decomposition mechanism, Density function theory
FundProject:
偶氮异丁腈分解反应机理的理论研究
林雪飞,孙成科*,杨思娅,李宗和*
摘要:
应用量子力学方法对偶氮异丁腈分解反应的机理进行了系统的研究.应用密度泛函理论,在B3LYP/6-311G*、B3LYP/6-311+G*和BHandH/6-31+G**水平上对此反应过程中的反应物、过渡态、中间体、复合物和产物的几何结构和能量进行了优化计算,并给出了反应详细的势能面信息和机理解析.结果表明,偶氮异丁腈在基态下采取两键(三体)同步解离的模式进行自由基热分解反应, 即(CH3)2CNC-N=N-CCN(CH3)2→2(CH3)2CNC·+N2;在三态下进行两键异步解离:(CH3)2CNCN=N-CCN(CH3)2→(CH3)2CN-CN=N· · ·CCN(CH3)2→2(CH3)2(CN)C·+N2.计算的结论与实验结果吻合.
关键词:  偶氮异丁腈,分解反应,密度泛函
DOI:10.1088/1674-0068/20/03/224-232
分类号: