Ab Initio Study on the Isomerization and Dehydrogenation of Methylnitrene  

作　　者：Chen Bin, Zhao Chengda, Fu Qiang and Huang Jingan (Deparment of Chemistry, Northeast Normal University, Changchun) 

出　　处：《Chemical Research in Chinese Universities》1989年第4期325-330,共6页高等学校化学研究（英文版）

基　　金：This work was supported by the State Natural Science Foundation of China

摘　　要：The ab initio calculations were performed at the RHF/4-31G level with the reaction pathways of the iso-merization and dehydrogenation of methylnitrene by the intrinsic reaction coordinate method. The results show that the transformation from methylnitrene to methylenimine would be very easy. This accountes for the experimental fact that one couldn' t find the methylnitrene, but only obtained the methylenimine in the pyrolysis of methyl azide. The mode-selective study reveals the reaction coordinates (IRC) of isomerization and dehydrogenation of methylnitrene are associated with the molecular deformation mode of 1191 cm-1 and the methyl group unsymmetrical stretch mode, respectively. The coupling between normal coordinates is favourable to select the reaction channel of isomerization.The ab initio calculations were performed at the RHF/4-31G level with the reaction pathways of the iso-merization and dehydrogenation of methylnitrene by the intrinsic reaction coordinate method. The results show that the transformation from methylnitrene to methylenimine would be very easy. This accountes for the experimental fact that one couldn' t find the methylnitrene, but only obtained the methylenimine in the pyrolysis of methyl azide. The mode-selective study reveals the reaction coordinates (IRC) of isomerization and dehydrogenation of methylnitrene are associated with the molecular deformation mode of 1191 cm-1 and the methyl group unsymmetrical stretch mode, respectively. The coupling between normal coordinates is favourable to select the reaction channel of isomerization.

关 键 词：ab initio IRC analysis mode-select 

分 类 号：O6[理学—化学]