Acta Chimica Sinica ›› 2004, Vol. 62 ›› Issue (9): 875-882. Previous Articles     Next Articles

单分子断键反应的理论研究

刘鲲, 赵红梅, 李宗和   

  1. 北京师范大学化学系,北京,100875
  • 投稿日期:2003-11-11 修回日期:2004-01-05 发布日期:2014-02-17
  • 通讯作者: 李宗和,E-mail:bnulk@yahoo.com.cn E-mail:bnulk@yahoo.com.cn

Theoretical Study on Bond Breaking in Monomolecular Reaction

LIU Kun, ZHAO Hong-Mei, LI Zong-He   

  1. Department of Chemistry, Beijing Normal University, Beijing 100875
  • Received:2003-11-11 Revised:2004-01-05 Published:2014-02-17

Using perturbation theory and symmetry rules, the reaction rules were obtained among the structure of reactant, transition state and the broken bond.According to the relation, we studied the ring opening reactions of cyclopropyl radical, cyclopropyl cation and cyclopropyl anion.The following conclusions can be predicted: (1) whether the reaction has a transition state; (2) reaction stereochemistry; (3) which reaction is easier correspondingly.For comparison, the dissociation of hydrogen peroxide was also studied.Subsequently, the reaction potential surfaces were calculated with UHF and CASSCF method.The results from calculations are in accord with those of theoretic predictions.

Key words: cyclopropyl radical, cyclopropyl cation, cyclopropyl anion, hydrogen peroxide, ab initio