单分子断键反应的理论研究  

Theoretical Study on Bond Breaking in Monomolecular Reaction

作　　者：刘鲲[1] 赵红梅[1] 李宗和[1] 

机构地区：[1]北京师范大学化学系,北京100875

出　　处：《化学学报》2004年第9期875-882,M004,共9页Acta Chimica Sinica

摘　　要：利用微扰理论和对称性规则 ,得到了单分子断键反应中反应物结构、过渡态和所断键之间的关系 .据此 ,对环丙基自由基及其正负离子的热开环反应和过氧化氢基态均裂反应作出预言 ,其中对环丙基自由基及其正负离子的热开环反应作出以下三方面的预言 :是否存在过渡态 ;产物的立体选择 ;反应的相对难易程度 .并分别使用UHF方法和CASSCF方法做势能面计算 。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.

关 键 词：单分子解离反应 微扰理论 对称性规则 热开环反应 过氧化氢基态均裂反应 环丙基自由基 过渡态 UHF方法 CASSCF方法 碳环化合物 单分子断键反应 

分 类 号：O641.1[理学—物理化学]