单分子断键反应的理论研究

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，结果和理论预言相符．

Theoretical Study on Bond Breaking in Monomolecular Reaction

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.