二氯卡宾消耗臭氧的反应机理研究

采用密度泛函理论对单重态势能面上的二氯卡宾1 CCl2与臭氧1 O3反应的微观机理进行了研究.在B3LYP/6-311G(d,p)水平上全参数优化反应物、中间体、过渡态和产物的几何构型,同时使用内禀反应坐标(IRC)在同一水平上对过渡态与中间体之间的联系进行了确认,并且在QCISD/6-311G(d,p)水平上计算了各驻点的单点能.研究得到1 CCl2与1 O3反应的8种产物通道,即P1(Cl2CO+1 O2)、P2(CO2+ClClO)、P3(CO3+Cl2)、P4(CO+ClOOCl)、P5(CO2+ClOCl)、P6(v-CO2+ClOCl)、P7(ClCClO+1 O2)和P8(COO+ClOCl),其中通道P1(Cl2CO+1 O2)是最主要的产物通道,通道P2(CO2+ClClO)、P3(CO3+Cl2)、P4(CO+ClOOCl)对反应体系的产物贡献依次减小,而通道P5(CO2+ClOCl)、P6(v-CO2+ClOCl)、P7(ClCClO+1 O2)和P8(COO+ClOCl)很难生成.

Reaction mechanism of the consumption of ozone by dichlorocarbene

The microcosmic reaction mechanism of^1CCl2 with ^1O3was studied using density ：＇unctional theory at the B3LYP/6-311G（d, p） level on the singlet potential energy surface. All structures of reactants, intermediates, transition states and products were optimized and at the same time the connection between transition states and intermediates was confirmed at the same level by intrinsic reaction coordinate. The QCISD/6-311G（d, p） single-point calculations were done by using the B3LYP/6-311G（d, p） optimized geometries to accurately determine the energetics. It was found that the reaction possessed eight product channels：P1（C12CO＋^1O2）、P2（CO2＋C1ClO）、P3（CO3＋Cl2）、P4（CO＋ClOOCl）、P5（Co2＋ClOCl）、P6（v-CO2＋ClOC）、P7（ClCCl0＋^1O2） and P8（COO＋ClOCl）,P1（C12CO＋^1O2）was the major one, and the contributions of P2（CO2＋C1ClO）、P3（CO3＋Cl2） and P4（CO＋ClOOCl）to the reaction products decreased in sequence.P5（Co2＋ClOCl）、P6（v-CO2＋ClOC）、P7（ClCCl0＋^1O2） and P8（COO＋ClOCl）were all difficult to generate.