双自由基CF2与O3的反应机理

主要用作致冷剂和发泡剂的氯氟烃（CFCs）是破坏臭氧层的主要物质之一．对氯氟烃类化合物及其降解产物（包括光解、光氧化、化学反应产物等）在大气中行为问题的研究是大气化学研究的重要内容．前人[1-3]从理论和实验两方面研究了自由基与臭氧的反应机制，但是氯氟烃光解过程中

The Reaction Mechanism of the Biradical CF_2 and O_3

The reaction mechanism of the singlet biradical CF2 with O3 has been studied by using ab initio method at 6-31G(d) level. The single pomt energy calculations of the reactants,intermediate, transition state and products of the reaction have been performed by MP2/6-31G(d)method The relative structure data of the reaction species are given The mechanism proposed here is that there are two stages in the reaction the reactant molecules combine first to form an stable energy-enriched intermediate, this stage has no energy barrier, and then the intermediate is decomposed to D=CF2O and O2 the energy barrier of this stge is 230.73 kJ mol-1(MP2/6-31G(d)HF/6-31G(d)). The reaction is exothermic by 461.06 kJ mol-1(MP2/6-31G(d)HF/6-31G(d)). The potential energy curve along the reaction path has been obtained by IRC calculations.