烯丙基自由基（C3H5）与氧气（O2）反应机理的理论计算

Theoretical Calculation of Reaction Mechanisms for C3H5 ＋ O2

用量子化学计算方法对CH3CHH与O2气的反应机理进行了理论研究,在B3LYP/6-311G(d,p)水平下优化稳定分子结构和寻找过渡态,并在此构型的基础上,采用CCSD(T)/6-311G(d,p)方法得到各驻点的高级单点能量.找到主要路径R(CH3CHH+O2)m1(trans-CH3CHCHOO)m2(形成COO三元环)m3(C—C键断裂,同时生成CH3CH—O—CHO)P2(C—O键断裂生成CH3CHO+CHO);并与C2H3等共轭体系进行了对比.

The theoretical calculation on the mechanisms for C3H5 ＋ O2 reaction was carried out based on the quantum chemical calculating methods. The calculation was undertaken at B3LYP level with the 6-311 G （d,p） basis set and the geometries and transition states were ascertained. The most favorable reaction pathway leading to the major CHO ＋ CH3 CHO products is as follows： R （CH3CH=CH ＋ O2 ） →ml （trans-CH3CH = CHOO） →m2 （form COO three-membered ring） →m3 （C—C bond ruptures, at the same time, forms CH3CH—O—CHO）→P2（ C—O bond ruptures and form CH3CHO ＋ CHO） This system was also compared with some others such as the system of C2H3.