自由基-分子反应:F+Propene(CH2CHCH3)的从头算研究

采用从头算CCSD(T)/6-311 G(2d,2p)//B3LYP/6-311G(d,p)方法,研究了自由基-分子反应F CH2CHCH3的各种不同的反应通道．该反应主要是通过复合物形成机制进行,即F分别加到碳碳双键的两端形成自由基复合物1和2．这两种亚稳态自由基会解离成三种产物:H C3H5F、CH3 C2H3F和HF C3H5．理论计算结果表明,生成CH3 C2H3F是反应的主要通道,而生成H C3H5F和HF C3H5对产物也有一定的贡献．这一结果和实验符合得很好．

Ab initio Study of Radical-Molecule Reaction: F+CH2CHCH3

The radical-molecule reaction F propene (CH2CHCH3) was studied in detail by using the Becke's three parameter Lee-Yang-Parr-B3LYP/6-311G(d,p) and coupled cluster with single, double, and triple excitations- CCSD(T)/6-311 G(2d,2p). It is shown that F propene reaction mainly occurs through complex-formation mechanism: F attacks the double bond of propene leading to the formation of complex 1 and complex 2. As the two radical complexes are metastable, they can quickly dissociate to H C3H5F, CH3 C2H3F and HF C3H5. Based on the ab initio calculations, the CH3 C2H3F is the main channel, and the H elimination and HF forming channels also provide some contribution to products. The calculated values are in good agreement with the recently reported experimental results.