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应用密度泛函理论(DFT),对氟氯酰(ClF3O)引发丙烷(C3H8)反应生成C3H7自由基或丙醇等产物的机理进行了研究.在B3PW91/6-311++G(d,p)水平上优化了9个不同反应通道上各驻点物(反应物、中间体、过渡态和产物)的几何构型,并计算了它们的振动频率和零点振动能.通过零点能校正计算了各反应路径的活化能,并应用过渡态理论计算了各反应路径常温下的速率常数k.计算结果表明:ClF3O与C3H8反应可经过不同路径生成HF,C3H7自由基和C1F2O自由基或C3H7OH和ClF3.其中,最可几反应路径为ClF3O分子的中间位F原子进攻丙烷β位H原子的反应,活化能仅为7.54kJ/mol,速率常数为0.153×106mol-1·dm3·s-1.
The mechanism of reaction of C3H8 with C3H8 to generate C3H7 radical or propanol was studied by using density functional theory (DFT). In B3PW91 / 6-311 ++ G (d, p ), The geometric configurations of each stationary (reactant, intermediate, transition state and product) on nine different reaction channels were optimized and their vibrational frequencies and zero vibrational energies were calculated. The activation energy of each reaction path and the transition state theory were used to calculate the rate constant k of each reaction path at room temperature. The calculated results show that the reaction of ClF3O with C3H8 can generate HF, C3H7 and C1F2O free radicals or C3H7OH and ClF3 through different pathways Among them, the most probable reaction path is the reaction of the middle F atom of the ClF3O molecule with the H atom of the beta position of propane, with an activation energy of only 7.54 kJ / mol and a rate constant of 0.153 × 106 mol-1 · dm3 · s-1.