用MP2方法对F、Cl原子与CH4的反应进行了研究.反应物、产物和过渡态的几何优化和振动分析在MP2/6-311 + G(d,p)水平下进行,反应路径的势能分析在CCSD(T)/6-311+G(3df,2p)水平上对MP2/6-311+G(d,p)优化的几何结构进行单点能校正.用传统过渡态理论和正则变分过渡态理论,并考虑小曲率隧道效应计算了正向反应的速率常数.%The reactions of F, Cl atoms with CH4 were studied using MP2 method . Geometry optimizations and frequency analysis of reactants, products and transition states were preformed at the MP2/6-311 + G( d,p) levels. The energy profiles along the reaction path were refined by the CCSD(T)/6-311 +G (3df,2p) single point energy calculations at the MP2/6-311 + G(d,p) optimized stationary points. The forward rate constants were calculated by the conventional transition state theory and canonical variational transition state theory together with small-curvature tunneling correction.
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