Cl与CH_4反应机理及动力学性质的理论研究  

Theoretical Investigation on the Mechanism and Dynamics of Cl with CH_4

作　　者：马咏梅[1,2] 张秀芹[1] 王艳丽[2] 

机构地区：[1]渭南师范学院化学与生命科学学院,陕西渭南714000 [2]西北工业大学理学院,西安710072

出　　处：《渭南师范学院学报》2013年第6期43-46,89,共5页Journal of Weinan Normal University

基　　金：西北工业大学基础研究基金项目(JC201269)

摘　　要：用MP2(FULL)/6-311G(d,p)方法优化了Cl与CH4反应的各驻点的几何构型,用高水平方法 QCISD(T)/aug-cc-pvtz计算了单点能,得到两个反应的表观活化能分别为15.82 kJ/mol和165.40 kJ/mol.采用变分过渡态理论加小曲率隧道效应的方法计算了两个反应在200～2000 K的速率常数,与实验值符合得较好.All equilibrium geometries of the reactants, products and stationary points were fully optimized at the MP2 （full）/6 -311 G （d, p） level. The single-point energies of all stationary points were refined by QCISD（T）/aug-cc-pvtz at the MP2 （full）ge- ometries. The two reaction phenomenon activation energies were 15.82 kJ/mol and 165.40 kJ/mol respectively. On the basis of the ab initio data, the rate constants for each channel were evaluated using canonical variational transition state theory （CVT） with the small-curvature tunneling correction（SCT） method over a wide temperature range of 200 - 2000 K. The total rate constants were in excellent agreement with the experiment values.

关 键 词：反应机理 QCISD(T) MP2(FULL) 速率常数 

分 类 号：O641[理学—物理化学]