Cl原子与CH_3COCH_3抽氢反应的动力学研究  

Dynamics Study on the Hydrogen Abstraction Reaction between Cl Atom and CH_3COCH_3

作　　者：马咏梅[1] 张秀芹[1] 

机构地区：[1]渭南师范学院化学化工系,陕西渭南714000

出　　处：《化学与生物工程》2011年第1期17-19,共3页Chemistry & Bioengineering

基　　金：渭南师范学院研究生科研资助项目(07YKZ030)

摘　　要：采用QCISD(T)/6-311++G(d,p)//B3LYP/6-31G(d,p)双理论方法研究了Cl原子与CH3COCH3的抽氢反应过程。在B3LYP/6-31G(d,p)水平上优化了反应物、产物、过渡态的几何构型,并作了最小能量路径分析。在从头算的基础上,用变分过渡态理论加小曲率隧道效应方法计算200～2500K范围内的速率常数,计算值与实验值相符,且在低温范围内隧道效应起了很重要的作用。Hydrogen abstraction reaction between Cl atom and CH3COCH3 is explored using the QCISD（T）/6-311＋＋G（d,p）//B3LYP/6-31G（d,p）method.The optimized geometries of reactants,products and transition states are calculated at the B3LYP/6-31G（d,p）level.The minimum-energy path（MEP）is calculated at the same level.On the basis of the ab initio data,the rate constant is evaluated using canonical variational transition state theory（CVT）with the small-curvature tunneling correction（SCT）method over a wide temperature range of 200~2500 K.The rate constant is in excellent agreement with the experiment value.Tunneling correction plays an important role in the lower temperature range for the reaction.

关 键 词：抽氢反应 QCISD(T)//B3LYP 速率常数 

分 类 号：O643.131[理学—物理化学]