节点文献

F和Cl原子与甲烷反应机理的理论研究

Theoretical Study on the Reaction Mechanism of Fluorine and Chlorine Atoms with Methane

推荐 CAJ下载
PDF下载
不支持迅雷等下载工具，请取消加速工具后下载。

【Author】 ZHOU Hongping1,LI Laicai2,3,TANG Zuohua3(1.Center of Analysis and Test, Southwest Jiaotong University, Chengdu 610031,China;2.Department of Chemistry, Sichuan Normal University,Chengdu 610066,China;3.The Faculty of Chemistry, Sichuan University,Chengdu 610064,China)Abatract: ab initio UMP2(full) method was performed to study the reaction mechanism of F and Cl atoms with methane.The geometry configuration of reactants, products, intermediates and transition states were optimized at UMP2(full)/631G* level and the energies of stationary points along the pathways were calculated at Gaussian3(G3) and G3MP2 level. The results show that the hydrogen bond forms during the process of the reaction F+CH4, the energy is 3.71kJ/mol. In addition, fluorine atoms react readily with methane to form the intermediate with a hydrogen bond, which easily result in the elimination of HF with stable properties. That is to say, the reaction F+CH4 is prior to the reaction F+O3 whe there is a competition between methane and ozone. But there is no hydrogen bond in the reaction Cl+CH4.

【机构】西南交通大学分析测试中心；四川师范大学化学系；四川大学化学系成都610031；成都610066；四川大学化学系；成都610064；成都610064；

【摘要】作者用量子化学从头计算UMP2(full)方法,在6 31G 水平上研究F和Cl原子与甲烷分子之间的反应机理,优化了反应物、产物、中间体和过渡态的几何构型,在Gaussian 3(G3)和G3MP2水平计算了它们的能量,研究结果表明:F原子在与甲烷分子反应过程中有氢键生成,键能为:3.71kJ/mol,而Cl原子甲烷分子在反应过程中则无此现象.同时作者还对F和Cl原子与甲烷分子在之间反应动力学速率常数进行了计算,作者的理论计算结果显示F原子与甲烷分子之间反应活性比Cl原子与甲烷分子之间反应活性强.F原子易与甲烷分子生成含有氢键的化合物,且很快分解生成化学性质非常稳定的HF,能同F+O3反应竞争.更多还原

【Abstract】 ab initio UMP2(full) method was performed to study the reaction mechanism of F and Cl atoms with methane.The geometry configuration of reactants, products, intermediates and transition states were optimized at UMP2(full)/631G* level and the energies of stationary points along the pathways were calculated at Gaussian3(G3) and G3MP2 level. The results show that the hydrogen bond forms during the process of the reaction F+CH4, the energy is 3.71kJ/mol. In addition, fluorine atoms react readily with methane to form the intermediate with a hydrogen bond, which easily result in the elimination of HF with stable properties. That is to say, the reaction F+CH4 is prior to the reaction F+O3 whe there is a competition between methane and ozone. But there is no hydrogen bond in the reaction Cl+CH4.更多还原

【关键词】臭氧；过渡态；从头计算方法；
【Key words】 ozone； translation states； ab initio；

【文献出处】四川大学学报(自然科学版) ,Journal of Sichuan University (Natural Science Edition) , 编辑部邮箱 ,2002年06期
【分类号】O621.25
【被引频次】1
【下载频次】96

打印本页

节点文献中：