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CH2Cl与OH自由基反应机理的理论研究
引用本文:刘颖,裴克梅,李海洋.CH2Cl与OH自由基反应机理的理论研究[J].化学物理学报,2004,17(6):670-674.
作者姓名:刘颖  裴克梅  李海洋
作者单位:中国科学院安徽光学精密机械研究所环境光谱学实验室 合肥230031 (刘颖,裴克梅),中国科学院安徽光学精密机械研究所环境光谱学实验室 合肥230031(李海洋)
基金项目:ProjectsupportedbytheNationalNaturalScienceFoundationofChina (2 0 0 730 4 2 ) .
摘    要:用量子化学从头算方法对CH2 Cl与OH自由基反应生成HCCl+H2 O、HCOCl+H2 和H2 CO +HCl的机理进行了研究 .在UMP2 (FC) / 6 311++G 水平上计算出了各物种的优化构型、振动频率 ;并在Gaussian 3(G3)水平上计算了他们的零点能 (ZPE)、相对能量及总能量 .结果表明 ,CH2 Cl和OH自由基反应首先经无垒过程生成一个富能中间体CH2 ClOH ,中间体再经过一系列原子转移、基团旋转和键断裂分别生成产物HCCl+H2 O、HCOCl+H2 和H2 CO +HCl;三者均为放热反应 ,放热量分别为 72 .81、338.5 4和 35 4 .0 8kJ/mol;生成H2 CO +HCl放出的热量比生成HCCl+H2 O放出的热量多 2 81.2 7kJ/mol,与实验结果吻合 .

关 键 词:从头算方法  CH2Cl自由基  OH自由基  Gaussian3(G3)  反应机理
收稿时间:2003/8/18 0:00:00

Theoretical Study of the Reaction Mechanism of CH2Cl with OH
Liu Ying,Pei Kemei and Li Haiyang.Theoretical Study of the Reaction Mechanism of CH2Cl with OH[J].Chinese Journal of Chemical Physics,2004,17(6):670-674.
Authors:Liu Ying  Pei Kemei and Li Haiyang
Institution:Liu Ying,Pei Kemei,Li Haiyang **
Abstract:The reaction mechanism of CH_2Cl radical with OH radical to produce HCCl+H_2O, HCOCl+H_2 and H_2CO+HCl has been studied by using quantum chemistry ab initio calculations. The optimized geometrical parameters, and vibrational frequencies of all species were obtained at the UMP2(FC) level of theory in conjunction with 6-311++G* basis set. Besides, the zero-point energies (ZPE), relative energies and total energies of all species were calculated using Gaussian-3(G3) model. The results of theoretical study indicate that the activated intermediate CH_2ClOH is first formed through a barrierless process, followed by atoms migration, radical groups rotation and bonds fission to produce HCCl+H_2O, HCOCl+H_2 and H_2CO+HCl, respectively. And all channels are exothermic by 72.81, 338.54 and 354.08 kJ/mol. The reaction heat of reactants to H_2CO+HCl is 281.27 kJ/mol more than that of reactants to HCCl+H_2O. This result accords with that of experiments.
Keywords:ab initio  CH_2Cl radical  OH radical  Gaussian-3(G3)  Reaction mechanism
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