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Theoretical Study of the Reaction Mechanism of CH2Cl with OH
Liu Ying,Pei Kemei,Li Haiyang*
Author NameAffiliationE-mail
Liu Ying Laboratory of Environmental SpectroscopyAnhui Institute of Optics and Fine MechanicsChinese Academy of SciencesHefei 230031  
Pei Kemei Laboratory of Environmental SpectroscopyAnhui Institute of Optics and Fine MechanicsChinese Academy of SciencesHefei 230031  
Li Haiyang* Laboratory of Environmental SpectroscopyAnhui Institute of Optics and Fine MechanicsChinese Academy of SciencesHefei 230031 hli@aiofm.ac.cn 
Abstract:
The reaction mechanism of CH2Cl radical with OH radical to produce HCCl+H2O,HCOCl+H2 and H2CO+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 CH2ClOH is first formed through a barrierless process,followed by atoms migration,radical groups rotation and bonds fission to produce HCCl+H2O,HCOCl+H2 and H2CO+HCl,respectively. And all channels are exothermic by 72.81,338.54 and 354.08 kJ/mol. The reaction heat of reactants to H2CO+HCl is 281.27 kJ/mol more than that of reactants to HCCl+H2O. This result accords with that of experiments.
Key words:  ab initio,CH2Cl radical,OH radical,Gaussian-3(G3),Reaction mechanism
FundProject:
CH2Cl与OH自由基反应机理的理论研究
刘颖,裴克梅,李海洋*
摘要:
用量子化学从头算方法对CH2Cl与OH自由基反应生成HCCl+H2O、 HCOCl+H2和H2CO+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, CH2Cl和OH自由基反应首先经无垒过程生成一个富能中间体CH2ClOH,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+H2O、 HCOCl+H2和H2CO+HCl;三者均为放热反应,放热量分别为72.81、 338.54和354.08 kJ/mol;生成H2CO+HCl放出的热量比生成HCCl+H2O放出的热量多281.27 kJ/mol,与实验结果吻合.
关键词:  从头算方法  CH2Cl自由基  OH自由基  Gaussian-3(G3)  反应机理
DOI:10.1088/1674-0068/17/6/670-674
分类号: