Theoretical Study on Gas Phase Reactions of OH Hydrogen-Abstraction from Formyl Fluoride with Different Catalysts  

气相中自由基OH在不同催化剂下对甲酰氟FCHO进行提氢反应的理论性研究

作　　者：王定美[1] 隆正文[1] 谭兴凤[2] 龙波[2] 张为俊[3,4] 

机构地区：[1]贵州大学物理系,贵阳550025 [2]贵州民族大学信息工程学院,贵阳550025 [3]中国科学院安徽光学精密机械研究所环境光学实验室,合肥230031 [4]中国科学院安徽光学精密机械研究所大气成分与光学重占章验室,合肥230031

出　　处：《Chinese Journal of Chemical Physics》2016年第3期325-334,I0001,共11页化学物理学报（英文）

摘　　要：The mechanisms and kinetics of the gas phase reactions that the hydrogen atom in formyl fluoride （FCHO） abstracted by OH in the presence of water, formic acid （FA）, or sulfuric acid （SA） are theoretically investigated at the CCSD（T）/6-311＋＋G（3df, 3pd）//MO6-2X/6- 311＋＋G（3df, 3pd） level of theory. The calculated results show that the barriers of the transition states involving catalysts are lowered to -2.89, -6.25, and -7.76 kcal/mol from 3.64 kcal/mol with respect to the separate reactants, respectively, which reflects that those catalysts play an important role in reducing the barrier of the hydrogen abstraction reaction of FCHO with OH. Additionally, using conventional transition state theory with Eckart tun- neling correction, the kinetic data demonstrate that the entrance channel X…FCHO＋OH （X=H2O, FA, or SA） is significantly more favorable than the pathway X…OH＋FCHO. More- over, the rate constants of the reactions of FCHO with OH radical with H2O, FA, or SA introduced are computed to be smaller than that of the naked OH＋FCHO reaction because the concentration of the formed X…FCHO or X…OH complex is quite low in the atmosphere.

关 键 词：Formyl fluoride Hydrogen abstraction Reaction mechanisms Rate constants 

分 类 号：O[理学]