Theoretical Study on Decomposition of CF3OH Catalyzed by Water Dimer and Ammonia  

双分子水和氨气催化CF3OH分子裂解的理论研究

作　　者：龙波[1] 谭兴凤[2] 隆正文[3] 任达森[1] 张为俊[4] 

机构地区：[1]贵州民族学院计算机与信息工程学院,贵阳550025 [2]重庆邮电大学光电工程学院,重庆400065 [3]贵州大学物理系,贵阳550025 [4]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

出　　处：《Chinese Journal of Chemical Physics》2011年第1期16-21,I0003,共7页化学物理学报（英文）

基　　金：This work was supported by the National Natural Science Foundation of China （No.10865003） and the Guizhou University for Nationalities （2010）. The authors thank professors W. T. Duncan, R. L. Bell, and T. N. Truong or providing the rate program through the internet.

摘　　要：The G3 and CBS-QB3 theoretical methods are employed to study the decomposition of CF3OH into FCFO and HF by water, water dimmer, and ammonia. The decomposition of CF3OH into FCFO and HF is unlikely to occur in the atmosphere due to the high activated energy of 88.7 k J/mol at the G3 level of theory. However, the computed results predict that the barrier for unimolecular decomposition of CF3OH is decreased to 25.1 kJ/mol from 188.7 k J/mol with the aid of NH3 at the G3 level of theory, which shows that the ammonia play a strong catalytic effect on the split of CF3OH. In addition, the calculated rate constants show that the decomposition of CF3OH by NH3 is faster than those of H2O and the water dimmer by 10^9 and 10^5 times respectively. The rate constants combined with the corresponding concentrations of these species demonstrate that the reaction CF3OH with NH3 via TS4 is of great importance for the decomposition of CF3OH in the atmosphere.

关 键 词：CF3OH AMMONIA Quantum chemical calculation Rate constant Reaction mechanism 

分 类 号：O[理学]