Atmospheric chemistry of CF3O2: a theoretical study on mechanisms and pathways of the CF3O2 + IO reaction
Atmospheric chemistry of CF3O2: a theoretical study on mechanisms and pathways of the CF3O2 + IO reaction
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CF3O2的大气化学：CF3O2 IO反应机理和路径的理论研究
DOI：
10.1039/c3cp43797c
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发表时间：
2013-01-01
影响因子：
3.3
通讯作者：
Wang, Rongshun
中科院分区：
文献类型：
--
作者：
Li, Hongwei;Tang, Yizhen;Wang, Rongshun
用量子化学方法研究了CF3O2+IO反应的反应机理和反应途径。研究发现，TITLE反应同时发生在单重态和三重态势能面上。在单重态PES上，最重要的产物包括CF3OOI、CF3OOIO、CF3OIO2和CF2O+FiO2，而其他产物如CF2O+FOIO、CF2O+FOOI、CF30OI+O(P-3)、CF3OI+O-2((1)Delta和(3)Sigma)和CF3O+OIO由于高势垒或地层不稳定而可以忽略不计。在三重态PES上，CF3O+OIO是主要产物，具有较低的势垒。对于FiO2及其异构体，最稳定的是FiO2。含时密度泛函理论(TDDFT)计算表明，CF3OOI、CF3OIO和CF3OIO2在太阳光下容易发生光解。此外，在CX3O2+IO(X=H和F)反应中，相对于氢的贡献很小。
The mechanisms and reaction pathways for the CF3O2 + IO reaction have been investigated by quantum chemistry methods. It has been found that the title reaction takes place on both the singlet and triplet potential energy surfaces (PES). On the singlet PES, the most important products include CF3OOOI, CF3OOIO, CF3OIO2, and CF2O + FIO2, while other products such as CF2O + FOIO, CF2O + FOOI, CF3OOI + O(P-3), CF3OI + O-2 ((1)Delta and (3)Sigma), and CF3O + OIO are negligible due to high barriers or unstable formations. On the triplet PES, CF3O + OIO is the dominant product with a lower barrier. As for FIO2 and it isomers, the most stable one is FIO2. TDDFT (Time Dependent Density Functional Theory) calculation indicates that CF3OOOI, CF3OOIO and CF3OIO2 undergo photolysis easily under sunlight. Moreover, a minor contribution relative to hydrogen is found in the CX3O2 + IO (X = H and F) reactions.