Atmospheric chemistry of CF₃O₂: A theoretical study on mechanisms and pathways of the CF₃O₂?+?I reaction

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• 作者：Yizhen Tang^a ; ^{yizhentang2009@gmail.com} ; Haofen Sun^a ; Jing Zhao^a ; Jinhu Liu^a ; Rongshun Wang^b
• 关键词：CF3O2 ; Atmospheric reaction ; Iodine ; Mechanisms ; Photolysis
• 刊名：Atmospheric Environment
• 出版年：2013
• 出版时间：February, 2013
• 年：2013
• 卷：65
• 期：Complete
• 页码：164-170
• 全文大小：540 K

文摘

Mechanisms and reaction channels of the CF₃O₂ with atomic iodine reaction were studied using quantum chemistry methods. The result indicates that the title reaction can take place on either the singlet or triplet potential energy surfaces (PES). On the singlet PES, addition and substitution mechanisms were located, and the former one is dominant. The most favorable channel involves the association of CF₃O₂ and I to form CF₃OOI via a barrierless process. CF₂O?+?FOI or CF₃O?+?IO and other products could be formed as well, but they can be neglected because of highly energy barriers and unstable products. On the triplet PES, the most feasible product should be CF₃O?+?IO via a modest barrier in the atmospheric condition, especially at higher temperature and lower pressure condition. However it is unfavorable thermodynamically to the overall reaction. Time-dependent DFT (TD-DFT) calculations indicate that CF₃OOI takes photolysis easily in the sunlight at the wavelength of 548 and 427?nm.