Computational study on the mechanisms and reaction pathways of the CX₃O₂ + Br (X = F and Cl) reactions

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• 作者：Yizhen Tang ; Haofen Sun ; Jinhu Liu ; Dalei Zhang ; Rongshun Wang ; Junhong Dai
• 关键词：CF3O2 ; CCl3O2 ; Bromine ; Atmospheric reactions ; Photolysis
• 刊名：Journal of Fluorine Chemistry
• 出版年：2013
• 出版时间：September, 2013
• 年：2013
• 卷：153
• 期：Complete
• 页码：130-136
• 全文大小：1319 K

文摘

The mechanisms for the reactions of CX₃O₂ (X = F and Cl) with atomic bromine were studied using quantum chemistry methods. The result indicates that the title reactions could take place on the singlet and triplet potential energy surfaces (PES). On singlet PES, the most favourable product is CX₃OOBr (IM1) formed via a barrierless of CX₃O₂ association with Br. As for the CCl₃OO + Br reaction, other products such as CCl₃O + BrO, CCl₂O + ClOBr, ClOCCl₂OBr and CCl₂O + Cl + OBr could make certain contributions in different conditions. On the triplet PES, substitution and direct abstraction mechanisms were located, but it could be negligible compared with that on the singlet PES. Time Dependent Density Functional Theory (TDDFT) calculation indicates that CX₃OOBr could take photolysis easily under the sunlight.