The gas-phase reaction between CFCl₂O₂ and ClO was researched by means of quantum chemical methods. B3LYP method with the 6-311++G(d,p) basis set was used to obtain the geometric parameters of all stationary points including in the CFCl₂O₂ + ClO reaction. The singlet and triplet potential energy surfaces were characterized at the CCSD(T)/6-311++G(2d,2p)//B3LYP/6-311++G(d,p) level. Addition/elimination and S_N2 displacement reaction mechanisms were identified on the singlet PES, and only substituent reaction mechanism was located on the triplet PES. The dominant reaction takes place on the singlet PES, and the major pathways are CFCl₂O₂ + ClO → IM1 (CFCl₂OOOCl) → IM2 (CFCl₂OOClO) → IM3 (CH₃OClO₂) → P6 (CFClO + (ClO)₂). RRKM theory was used to calculate rate constants, which is consistent with the experimental data. The atmospheric lifetime of CFCl₂O₂ in ClO is around 8.84 h. TD-DFT computations imply that IM1 (CFCl₂OOOCl), IM2 (CFCl₂OOClO), and IM3 (CFCl₂OClO₂) will photolyze under the sunlight.

Graphical abstract

中文翻译：

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CFCl2O2的大气化学：CFCl2O2 + ClO反应机理和动力学的理论研究。

利用量子化学方法研究了CFCl ₂ O ₂与ClO之间的气相反应。使用具有6-311 ++ G（d，p）基集的B3LYP方法来获得包括CFCl ₂ O ₂ + ClO反应在内的所有固定点的几何参数。单线态和三线态势能表面的特征在于CCSD（T）/ 6-311 ++ G（2d，2p）// B3LYP / 6-311 ++ G（d，p）水平。在单重态PES上确定了加/消除和S _N 2置换反应机理，而在三重态PES上仅存在取代基反应机理。主导反应发生在单线态PES上，主要途径为CFCl ₂ O ₂ + ClO→IM1（CFCl₂ OOOCl）→IM2（CFCl ₂ OOClO）→IM3（CH ₃ OClO ₂）→P6（CFClO +（ClO）₂）。RRKM理论用于计算速率常数，与实验数据一致。CFCl ₂ O ₂在ClO中的大气寿命约为8.84 h。TD-DFT计算暗示IM1（CFCl ₂ OOOCl），IM2（CFCl ₂ OOClO）和IM3（CFCl ₂ OClO ₂）在阳光下会发生光分解。

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