The gas‐phase reaction between CFCl₂O₂ and Cl was researched by means of quantum chemical methods. B3LYP method with the 6‐311++G(d,p) basis set were employed to obtain the geometrical parameters of all stationary points including in the reaction. The singlet and triplet potential energy surfaces (PESs) were characterized at the Multicoefficient Correlation Method (BMC‐CCSD)//B3LYP/6‐311++G(d,p) level. Addition/elimination and S_N2 displacement reaction mechanisms were identified on the singlet PES, and only S_N2 displacement reaction mechanism was located on the triplet PES. The dominant reaction takes place on the singlet PES, and the primary pathways are CFCl₂O₂ + Cl → IM1 (CFCl₂OOCl) → P1 (ClClO + CFClO) and CFCl₂O₂ + Cl → IM1 (CFCl₂OOCl) → IM3 (CFCl (OCl)₂) → P2 (ClOCl + CFClO). Rice–Ramsperger–Kassel–Marcus (RRKM) theory was used to calculate rate constants, which is consistent with the experimental data. The atmospheric lifetime of CFCl₂O₂ in Cl is about 4.9 h in the marine boundary layer. Time dependent density functional theory (TDDFT) computations imply that IM1 (CFCl₂OOCl), IM2 (CFCl₂OClO), IM3 (CFCl (OCl)₂), IM4 (FOCCl₂OCl) will photolyze under the sunlight.

中文翻译：

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CF引发的大气中CFCl2O2降解反应的机理和动力学研究

利用量子化学方法研究了CFCl ₂ O ₂与Cl之间的气相反应。采用B3-LYP方法（基数为6-311 ++ G（d，p））来获得包括反应在内的所有固定点的几何参数。单重态和三重态势能面（PESs）在多系数相关方法（BMC-CCSD）// B3LYP / 6-311 ++ G（d，p）级别进行表征。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上只有S _N 2置换反应机理。主导反应发生在单线态PES上，主要途径为CFCl ₂ O ₂ + Cl→IM1（CFCl₂ OOCl）→P1（ClClO + CFClO）和CFCl ₂ O ₂ + Cl→IM1（CFCl ₂ OOCl）→IM3（CFCl（OCl）₂）→P2（ClOCl + CFClO）。赖斯-拉姆斯伯格-卡塞尔-马库斯（RRKM）理论用于计算速率常数，与实验数据一致。在海洋边界层中，Cl中CFCl ₂ O ₂的大气寿命约为4.9 h。随时间变化的密度泛函理论（TDDFT）计算表明IM1（CFCl ₂ OOCl），IM2（CFCl ₂ OClO），IM3（CFCl（OCl）₂），IM4（FOCCl ₂ OCl）在阳光下会发生光分解。