The triplet and complex singlet potential energy surfaces (PES) of the Cl + CHX₂O₂ (X=F, Cl) reactions have been investigated at the BMC−CCSD//B3LYP/6-311++G(d,p) level. Addition/elimination and S_N2 displacement mechanisms are revealed on the singlet PES. H-abstraction and S_N2 displacement mechanisms are located on the triplet PES. Rice-Ramsperger-Kassel-Marcus (RRKM) theory and transition-state theory (TST) are employed to calculate the overall and individual rate constants over a wide range of temperatures and pressures. It is predicted that IM1_X (CHX₂OOCl (X=F, Cl)) formed by collisional stabilization is dominated at T≤800 K and T≤400 K, respectively; P1_X (CX₂O(X=F, Cl) + HClO) was the major products at 800–2800 K and 400–3000 K, respectively; and the channel of production P3_F (CF₂O₂ + HCl) dominant the reaction at T ≥ 2800 K. The lifetimes of CHX₂O₂ (X=F, Cl) in the presence of Cl are predicted to around 1.17 and 2.98 weeks, respectively. Moreover, time-dependent density functional theory (TDDFT) calculations suggest that IM1_X (CHX₂OOCl (X=F, Cl)) will photolyze under the sunlight.

在BMC-CCSD // B3LYP / 6-311 ++ G（d，p）上研究了Cl + CHX ₂ O ₂（X = F，Cl）反应的三重态和复杂单重态势能面（PES）。水平。单重态PES揭示了加/消除和S _N 2置换机理。H-提取和S _N 2置换机制位于三重态PES上。赖斯-拉姆斯伯格-卡塞尔-马库斯（RRKM）理论和过渡态理论（TST）用于计算在宽温度和压力范围内的总体和单个速率常数。可以预测，由碰撞稳定形成的IM1 _X（CHX ₂ OOCl（X = F，Cl））分别在T≤800K和T≤400K时占主导地位。P1 _X（CX ₂ O（X = F，Cl）+ HClO）分别是800-2800 K和400-3000 K的主要产物；在T≥2800 K时，反应产物P3 _F（CF ₂ O ₂ + HCl）占主导地位。在存在Cl的情况下，CHX ₂ O ₂（X = F，Cl）的寿命预计约为1.17和2.98。周。此外，随时间变化的密度泛函理论（TDDFT）计算表明IM1 _X（CHX ₂ OOCl（X = F，Cl））将在阳光下光解。