The adiabatic mechanism of the reaction of trichloroethylene with O(³P), exploring the various O‐atom addition and H‐atom abstraction channels, is theoretically studied at the MP2/6‐311++G(2d, 2p), MP2/aug‐cc‐pVTZ, CCSD/6‐31G(d), G3, and CBS‐QB3 levels of theory. From a kinetic point of view, the addition to the less substituted carbon atom of the double bond is more favorable than the addition to the more substituted carbon. Such O‐atom addition reactions are favored over the one possible hydrogen‐abstraction reaction. Calculations of the present study showed that five products are obtained: HCCl + C(O)Cl₂ (P1), Cl + ClC(O)CHCl (P2), H + ClC(O)CCl₂ (P3), Cl + HC(O)CCl₂ (P4), and CH(O)Cl + CCl₂ (P5). The products P2 and P4 are found to be the most favored ones. The kinetic calculations of rate constant in the range of 285–395 K are performed at the CBS‐QB3 level of theory and are in conformity with the experimental outcomes.

中文翻译：

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三氯乙烯与O（3P）反应的量子化学研究

在MP2 / 6-311 ++ G（2d，2p），MP2 /上理论研究了三氯乙烯与O（³ P）的绝热机理，探索了各种O原子加成和H原子抽象通道。 aug-cc-pVTZ，CCSD / 6-31G（d），G3和CBS-QB3的理论水平。从动力学的观点来看，双键添加到取代度较低的碳原子上比添加到取代度更高的碳原子上更为有利。这种O原子加成反应优于一种可能的吸氢反应。本研究的计算表明获得了五种产物：HCCl + C（O）Cl ₂（P1），Cl + ClC（O）CHCl（P2），H + ClC（O）CCl ₂（P3），Cl + HC （O）CCl ₂（P4）和CH（O）Cl + CCl ₂（P5）。发现产品P2和P4是最受欢迎的产品。速率常数在285–395 K范围内的动力学计算是在CBS-QB3理论水平上进行的，并且与实验结果相符。