Density functional theory was adopted in this work to reveal the reaction mechanism of CH₂SH with HO₂. Reaction rate constants were computed from 200 to 2000 K using the transition state theory combined with Wigner and Eckart tunneling correction. Moreover, localized orbital locator, atoms in molecules and Mayer bond order analyses were used to study the essence of chemical bonding evolution. Eleven singlet paths and three triplet ones are located on the potential surface (PES). The results show that the main products on the singlet PES are ¹CH₂S and H₂O₂, whereas on the triplet PES they are CH₃SH + ³O₂, which are coincident with the similar reaction of CH₃S and HO₂. This conclusion is also supported by rate constant calculation results. Interestingly, all the possible paths are involved in the hydrogen transfer. The results have provided underlying insights to the analogous reactions and further experimental studies.

中文翻译：

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透视CH2SH与HO2的反应机理：密度泛函理论研究

本文采用密度泛函理论揭示了CH ₂ SH与HO ₂的反应机理。使用过渡态理论结合Wigner和Eckart隧穿校正，可计算出200至2000 K的反应速率常数。此外，使用局部轨道定位器，分子中的原子和Mayer键序分析来研究化学键演化的本质。潜在表面（PES）上有11条单重态路径和3条三重态路径。结果表明，单重态PES的主要产物为¹ CH ₂ S和H ₂ O ₂，三重态PES的主要产物为CH ₃ SH +  ³ O _2。，这与CH ₃ S和HO ₂的相似反应相吻合。速率常数计算结果也支持该结论。有趣的是，所有可能的路径都与氢转移有关。结果为类似的反应和进一步的实验研究提供了潜在的见解。