Vibrational excitation of the H₂O, HOD, and D₂O product molecules from the reactions of OH and OD radicals with CH₃SH, CH₃C(O)SH, (CH₃)₃CSH, H₂S, and CH₃SCH₃ was determined by modeling the infrared emission spectra using a renovated and extended set of model spectroscopic bands. Using the deuterated reactant, CH₃SD, it was possible to separate spectra of abstraction from C‐ and S‐sites, which allowed measurement of branching fractions and kinetic isotope effects for individual channels. For the OH + CH₃SH reaction, branching fractions of 0.13 ± 0.03 (C─H) and 0.87 ± 0.03 (S─H) were obtained. The vibrational energy released to water from abstraction of H‐atoms from the C─H and S─H sites of the reactant molecules is described. The results reported in this paper take precedence over an earlier study of CH₃SH. The vibrational energy partitioning between the stretch and bend modes of water molecules from the reactions of the thiols and related reactions of H₂S and CH₃SCH₃ are discussed. The mechanism for the OH + CH₃SSCH₃ reaction was confirmed to be addition followed mainly by decomposition to CH₃SH and CH₃SO.

中文翻译：

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通过同位素水产品的红外化学发光研究OH和OD自由基与简单的硫醇和硫化物的反应：重新讨论了OH + CH3SH反应

OH和OD自由基与CH ₃ SH，CH ₃ C（O）SH，（CH ₃）₃ CSH，H ₂ S和CH反应生成的H ₂ O，HOD和D ₂ O产物分子的振动激发₃ SCH ₃是通过使用一组经过改进和扩展的模型光谱带对红外发射光谱建模来确定的。使用氘代反应物CH ₃ SD，可以从C和S位置分离抽象光谱，从而可以测量单个通道的支化分数和动力学同位素效应。对于OH + CH ₃SH反应得到的支化度分别为0.13±0.03（CH）和0.87±0.03（CH）。描述了从反应物分子的C-H和S-H位提取H原子释放到水中的振动能。本文报道的结果优先于CH ₃ SH的早期研究。讨论了由硫醇的反应以及H ₂ S和CH ₃ SCH _3的相关反应在水分子的拉伸和弯曲模式之间的振动能分配。确认OH + CH ₃ SSCH ₃反应的机理是添加，然后主要分解为CH ₃ SH和CH ₃ SO。