Temperature-Dependent Rate Coefficient for the Reaction of CH₃SH with the Simplest Criegee Intermediate

The kinetics of the reaction of the simplest Criegee intermediate CH₂OO with CH₃SH was measured with transient IR absorption spectroscopy in a temperature-controlled flow reaction cell, and the bimolecular rate coefficients were measured from 278 to 349 K and at total pressure from 10 to 300 Torr. The measured bimolecular rate coefficient at 298 K and 300 Torr is (1.01 ± 0.17)   ×  10^-12 cm³ s^-1. The results exhibit a weak negative temperature dependence: the activation energy E_a ( k = Ae^{- E}) is -1.83 ± 0.05 kcal mol^-1, measured at 30 and 100 Torr. Quantum chemistry calculations of the reaction rate coefficient at the QCISD(T)/CBS//B3LYP/6-311+G(2d,2p) level (1.6  ×  10^-12 cm³ s^-1 at 298 K; E_a = - 2.80 kcal mol^-1) are in reasonable agreement with the experimental results. The experimental and theoretical results of the reaction of CH₂OO with CH₃SH are compared to the reactions of CH₂OO with methanol and hydrogen sulfide, and the trends in reactivity are discussed. The results of the present work indicate that this reaction has a negligible influence to atmospheric CH₂OO or CH₃SH.