Unimolecular Decomposition Rate of the Criegee Intermediate (CH3)2COO Measured Directly with UV Absorption Spectroscopy
作者： Mica C. Smith , Wen Chao , Kaito Takahashi , Kristie A. Boering , Jim Jr-Min Lin
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摘要: The unimolecular decomposition of (CH3)2COO and (CD3)2COO was measured by direct detection the Criegee intermediate at temperatures from 283 to 323 K using time-resolved UV absorption spectroscopy. rate coefficient kd for shows a strong temperature dependence, increasing 269 ± 82 s–1 916 56 with an Arrhenius activation energy ∼6 kcal mol–1. bimolecular reaction SO2, kSO2, also determined in range 303 K. Our temperature-dependent values kSO2 are consistent previously reported relative coefficients kd/kSO2 formed ozonolysis tetramethyl ethylene. Quantum chemical calculations experiment, combination experiment theory indicates that tunneling plays significant role decomposition. fast rates (CH3...
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