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Experimental and Computational Studies of the Kinetics of the Reaction of Atomic Hydrogen with Methanethiol

机译:原子氢与甲硫醇反应动力学的实验和计算研究

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The overall rate constant for H + CH3SH has been studied over 296-1007 K in an Ar bath gas using the laser flash photolysis method at 193 nm. H atoms were generated from CH3SH and in some cases NH3, They were detected via time-resolved resonance fluorescence. The results are summarized as k = (3.45 +/- 0.19) X 10(-11) cm(3) molecule(-1) s(-1) exp (-6.92 +/- 0.16 kJ mol(-1)/RT) where the errors in the Arrhenius parameters are the statistical uncertainties, at the 2 sigma level. Overall error limits of 9% for k are proposed. In the overlapping temperature range there is very good agreement with the resonance fluorescence measurements of Wine et al Ab initio data and transition state theory yield moderate accord with the total rate constant, but not with prior mass spectrometry measurements of the main product channels leading to CH3S + H-2 and CH3 + H2S by Amano et al.
机译:使用激光闪光光解法在193 nm的Ar浴气体中研究了H + CH3SH的总速率常数,超过296-1007K。 H原子由CH3SH生成,在某些情况下由NH3生成,通过时间分辨共振荧光检测到。结果总结为k =(3.45 +/- 0.19)X 10(-11)cm(3)分子(-1)s(-1)exp(-6.92 +/- 0.16 kJ mol(-1)/ RT ),其中Arrhenius参数的误差是统计不确定性,在2 sigma级别。建议将k的总误差限制为9%。在重叠的温度范围内,与Wine等从头算数据的共振荧光测量非常吻合,过渡态理论得出的结果与总速率常数适度一致,但与导致CH3S的主要产物通道的先前质谱测量却不一致Amano等人的+ H-2和CH3 + H2S。

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