Analysis of the Pressure and Temperature Dependence of the Complex-Forming Bimolecular Reaction CH3OCH3 + Fe(.).
Analysis of the Pressure and Temperature Dependence of the Complex-Forming Bimolecular Reaction CH3OCH3 + Fe(.).
复制标题
分析形成配合物的双分子反应 CH3OCH3 Fe(.) 的压力和温度依赖性。
DOI：
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发表时间：
2016
影响因子：
2.9
通讯作者：
A. Viggiano
中科院分区：
文献类型：
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作者：
S. Ard;Ryan S. Johnson;Oscar E. Martínez;N. Shuman;Hua Guo;J. Troe;A. Viggiano
研究了CH3OCH3+Fe(+)在250~600K的He缓冲气体中，在0.4~1.6Torr压力下的反应动力学。测定了生成Fe(+)O(CH3)2加合物和Fe(+)OCH2+CH4产物的总速率常数和支化比。量子化学计算提供了根据统计单分子速率理论进行分析所需的参数。该分析采用了最近开发的形成络合物的双分子反应、分离缔合和化学活化贡献的速率的简化表示。实验结果与动力学模型之间获得了令人满意的一致性，允许在广泛的条件范围内对数据进行外推。结合动力学模拟结果，讨论了存在或不存在自旋反转的可能反应途径。
The kinetics of the reaction CH3OCH3 + Fe(+) has been studied between 250 and 600 K in the buffer gas He at pressures between 0.4 and 1.6 Torr. Total rate constants and branching ratios for the formation of Fe(+)O(CH3)2 adducts and of Fe(+)OCH2 + CH4 products were determined. Quantum-chemical calculations provided the parameters required for an analysis in terms of statistical unimolecular rate theory. The analysis employed a recently developed simplified representation of the rates of complex-forming bimolecular reactions, separating association and chemical activation contributions. Satisfactory agreement between experimental results and kinetic modeling was obtained that allows for an extrapolation of the data over wide ranges of conditions. Possible reaction pathways with or without spin-inversion are discussed in relation to the kinetic modeling results.