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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Products of the Benzene + O(3P) Reaction
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Products of the Benzene + O(3P) Reaction

机译：苯+ O（3P）反应的产物

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The gas-phase reaction of benzene with O(3P) is of considerable interest for modeling of aromatic oxidation, and also because there exist fundamental questions concerning the prominence of intersystem crossing in the reaction. While its overall rate constant has been studied extensively, there are still significant uncertainties in the product distribution. The reaction proceeds mainly through the addition of the O atom to benzene, forming an initial triplet diradical adduct, which can either dissociate to form the phenoxy radical and H atom or undergo intersystem crossing onto a singlet surface, followed by a multiplicity of internal isomerizations, leading to several possible reaction products. In this work, we examined the product branching ratios of the reaction between benzene and O(3P) over the temperature range 300-1000 K and pressure range 1-10 Torr. The reactions were initiated by pulsed-laser photolysis of NO2 in the presence of benzene and helium buffer in a slow-flow reactor, and reaction products were identified by using the multiplexed chemical kinetics photoionization mass spectrometer operating at the Advanced Light Source (ALS) of Lawrence Berkeley National Laboratory. Phenol and phenoxy radical were detected and quantified. Cyclopentadiene and cyclopentadienyl radical were directly identified for the first time. Finally, ab initio calculations and master equation/RRKM modeling were used to reproduce the experimental branching ratios, yielding pressure-dependent rate expressions for the reaction channels, including phenoxy + H, phenol, cyclopentadiene + CO, which are proposed for kinetic modeling of benzene oxidation.
机译：苯与O（3P）的气相反应对于芳香族氧化的建模非常感兴趣，并且还因为存在有关反应中系统间交叉突出的基本问题。尽管已对其整体速率常数进行了广泛研究，但产品分布仍存在很大的不确定性。该反应主要通过向苯中添加O原子来进行，从而形成初始的三重态双自由基加合物，该自由基可以解离形成苯氧基和H原子，或者发生系统间相交到单重态表面，然后进行多种内部异构化，导致几种可能的反应产物。在这项工作中，我们研究了在300-1000 K的温度范围和1-10 Torr的压力范围内苯与O（3P）之间反应的产物支化比。在慢流量反应器中，在苯和氦气缓冲液存在下，通过脉冲激光对NO2进行激光光解来启动反应，并通过使用在高级光源（ALS）上运行的多路化学动力学光电离质谱仪来鉴定反应产物。劳伦斯伯克利国家实验室。检测并定量苯酚和苯氧基自由基。首次直接鉴定出环戊二烯和环戊二烯基。最后，采用从头算和主方程/ RRKM建模来再现实验支化比，得出反应通道的压力依赖性速率表达式，其中包括苯氧基+ H，苯酚，环戊二烯+ CO，用于苯的动力学建模。氧化。

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