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Reaction Kinetics of Hydrogen Atom Abstraction from C4–C6 Alkenes by the Hydrogen Atom and Methyl Radical
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2018-05-23 00:00:00 , DOI: 10.1021/acs.jpca.8b03659
Quan-De Wang 1 , Zi-Wu Liu 1
Affiliation  

Alkenes are important ingredients of realistic fuels and are also critical intermediates during the combustion of a series of other fuels including alkanes, cycloalkanes, and biofuels. To provide insights into the combustion behavior of alkenes, detailed quantum chemical studies for crucial reactions are desired. Hydrogen abstractions of alkenes play a very important role in determining the reactivity of fuel molecules. This work is motivated by previous experimental and modeling evidence that current literature rate coefficients for the abstraction reactions of alkenes are still in need of refinement and/or redetermination. In light of this, this work reports a theoretical and kinetic study of hydrogen atom abstraction reactions from C4–C6 alkenes by the hydrogen (H) atom and methyl (CH3) radical. A series of C4–C6 alkene molecules with enough structural diversity are taken into consideration. Geometry and vibrational properties are determined at the B3LYP/6-31G(2df,p) level implemented in the Gaussian-4 (G4) composite method. The G4 level of theory is used to calculate the electronic single point energies for all species to determine the energy barriers. Conventional transition state theory with Eckart tunneling corrections is used to determine the high-pressure-limit rate constants for 47 elementary reaction rate coefficients. To faciliate their applications in kinetic modeling, the obtained rate constants are given in the Arrhenius expression and rate coefficients for typical reaction classes are recommended. The overall rate coefficients for the reaction of H atom and CH3 radical with all the studied alkenes are also compared. Branching ratios of these reaction channels for certain alkenes have also been analyzed.

中文翻译:

氢原子与甲基自由基从C4–C6烯烃中提取氢原子的反应动力学

烯烃是实际燃料的重要成分,并且在一系列其他燃料(包括烷烃,环烷烃和生物燃料)的燃烧过程中也是重要的中间体。为了深入了解烯烃的燃烧行为,需要对关键反应进行详细的量子化学研究。烯烃的氢提取在确定燃料分子的反应性方面起着非常重要的作用。这项工作是受先前的实验和建模证据推动的,即目前有关烯烃抽象反应的文献速率系数仍需要改进和/或重新确定。有鉴于此,这项工作报告了通过氢(H)原子和甲基(CH 3)从C4-C6烯烃中提取氢原子的理论和动力学研究。) 激进的。考虑了一系列具有足够结构多样性的C4-C6烯烃分子。几何形状和振动特性是在高斯4(G4)复合方法中实现的B3LYP / 6-31G(2df,p)级别确定的。G4理论水平用于计算所有物种的电子单点能量,以确定能垒。使用具有Eckart隧道校正的常规过渡态理论来确定47个基本反应速率系数的高压极限速率常数。为了简化其在动力学建模中的应用,在Arrhenius表达式中给出了获得的速率常数,并推荐了典型反应类别的速率系数。H原子与CH 3反应的总速率系数自由基与所有研究的烯烃也进行了比较。还分析了这些反应通道对某些烯烃的支化比。
更新日期:2018-05-23
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