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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Theoretical Study of the Kinetics of the Hydrogen Abstraction from Methanol. 1. Reaction of Methanol with Fluorine Atoms
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Theoretical Study of the Kinetics of the Hydrogen Abstraction from Methanol. 1. Reaction of Methanol with Fluorine Atoms

机译：从甲醇中提取氢的动力学的理论研究。 1.甲醇与氟原子的反应

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摘要

Ab initio calculations at different levels of theory and using several basis sets were performed for the title two-channel hydrogen-abstraction reaction. Conclusions are drawn from G2 energies. These calculations have shown that this reaction, which can give two products (namely, CH_3O and CH_2OH), proceeds through the formation of intermediate complexes followed by transition states with quite negligible activation energy. We propose a method for the calculation of the rate constant of a bimolecular reaction proceeding through the formation of two intermediate complexes. General equations, taking into account the rotational energy, are derived from RRKM theory, using the simplified version of the SACM theory. The resulting calculated overall rate constant as well as the yield of the methoxy branching ratio are in very good agreement with experimental findings. The expressions for the site-specific rate constants k(CH_3O) and k(CH_2OH) allow the description of the reaction kinetics over a wide range of temperatures. A temperature rate constant fit, convenient for chemical modeling studies, is k(CH_3O) = 1.0 * 10~(-10) (T/300)~(0.5) cm~3 molecule~(-1) s~(-1) and k(CH_2OH) = 6.9 * 10~(-11) (T/300)~(0.27) cm~3 molecule~(-1) s~(-1).
机译：在标题的两通道吸氢反应中，从理论上的不同高度和使用几个基本集合进行了从头算。结论是从G2能量得出的。这些计算表明，该反应可产生两种产物（即CH_3O和CH_2OH），通过形成中间体配合物，然后是过渡态而具有非常可忽略的活化能进行。我们提出了一种计算通过形成两个中间配合物进行的双分子反应速率常数的方法。使用SACM理论的简化版本，从RRKM理论推导出考虑了旋转能量的通用方程。所得的计算出的总速率常数以及甲氧基支化比的产率与实验结果非常吻合。特定位置速率常数k（CH_3O）和k（CH_2OH）的表达式可以描述在宽温度范围内的反应动力学。便于化学建模研究的温度速率常数拟合为k（CH_3O）= 1.0 * 10〜（-10）（T / 300）〜（0.5）cm〜3分子〜（-1）s〜（-1） k（CH_2OH）= 6.9 * 10〜（-11）（T / 300）〜（0.27）cm〜3分子〜（-1）s〜（-1）。

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