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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Computational Study of the Reactions of H Atoms with Chlorinated alkanes. Isodesmic Reactions for Transition States
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Computational Study of the Reactions of H Atoms with Chlorinated alkanes. Isodesmic Reactions for Transition States

机译：H原子与氯化烷烃反应的计算研究。过渡态的等渗反应

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摘要

Reactions of H atoms with methane, ethane, and chlorinated methanes and ethanes were studied by computational methods. An approach to estimating reaction rare constants based on the use of iosdesmic reactions for transition states was developed and implemented. Reactions of H atoms with CH_4 and CCl_4 (clear cases of H and Cl abstraction, respectively) were used as reference reactions. Rate constants of all other reactions from the series were calculated using the isodesmic reactions approach. For the seven reactions for which directly obtained experimental data are available, the resultant calculated temperature dependences of the rate constants demonstrate agreement with experiment. Average deviations between calculations and experiment are 17-24%, expending on the quantum chemical method used, although channel-specific rates show larger divergence. Rate constants of all 30 reaction members of the H + chloromethane and H + chloroethane classes are calculated as functions of temperature using the described approach. Individual channels of H and Cl abstraction and the corresponding reverse reactions are quantitatively characterized. In a separate part of the investigation, it is demonstrated that correlations between the energy barriers and reaction enthalpies do not provide a good predictive tool for evaluating temperature dependences of the reaction rate constants of the H + chloroalkanes class.
机译：通过计算方法研究了氢原子与甲烷，乙烷以及氯化甲烷和乙烷的反应。开发和实现了一种基于等渗反应过渡态估计反应稀有常数的方法。 H原子与CH_4和CCl_4的反应（分别为H和Cl的明显情况）用作参考反应。使用等渗反应方法计算了该系列中所有其他反应的速率常数。对于可直接获得实验数据的七个反应，速率常数的所得计算温度依赖性证明与实验一致。计算和实验之间的平均偏差为17-24％，使用的是量子化学方法，尽管特定于通道的速率显示出较大的差异。使用所述方法，计算H +氯甲烷和H +氯乙烷类别的所有30个反应成员的速率常数作为温度的函数。定量表征了H和Cl提取的各个通道以及相应的逆反应。在研究的另一部分中，证明了能垒与反应焓之间的相关性不能提供一个评估H +氯代烷烃类反应速率常数对温度的依赖性的良好预测工具。

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