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Classical Monte Carlo Analysis of Four‐Body Reactions: K + C2H5I System

机译:四连字符体反应的经典蒙特卡罗分析:K + C2H5I 系统

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The analysis of the classical four‐body problem as applied by Monte Carlo techniques to chemical reactions of the type A+BCD→AB+CD is reported. Using a modified form of a Blais—Bunker interaction potential surface, the model is applied to the reaction of K with C2H5I by approximating the C2H5radical as being two carbon atoms, one of mass 14 amu, the other of mass 15 amu. Hamilton's equations are solved numerically, and by Monte Carlo averaging over the initial variables for 1060 different trajectories, various attributes of the reaction are calculated; these include the total reaction cross section, the differential reaction cross section, and the distribution of the heat of reaction among the available degrees of freedom of the products. It is found that the total reaction cross section is 15.9 Å2. This result, which is less than that obtained by similar methods for the (K, CH3I) system, is interpreted as reflecting the increased steric hindrance present in the more bulky system.The differential reaction cross section for C2H5scattering is peaked at small angles, and an average of about 90 of the available reaction energy finds its way into internal degrees of freedom of the products. These results are in reasonable agreement with the available experimental data. It is also found that the Csngbnd;C vibrational mode of the ethyl radical is important in absorbing the heat of reaction. On the average it accounts for about 14 of the available energy. Two modes of reaction are observed, one a direct interaction, the second through complex formation. This second mechanism is found to enhance the importance of the organic radical in absorbing the heat of reaction. This is interpreted as being due to the increased opportunity for energy exchange during complex formation.
机译:报道了蒙特卡罗技术应用于A+BCD→AB+CD型化学反应的经典四体问题的分析。该模型使用改进形式的Blais-Bunker相互作用势面,通过将C2H5自由基近似为两个碳原子,一个质量为14 amu,另一个质量为15 amu,将模型应用于K与C2H5I的反应。汉密尔顿方程以数值方式求解,通过蒙特卡洛对 1060 个不同轨迹的初始变量进行平均,计算反应的各种属性;这些包括总反应截面、差分反应截面以及反应热在产物的可用自由度之间的分布。结果表明,总反应截面为15.9 Å2。该结果小于通过类似方法获得的(K,CH3I)系统的结果,被解释为反映了更笨重的系统中存在的空间位阻增加。C2H5散射的差分反应截面以小角度达到峰值,平均约90%的可用反应能量进入产物的内部自由度。这些结果与现有的实验数据合理一致。还发现乙基自由基的C&sngbnd;C振动模式在吸收反应热方面很重要。平均而言,它约占可用能源的 14%。观察到两种反应模式,一种是直接相互作用,第二种是通过复合物形成。发现第二种机制增强了有机自由基在吸收反应热中的重要性。这被解释为由于在复合物形成过程中能量交换的机会增加。

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