The Recombination of Propargyl Radicals and Other Reactions on a C6H6 Potential
The Recombination of Propargyl Radicals and Other Reactions on a C6H6 Potential
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DOI：
10.1021/jp030375h
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发表时间：
2003-09
影响因子：
2.9
通讯作者：
James A. Miller and;S. Klippenstein
中科院分区：
文献类型：
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作者：
James A. Miller and;S. Klippenstein
利用电子结构方法的组合，我们详细地探索了C6H6电位的一些区域，这些区域对描述丙炔（C3H3）自由基的重组很重要。在基于rrkm的主方程中使用这些信息，我们已经能够预测各种基本反应的速率系数，包括C3H3 + C3H3重组本身。一般来说，理论与有限的实验信息之间的一致性非常好，尽管仍然存在一些差异。本分析的最重要的新特征（与我们之前的分析相比）是在电位上包含了一条连接1,2,4,5-六四烯和1,3-己二烯-5-炔的路径，然后在不经过富勒烯的情况下连接苯和苯基+ H。在分析中包含这条路径使得理论可以解释许多实验观察。根据主方程的计算结果，我们提出了一个简单的、收缩的模型。
Using a combination of electronic-structure methods, we have explored in some detail the regions of the C6H6 potential that are important for describing the recombination of propargyl (C3H3) radicals. Using this information in an RRKM-based master equation, we have been able to predict rate coefficients for a variety of elementary reactions, including the C3H3 + C3H3 recombination itself. Generally, the agreement between the theory and the limited amount of experimental information available is very good, although some discrepancies remain. The most important new feature of the present analysis (over our previous one) is the inclusion of a path on the potential that connects 1,2,4,5-hexatetraene to 1,3-hexadien-5-yne and then goes on to benzene and phenyl + H without passing through fulvene. The inclusion of this path in the analysis allows a number of experimental observations to be accounted for by the theory. From the results of the master equation calculations, we propose a simple, contracted model fo...