The hydrogen‐abstraction‐C₂H₂‐addition (HACA) chemistry of naphthalenyl radicals has been studied extensively, but there is a significant discrepancy in product distributions reported or predicted in literature regarding appearance of C₁₄H₈ and C₁₄H₁₀ species. Starting from ab initio calculations, a comprehensive theoretical model describing the HACA chemistry of both 1‐ and 2‐naphthalenyl radicals is generated. Pressure‐dependent kinetics are considered in the C₁₂H₉, C₁₄H₉, and C₁₄H₁₁ potential energy surfaces including formally direct well‐skipping pathways. On the C₁₂H₉ PES, reaction pathways were found connecting two entry points: 1‐naphthalenyl (1‐C₁₀H₇) + acetylene (C₂H₂) and 2‐C₁₀H₇ + C₂H₂. A significant amount of acenaphthylene is predicted to be formed from 2‐C₁₀H₇ + C₂H₂, and the appearance of C₁₄H₈ isomers is predicted in the model simulation, consistent with high‐temperature experimental results from Parker et al. At 1500 K, 1‐C₁₀H₇ + C₂H₂ mostly generates acenaphthylene through a formally direct pathway, which predicted selectivity of 66% at 30 Torr and 56% at 300 Torr. The reaction of 2‐C₁₀H₇ with C₂H₂ at 1500 K yields 2‐ethynylnaphthalene as the most dominant product, followed by acenaphthylene mainly generated via isomerization of 2‐C₁₀H₇ to 1‐C₁₀H₇. Both the 1‐C₁₀H₇ and 2‐C₁₀H₇ reactions with C₂H₂ form some C₁₄H₈ products, but negligible phenanthrene and anthracene formation is predicted at 1500 K. A rate‐of‐production analysis reveals that C₁₄H₈ formation is strongly affected by the rates of H‐abstraction from acenaphthylene, 1‐ethynylnaphthalene, and 2‐ethynylnaphthalene, so the kinetics of these reactions are accurately calculated at the high level G3(MP2,CC)//B3LYP/6‐311G^** level of theory. At intermediate temperatures like 800 K, acenaphthylene + H are the leading bimolecular products of 1‐C₁₀H₇ + C₂H₂, and 1‐acenaphthenyl radical is the most abundant C₁₂H₉ isomer due to its stability. The predicted product distribution of 2‐C₁₀H₇ + C₂H₂ at 800 K, in contrast to the results of Parker et al is predicted to consist primarily of species containing three fused benzene rings—for example, phenanthrene and anthracene—as the leading products, indicating HACA chemistry is valid from two to three ring polycyclic aromatic hydrocarbons under some conditions. Further experiments are needed for validation.

中文翻译：

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萘基和乙炔的HACA化学的理论研究：C12H8，C14H8和C14H10物种的形成

萘基自由基的吸氢C ₂ H ₂加成（HACA）化学已得到广泛研究，但有关C ₁₄ H ₈和C ₁₄ H ₁₀种类的文献报道或预测的产品分布存在显着差异。从头算开始，生成了描述1–和2–萘基的HACA化学性质的综合理论模型。在C ₁₂ H ₉，C ₁₄ H ₉和C ₁₄ H ₁₁中考虑了压力依赖性动力学势能面，包括形式上直接的跳井路径。在C ₁₂ H ₉ PES上，发现了连接两个入口点的反应路径：1-萘基（1-C ₁₀ H ₇）+乙炔（C ₂ H ₂）和2-C ₁₀ H ₇ + C ₂ H ₂。预计大量的of烯是由2–C ₁₀ H ₇ + C ₂ H ₂和C ₁₄ H ₈的外观形成的模型模拟中预测了异构体，这与Parker等人的高温实验结果一致。在1500 K下，1–C ₁₀ H ₇ + C ₂ H ₂主要通过形式直接途径生成generates烯，预计在30 Torr时选择性为66％，在300 Torr时选择性为56％。2‐C ₁₀ H ₇与C ₂ H ₂在1500 K下的反应生成2-乙炔基萘为最主要的产物，随后是mainly烯，主要是通过2‐C ₁₀ H ₇异构化为1‐C ₁₀ H _7生成的。1‐C ₁₀ H _7都和2‐C ₁₀ H ₇与C ₂ H _2的反应会形成一些C ₁₄ H ₈产物，但预计在1500 K时菲和蒽的形成可忽略不计。生产率分析表明，C ₁₄ H _8的形成受到很大影响根据from，1-乙炔基萘和2-乙炔基萘中H的吸收率，因此可以在理论水平高的G3（MP2，CC）// B3LYP / 6-311G ^**下精确计算这些反应的动力学。在800 K等中等温度下，烯+ H是1–C ₁₀ H ₇ + C的主要双分子产物。₂ H ₂和1-‐烯基由于其稳定性而成为最丰富的C ₁₂ H ₉异构体。与Parker等人的结果相反，在800 K时2–C ₁₀ H ₇ + C ₂ H ₂的预测产物分布主要由包含三个稠合苯环的物质组成，例如菲和蒽。主导产品，表明HACA化学方法在某些条件下对2至3个环多环芳烃有效。验证需要进一步的实验。