燃烧条件下 C7H7 势能面的综合动力学,The Journal of Physical Chemistry A

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燃烧条件下 C7H7 势能面的综合动力学
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2023-02-20 , DOI: 10.1021/acs.jpca.2c08035
Carles Martí ₁ , Hope A Michelsen ₂ , Habib N Najm ₁ , Judit Zádor ₁

Affiliation

自动化动力学工作流程代码 KinBot 用于探索和表征 C ₇ H _7的区域与燃烧环境相关的势能面，尤其是烟灰生成。我们首先探索了最低能量区域，其中包括苄基、富维烯 + H 和环戊二烯基 + 乙炔入口点。然后我们扩展模型以包括两个更高能量的入口点，乙烯基炔丙基 + 乙炔和乙烯基乙炔 + 炔丙基。自动搜索能够从文献中发现途径。此外，还发现了三个重要的新路线：连接苄基和乙烯基环戊二烯基的低能量途径，导致侧链氢原子损失以产生富烯丙二烯 + H 的苄基分解机制，以及更短和更低能量的二亚甲基-环戊烯中间体。我们系统地将扩展模型简化为由 63 个孔、10 个双分子产物、87 个障碍和 1 个无障碍通道组成的化学相关域，并使用 CCSD(T)-F12a/cc-pVTZ//ωB97X-D/ 构建了一个主方程6-311++G(d,p) 理论水平，为化学建模提供速率系数。我们计算出的速率系数与测量值非常吻合。我们还模拟了浓度分布并计算了重要入口点的分支分数，以提供对这一重要化学景观的解释。我们计算出的速率系数与测量值非常吻合。我们还模拟了浓度分布并计算了重要入口点的分支分数，以提供对这一重要化学景观的解释。我们计算出的速率系数与测量值非常吻合。我们还模拟了浓度分布并计算了重要入口点的分支分数，以提供对这一重要化学景观的解释。

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Comprehensive Kinetics on the C7H7 Potential Energy Surface under Combustion Conditions

The automated kinetics workflow code, KinBot, was used to explore and characterize the regions of the C₇H₇ potential energy surface that are relevant to combustion environments and especially soot inception. We first explored the lowest-energy region, which includes the benzyl, fulvenallene + H, and cyclopentadienyl + acetylene entry points. We then expanded the model to include two higher-energy entry points, vinylpropargyl + acetylene and vinylacetylene + propargyl. The automated search was able to uncover the pathways from the literature. In addition, three important new routes were discovered: a lower-energy pathway connecting benzyl with vinylcyclopentadienyl, a decomposition mechanism from benzyl that results in side-chain hydrogen atom loss to produce fulvenallene + H, and shorter and lower energy routes to the dimethylene-cyclopentenyl intermediates. We systematically reduced the extended model to a chemically relevant domain composed of 63 wells, 10 bimolecular products, 87 barriers, and 1 barrierless channel and constructed a master equation using the CCSD(T)-F12a/cc-pVTZ//ωB97X-D/6-311++G(d,p) level of theory to provide rate coefficients for chemical modeling. Our calculated rate coefficients show excellent agreement with measured ones. We also simulated concentration profiles and calculated branching fractions from the important entry points to provide an interpretation of this important chemical landscape.

更新日期：2023-02-20

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