Department of Chemistry and Biochemistry, Florida International University, Miami, Florida, 33199, USA.
Department of Mechanical Engineering, University of California at Berkeley, Berkeley, California, 94720-1740, USA.
Faraday Discuss. 2022 Oct 21;238(0):512-528. doi: 10.1039/d2fd00012a.
The present study undertakes a theoretical evaluation of thermal decomposition of aromatic-ring radicals. Potential energy surfaces and associated reaction rate coefficients were calculated for 1- and 2-naphthalenyl, acetanaphthylenyl, and pyrenyl radicals. Kinetic Monte-Carlo simulations were performed to examine the rates of ring cleavage in two sooting laminar premixed flames of ethylene. The simulations showed that the thermal aromatic-ring cleavage is comparable in rate to oxyradical decomposition in a heavier-sooting flame. The simulation also revealed, unexpectedly, fast internal ring radical migration, comparable in frequency to reaction events of aromatic growth.
本研究对芳环自由基的热分解进行了理论评估。计算了 1-和 2-萘基、乙酰萘基和芘基自由基的位能面和相关反应速率系数。进行了动力学蒙特卡罗模拟，以研究两种乙烯富燃料层流预混火焰中环的断裂速率。模拟表明，热芳环断裂的速率与重烟火焰中氧化自由基分解相当。模拟还出人意料地揭示了快速的内环自由基迁移，其频率与芳构化反应事件相当。
