Reaction of Hydroxyl Radicals with Two-and Three-Ring Polycyclic Aromatic Hydrocarbons: Determination of Hydrogen Abstraction and Hydrozyl Addition Rates under Combustion and Post-

本文研究了羟基(OH)自由基与二环和三环多环自动芳香烃(PAHs)的气相反应动力学和机理，这是燃烧和大气化学中的基本问题。实验数据是在扩展的温度(300-1200oK)和压力(50-750torr)范围内收集的。用脉冲激光光解/激光诱导荧光(PLP/LIF)技术对半挥发性化合物进行了动力学和力学测量。实验包括测量压力对观察到的反应速率和动力学同位素效应的影响。通过从头算量子化学方法对加成反应和阻碍反应进行理论研究，对实验进行了补充。过渡态理论(TST)被用来获得速率约束和支化比例，而莱斯-拉姆伯格-卡塞尔-马库斯(RRKM)理论被用来估计中间体的寿命。

This is a study of the kinetics and mechanism of the gas-phase reaction of hydroxyl (OH) radicals with two-and three-ring polycyclic automatic aromatic hydrocarons (PAHs); this matter is of fundamental concern in both combustion and atmospheric chemistry. Experimental data are collected over extended temperature (300-1200oK) and pressure (50-750 torr) ranges. A pulsed laser photolysis/laser-induced fluorescence (PLP/LIF) technique refined for the study of semivolatile compounds is used for the kinetic and mechanistic measurements. Experiments include measurements of the effects of pressure on observed reaction rates and kinetic isotope effects. Experiments are complemented with a theoretical study of addition and obstruction reactions using ab initio quantum chemical methods. Transition-state theory (TST) is used to obtain rate constraints and branching rations, and Rice-Ramperger-Kassel-Marcus (RRKM) theory to estimate lifetimes of intermediates.