To get a better understanding of oxidative degradation of polycyclic aromatic hydrocarbons (PAH) in the atmospheric and combustion chemistry, benzo[ghi]perylene (BP) was selected as their prototype to be investigated by combining ab initio electronic structure theory calculations (M06-2X/6-31G(d,p)) and the conventional transition state theory. For BP-OH adducts, O₂ addition favored the armchair edge comparing with the free and zigzag ones. The overall rate constant was increased due to the presence of armchair site; and thereby it has a prompt effect on the oxidation reactivity. This implies that given an arbitrary shaped PAH, OH attack preferentially occurs at the free-edge sites and subsequent O₂ attack favors the armchair-edge sites. Morever, the current study provides new kinetics and thermodynamics data for OH-initiated oxidative degradation mechanism of benzo[ghi]perylene in a wider temperature range, which can be used for modeling the fate of large PAHs during combustion and in the atmosphere.

为了更好地理解大气和燃烧化学中多环芳烃（PAH）的氧化降解，选择苯并per（BP）作为其原型，通过结合从头算电子结构理论计算（M06-2X / 6-31G（d，p））和传统的过渡态理论。对于BP-OH加合物，与游离和锯齿形相比，O _2的添加有利于扶手椅边缘。总速率常数由于扶手椅位的存在而增加。从而对氧化反应性具有迅速的影响。这意味着给定任意形状的PAH，OH攻击优先发生在自由边缘位置，随后发生O ₂攻击有利于扶手椅边缘的站点。此外，当前的研究为在更宽的温度范围内OH引发的苯并per萘的氧化降解机理提供了新的动力学和热力学数据，其可用于模拟燃烧过程中和大气中大型PAH的命运。