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A thorough theoretical mechanistic study of OH-initiated oxidative degradation mechanism for large polycyclic aromatic hydrocarbons
Computational and Theoretical Chemistry ( IF 3.0 ) Pub Date : 2020-01-30 , DOI: 10.1016/j.comptc.2020.112730
Lili Xing , Qinghui Meng , Lidong Zhang

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.



中文翻译:

大型多环芳烃的OH引发的氧化降解机理的详尽理论机理研究

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。

更新日期:2020-01-31
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