| OH引发的正辛烷大气反应机理的理论研究 |
| |
| 引用本文： | 赵燕,王慧,张庆竹,孙孝敏,王文兴. OH引发的正辛烷大气反应机理的理论研究[J]. 中国化学, 2009, 27(2): 281-288. DOI: 10.1002/cjoc.200990045 |
| |
| 作者姓名： | 赵燕 王慧 张庆竹 孙孝敏 王文兴 |
| |
| 作者单位： | 山东大学环境研究院、清华大学环境科学与工程系 |
| |
| 摘 要： | 采用量子化学密度泛函理论研究了正辛烷与OH自由基的大气氧化反应机理。在B3LYP/6-31G(d)水平上对该反应体系的反应物、中间体、过渡态及产物进行了几何构型优化和频率计算,并在B3LYP/6-311＋G(3df,2p)水平上进行了单点能计算，得出了各反应通道的势能剖面图. 计算结果表明: 羟基硝酸酯和含有羟基羰基官能团的化合物是主要的反应产物，并且它们的挥发性较低，容易形成二次有机气溶胶。另外，本文将理论计算结果与可用的实验观测结果进行了比较。
|
| 关 键 词： | 正辛烷 OH自由基 反应机理 大气氧化反应 |
| 收稿时间： | 2008-07-24 |
| 修稿时间： | 2008-12-19 |
Mechanism for OH‐Initiated Oxidation of n‐Octane in the Presence of O2 and NO: A DFT Study |
| |
| Yan ZHAO,Hui WANG,Xiaomin SUN,Qingzhu ZHANG,Wenxing WANG. Mechanism for OH‐Initiated Oxidation of n‐Octane in the Presence of O2 and NO: A DFT Study[J]. Chinese Journal of Chemistry, 2009, 27(2): 281-288. DOI: 10.1002/cjoc.200990045 |
| |
| Authors: | Yan ZHAO Hui WANG Xiaomin SUN Qingzhu ZHANG Wenxing WANG |
| |
| Affiliation: | 1. Environment Research Institute, Shandong University, Jinan, Shandong 250100, China;2. Environment Science and Engineering Institute, Tsinghua University, Beijing 100080, China;3. Fax: 0086‐0531‐88364435 |
| |
| Abstract: | Density functional theory was used to study the mechanism for the OH‐initiated atmospheric oxidation of n‐octane in the presence of O2 and NO. The geometries and frequencies of the reactants, transition states, intermediates, and products were calculated at the B3LYP/6‐31G(d) level and single‐point energy calculations were carried out with a large basis set, 6‐311+G(3df, 2p). All of the possible product channels have been studied, but only the main ones are reported. The main products obtained are hydroxynitrates and hydroxycarbonyls, which have relative low vapor pressure and are inclined to form secondary organic aerosol. The theoretical results were compared with the available experimental observations. |
| |
| Keywords: | n‐octane OH radical reaction mechanism atmospheric oxidation |
|
| 点击此处可从《中国化学》浏览原始摘要信息 |
|
点击此处可从《中国化学》下载全文 |
|
