大气中芳樟醇与臭氧反应机理的理论研究  

Theoretical Study on the Reaction Mechanism of the Linalool with Ozone in Atmosphere

作　　者：孙廷利[1] 王玉东[1] 张晨曦[1] 孙孝敏[1,2] 胡敬田[1] 

机构地区：[1]山东大学环境研究院,济南250100 [2]中国科学院兰州化学物理研究所固体润滑国家重点实验室,兰州730000

出　　处：《化学学报》2011年第17期1965-1972,共8页Acta Chimica Sinica

基　　金：国家自然科学基金(Nos.20777047;20737001;20903062;20873074);山东省自然科学基金(No.Q2008B07);山东大学自主创新基金(No.2010TS064);中科院生态环境研究中心环境化学与生态毒理学国家重点实验室开放基金课题(No.KF2009-10)资助项目

摘　　要：采用密度泛函理论研究了大气中芳樟醇臭氧化反应机理.在B3LYP/6-31G*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,在B3LYP/6-311+G(3df,2pd)水平下进行单点能量计算,构筑了反应的势能剖面.对反应中间体与H2O和NO可能的氧化机理进行了详细的描述.并对转化过程中各竞争反应的反应势垒、反应热和Gibbs自由能等物理化学参数进行了详细分析.生成的产物极性和水溶性增强,易通过成核、水合或吸附反应形成二次有机气溶胶.The reaction mechanism of the linalool with ozone in atmosphere has been studied using density functional theory.The geometries of the stationary points were optimized,and the harmonic vibration fre-quencies were calculated at the B3LYP/6-31G（d） level.The single point energies of the stationary point were calculated at the B3LYP/6-311＋G（3df,2pd） level and the detailed profiles of the potential energy sur-faces for the reactions were constructed.The potential oxidation mechanisms of the intermediates with H2O or NO were discussed in detail.The physicochemical parameters of the competing reaction channels includ-ing reaction barrier,enthalpy change,and Gibbs free energy change have been analyzed.Most of the prod-ucts can contribute to the formation of secondary organic aerosol through nucleation,hydration or absorption since their polarity and water-solubility enhance.

关 键 词：芳樟醇 臭氧化 反应机理 二次有机气溶胶 

分 类 号：O643.12[理学—物理化学]