Cl原子引发3-甲基-2-丁烯醛大气氧化机制的理论研究  

Theoretical Study on Atmospheric Oxidation Mechanism of 3-methyl-2-butenal Initiated by Cl Atoms

作　　者：石博[1] 赵彬 曾艳丽[1] SHI Bo;ZHAO Bin;ZENG Yanli(College of Chemistry and Materials Science,Hebei Normal University,Hebei Shjiazhuang 050024,China)

机构地区：[1]河北师范大学化学与材料科学学院,河北石家庄050024

出　　处：《河北师范大学学报（自然科学版）》2022年第5期488-493,共6页Journal of Hebei Normal University：Natural Science

基　　金：河北省自然科学基金(B2021205023);中国博士后基金(2020M670684);河北省教育厅基金(QN2020190);河北省博士后基金(B2020003017);河北师范大学重点项目(L2020Z04);河北师范大学博士启动基金(L2020B12)。

摘　　要：醛、酮类化合物作为大气中典型的含氧挥发性有机物,对大气自由基及臭氧的生成均具有潜在的重要贡献.采用密度泛函理论(DFT),从微观角度深入研究了3-甲基2-丁烯醛与Cl原子间的大气反应机制,对所有可能发生的反应路径进行了搜寻计算,并从热力学角度对各反应路径进行了对比分析.结果表明,标题反应的路径可以分为2种类型:加成反应和抽氧反应.其中,加成反应通道为无能垒的反应过程,是3甲基2丁烯醛与Cl原子反应的主反应途径;而在抽氧反应通道中,抽取醛基氢(-OC^(12)(H))和甲基氢(-CH_(3))是抽氧反应类型中相对最优路径.此外,还对标题反应过程中的关键性中间体在O_(2)和NO存在条件下的后续反应机制进行了计算分析,为研究该类污染物在大气中的氧化过程提供了详细的理论数据.Aldehydes and ketones, as typical oxygen-containing volatile organic compounds in the atmosphere, have potentially important contributions to the formation of atmospheric free radicals and ozone.The atmospheric reaction mechanism between 3-methyl-2-butenal and Cl atom has been investigated using density functional theory(DFT),and all the possible reaction pathways have been searched and compared from thermodynamic point of view.The results show that all the channels of the title reaction can be divided into two types: addition reaction and abstract-H reaction.Among them, addition channel is a reaction process without energy barrier, which is the main reaction channel of 3-methyl-2-butenal with Cl_(12) atom.In the abstract-H reaction channel, the extractions of hydrogen from the aldehyde(-OC(H)) and methyl group(-CH_(3)) are relatively favorable channels.In addition, the subsequent reaction mechanism of the key intermediates in the reaction process with the presence of Oand NO is also calculated and analyzed, which could provide detailed theoretical data for studing the oxidation process of this type of pollutants in the atmosphere.

关 键 词：3-甲基-2-丁烯醛 大气反应机制 DFT计算 CL原子 

分 类 号：O642.1[理学—物理化学]