丙烯酸与臭氧反应机理的量子化学研究.docxVIP

丙烯酸与臭氧反应机理的量子化学研究 丙烯酸与臭氧反应机理的量子化学研究 第 32 卷第 2 期 Vol. 32 No. 2 唐山师范学院学报 Journal of Tangshan Teachers College 2021 年 3 月 Mar. 2021 丙烯酸与臭氧反应机理的量子化学研究 （唐山师范学院 化学系，河北 唐山 063000） 摘 要：采用密度泛函理论在 MPW1K/6-31+G(d,p)水平上研究了丙烯酸分子 CH2CHCOOH 与臭氧 O3 分子的 反应机理，优化了反应势能面上各驻点的几何构型，对每一个驻点能量进行零点能校正，并采用相同的基组在 MPWB1K 水平和 BHandHLYP 水平上对各驻点的构型及能量进行验证。 通过同一水平的振动频率分析确认了各稳 定点和过渡态，另用内禀反应坐标（IRC）对过渡态进行验证。结果表明：丙烯酸的臭氧化反应具有较高的反应 活性，并且为多通道反应， 多数反应通道有 OH 自由基生成。 反应过程中有顺反异构的 COOHHCOO 自由基生成， 二者会沿不同的反应通道进行反应，其中 syn-COOHHCOO 的反应活化能较高。 关键词：丙烯酸；密度泛函理论；臭氧化；羟基自由基 中图分类号： O621.14+2 文献标识码：A 文章编号： 1009-9115(2021)02-0001-06 A Quantum Chemistry Investigation on the Mechanisms of Ozonolysis of Crylic Acid YANG Jing (Department of Chemistry, Tangshan Teachers College, Tangshan 063000, China) Abstract: The reaction mechanism between ozone molecule and crylic acid has been studied using the density functional theory(DFT) methods. The geometries of all the stationary points involved in the reaction are completely optimized by the MPW1K/6-31+G(d,p) level of theory. The relative energy obthained at the MPW1K/6-31+G(d,p) level of theory are further refined with the zero point energy correction(ZPE). The geometries and energy for stationary points are validated by the MPWB1K/6-31+G(d,p) level of theory and the BHandHLYP/6-31+G(d,p) level of theory. In addition, all the transition states and intermediates are verified by the frequency analysis calculations. The results indicate that ozone reacts with crylic acid feasibly because of the low barrier on its energy profile.. And OH yields can be product in a variety of reaction channels. Beside, there will be two isomers of COOHHCOO radicals produced from the decomposition of different transition states. The isomers have their own reaction pathways. And syn-COOHHCOO has higher activation energies and can decomposes OH radicals. Key words: crylic acid; density functional theory(DFT); ozonolysis; hydroxyl radicals 1 引言 被大量耗损后，其吸收紫外线的能力将大大减弱，导致到达