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。
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 MPW1 K/6-31 ＋G（d,p） level of theory. The relative energy obthained at the MPW1 K/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.
出处
《唐山师范学院学报》
2010年第2期1-6,共6页
Journal of Tangshan Normal University
基金
河北省教育厅科学研究计划项目(Z2007204)
关键词
丙烯酸
密度泛函理论
臭氧化
羟基自由基
crylic acid
density functional theory（DFT）
ozonolysis
hydroxyl radicals
