Criegee自由基大气化学反应机理与二次有机气溶胶形成

项目名称： Criegee自由基大气化学反应机理与二次有机气溶胶形成

项目编号： No.21473108

项目类型： 面上项目

立项/批准年度： 2015

项目学科： 数理科学和化学

项目作者： 王文亮

作者单位： 陕西师范大学

项目金额： 84万元

中文摘要： Criegee自由基RR'COO与有机过氧自由基ROO虽然不是地球大气的主要组成部分，但它们均是大气中的高活性成分，对光化学烟雾与有机气溶胶形成等环境问题有重要影响。本项目针对Criegee自由基大气化学反应研究中存在的双自由基计算方法选取、优势通道PES多重度规律确定、反应机理揭示、水分子如何催化等几个重要基本科学问题开展全面计算研究。基于对称性破损与多参考态相互作用等精确计算相结合方案，探索建立一种既有较高计算精度又有较高效率的适合于较大双自由基体系的组合计算方法；系统研究RR'COO低聚及与ROO, SO2, NO2等典型大气物种反应体系，并详细考察水分子存在对反应机理与动力学性质的影响；深入揭示自由基-自由基反应优势通道多重度规律、二次有机气溶胶ROO(CH2OO)nH形成及RR'COO自由基大气化学反应机理。本项目研究为消除大气雾霾污染、改善大气环境质量等相关应用研究提供理论指导

中文关键词： Criegee自由基；有机气溶胶；大气化学；反应机理；量子化学计算

英文摘要： Criegee radicals RR'COO and organic peroxy radicals ROO, although not a primary component in atmosphere are highly active ingredients and an important participant for the atmospheric chemical pollution on the troposphere, which having a crucial impact on organic aerosols and photochemical smog formation, climate change and other environmental problem. The atmospheric reaction mechanism of Criegee radicals will be investigated systematically with quantum chemical calculations methods. The project aims at fundamental scientific issues, the proper method for the open-shell diradical, the law of multi-degree of PES for the favorable reaction channel, the reaction mechanism and water molecules catalysis the reaction. To the end, a high accurate and high efficient method will be established for the system with large open-shell diradicals using the combination of the broken symmetric theory and accurate methods MRCI and others. A basic law for the PES multi-degree of favorable reaction channel will be summarized. The Chemical reaction mechanism of Criegee radicals with typical species and the formation mechanism of atmospheric secondary organic aerosol ROO (CH2OO)nH will be revealed and the reaction mechanism and kinetics of atmospheric RR'COO will be investigated under the presence of water clusters. The results can be expected to provide theoretical guidance to eliminate atmospheric haze pollution to improve the atmospheric environment and other related applied research.

英文关键词： Criegee Radicals;Organic Aerosol;Atmospheric Chemistry;Reaction Mechanism;Quantum Chemistry Calculation