Kinetics and spectroscopy of free radical intermediates in tropospheric reactions

对流层反应中自由基中间体的动力学和光谱

• 批准号: 1413712
• 负责人: Mitchio Okumura
• 金额: $ 41.5万
• 依托单位: California Institute of Technology
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2014
• 资助国家: 美国
• 起止时间: 2014-11-15 至 2019-10-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1413712&HistoricalAwards=false
• 关键词: Kinetics; spectroscopy; free; radical; intermediates

In this project funded by the Environmental Chemical Sciences program of the Chemistry Division at the National Science Foundation, Professor Mitchio Okumura of the California Institute of Technology is researching the oxidation mechanisms of volatile organic compounds that form air pollution. Professor Okumura will provide excellent training for his graduate students utilizing modern experimental physical tools, as well as with scientific reasoning. They will utilize fast laser spectroscopic techniques to detect free radical species and observe how changes occur as they flow through atmospheric oxidation processes. The award will contribute to building the nation's scientific infrastructure through collaborations within the university, among three other universities, and two government funded research laboratories. International collaboration will also be expanded with individuals from the French National Synchrotron. Professor Okumura has a proven record in encouraging the participation of women and underrepresented minorities, which will be strengthened through outreach to underrepresented groups by the expansion of formal connections to classrooms in local K-12 schools. Prior outreach programs created by the Okumura Group will continue to be developed to teach elementary school students about air pollution while inspiring their interest in science. This work focuses on characterizing the fates of peroxy radicals, which are ubiquitous intermediates in atmospheric oxidation. These species will be studied using many techniques: Cavity Ringdown Spectroscopy, Multiplexed Photoionization Mass Spectrometry, and Photoelectron-Photoion Coincidence Spectroscopy. The complementary approaches are designed to fully reveal how peroxy radicals evolve in atmospheric mechanisms and to characterize how their diverse chemical fates can lead to photochemical smog and secondary organic aerosol. Specific systems studied include the peroxy radicals derived from isoprene, the most important non-methane hydrocarbon emitted into the troposphere, and acetyl peroxy, whose reactions are believed to recycle oxidant in the tropics. The research will quantitatively address open questions about how unsaturated species are oxidized in the atmosphere and will lead to an understanding of organic aerosol formation and hydroxyl radical recycling mechanisms.

加州工业大学的奥村美千雄教授在国家科学基金会化学部环境化学科学项目的资助下，研究了形成空气污染的挥发性有机化合物的氧化机理。Okumura教授将为他的研究生提供利用现代实验物理工具以及科学推理的优秀培训。他们将利用快速激光光谱技术来检测自由基物种，并观察它们在流过大气氧化过程时如何发生变化。该奖项将通过大学内部的合作，与其他三所大学和两个政府资助的研究实验室合作，为建设国家的科学基础设施做出贡献。国际合作也将扩大与法国国家同步加速器的个人。Okumura教授在鼓励妇女和代表性不足的少数民族参与方面有着良好的记录，这将通过扩大与当地K-12学校教室的正式联系来扩大代表性不足的群体。奥村集团之前创建的外展计划将继续发展，向小学生传授空气污染知识，同时激发他们对科学的兴趣。这项工作的重点是表征过氧自由基的命运，这是无处不在的中间体在大气氧化。这些物种将使用许多技术进行研究：腔衰荡光谱，多路复用光电离质谱，和光电子-光离子符合光谱。互补的方法旨在充分揭示过氧自由基如何在大气机制中演变，并描述其不同的化学命运如何导致光化学烟雾和二次有机气溶胶。研究的具体系统包括来自异戊二烯的过氧自由基，异戊二烯是排放到对流层的最重要的非甲烷烃，以及乙酰过氧，其反应被认为是在热带地区循环氧化剂。这项研究将定量地解决有关不饱和物种如何在大气中氧化的公开问题，并将导致对有机气溶胶形成和羟基自由基再循环机制的理解。

项目成果

Just add water dimers

• DOI: 10.1126/science.aaa5506
• 发表时间: 2015-02
• 期刊: Science
• 影响因子: 56.9
• 作者: M. Okumura