State-Resolved Photodissociation Dynamics of Small Free Radicals: Structure, Energetics, and Photochemical Reactivity

小自由基的状态分辨光解离动力学：结构、能量学和光化学反应性

• 批准号: 0111635
• 负责人: Jingsong Zhang
• 金额: $ 32.3万
• 依托单位: University of California-Riverside
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2001
• 资助国家: 美国
• 起止时间: 2001-08-01 至 2004-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0111635&HistoricalAwards=false
• 关键词: State; Resolved; Photodissociation; Dynamics; Small

Dr. Jingsong Zhang of the University of California Riverside is funded for his research on state-resolved photodissociation dynamics of small free radicals, structure, energetics, and photochemical reactivity by the Physical Chemistry Program of the Chemistry Division. Fundamentally new insigts and quantitative understanding of photochemical reactivity of small prototypical free radicals will be generated experimentally uisng laser excitation, laser probing, and time of flight mass spectroscopy. Laser spectroscopy and state-resolved photodissociation dynamics will be used to fully characterize prototypical reactive intermediates and small alkyl, unsaturated aliphatic, alkoxy, and aromatic radicals, as well as the HOCO radical. These systems will also be examined at a high level of theory (electronic and dynamic) with little or no approximation. Detailed mechanisms involving dissociation and nuclear rearrangement will be generated. Open-shell electronic states, structures and multiple potential energy surfaces of free radicals and their influences on photodissociation and unimolecular reactions will be deduced. Competitive dissociation pathways and decomposition mechanims of free radicals and product energy disposal will be mapped. Free-radical electronic states, thermodynamics, and energetics will be tabulated.The energetics and dynamics of small free radicals are important areas of physical chemistry and have practical importance in combustion and atmospheric chemistries. The experimental and theoretical analyses by Dr. Zhang will provide detailed advances in our understanding of important carbon-based radicals and the hydrogen extraction chemistry of these radicals. In addition, important teaching and training will be provided students at one of our nation's most culturally diverse universities. Multi-disciplinary approaches, for example, connections between fundamental molecular-level knowledge and practical atmospheric and combustion chemistry, as well as those between modern techniques and scientific advances, will be stressed.

加州大学滨江分校的张劲松博士获得了化学系物理化学项目的资助，用于研究小自由基的状态分辨光解动力学、结构、能量学和光化学反应性。 利用激光激发、激光探测和飞行时间质谱，将从根本上产生新的实验结果，并定量地了解小的原型自由基的光化学反应性。 激光光谱和状态分辨光解动力学将用于充分表征原型反应中间体和小烷基，不饱和脂肪族，烷氧基和芳香族基团，以及HOCO自由基。 这些系统也将在高水平的理论（电子和动态）进行检查，很少或没有近似。 详细的机制，包括解离和核重排将产生。 推导自由基的开壳层电子态、结构和多重势能面，以及它们对光解离和单分子反应的影响。 竞争性解离途径和自由基的分解机制和产物能量处置将被映射。 自由基的电子态、热力学和能量学将被制成表格。小自由基的能量学和动力学是物理化学的重要领域，在燃烧和大气化学中具有实际的重要性。 张博士的实验和理论分析将为我们对重要的碳基自由基和这些自由基的氢提取化学的理解提供详细的进展。 此外，重要的教学和培训将在我们国家最具文化多样性的大学之一提供学生。 将强调多学科办法，例如，基本分子知识与实际大气和燃烧化学之间的联系，以及现代技术与科学进步之间的联系。