Molecular Beam and Imaging Studies of Radical Reaction Pathways and Chemical Product Branching

自由基反应途径和化学产物支化的分子束和成像研究

• 批准号: 0403471
• 负责人: Laurie Butler
• 金额: $ 46.09万
• 依托单位: University of Chicago
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2004
• 资助国家: 美国
• 起止时间: 2004-07-15 至 2008-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0403471&HistoricalAwards=false
• 关键词: Molecular; Beam; Imaging; Studies; Radical

In this project, funded by the Experimental Physical Chemistry Program of the Chemistry Division, Professor Laurie J. Butler of the University of Chicago will study the unimolecular decay of selected radical species as a function of energy of the radical. Molecular beam and imaging techniques will be used to perform two sets of experiments. 1) The first set will probe competing unimolecular dissociation channels of isomerically-selected hydrocarbon radicals as function of internal energy in the dissociating radical isomer on the ground state potential surface. Two key C4H7 radical isomers will be investigated. 2) The second part of the research deals with the dynamics of the carbene biradical intermediates of the oxygen-triplet-P + alkyne reactions. In the oxygen + acetylene system, the dynamics is claimed to proceed via intersystem crossing from the triplet to singlet ketene. This work will probe the importance of intersystem crossing in this class of bimolecular reactions and thereby provide data to test theoretical models for this reaction. The work will also address larger alkyne + oxygen reactions. The experiments of the first part will be carried out at the Advanced Light Source of the Lawrence Berkeley National Laboratory, while those of the second part will be done in the laboratory of the PI's home institution. This research will be done with student participants. The students will acquire knowledge and skills in one of the forefront areas of contemporary physical chemistry. They will thereby be prepared for advanced studies or employment in academia, industry, or national laboratories.

在这个由化学学部实验物理化学项目资助的项目中，芝加哥大学的Laurie J. Butler教授将研究选定的自由基的单分子衰变作为自由基能量的函数。分子束和成像技术将用于进行两组实验。1)第一组将探索在基态电位表面上，异构选择的烃类自由基的竞争单分子解离通道作为解离自由基异构体内能的函数。两个关键的C4H7自由基异构体将被研究。2)第二部分研究了氧-三联体- p +炔反应中碳双自由基中间体的动力学。在氧+乙炔体系中，动力学被认为是通过从三重态到单重态烯烯的系统间交叉进行的。这项工作将探讨系统间交叉在这类双分子反应中的重要性，从而为测试该反应的理论模型提供数据。这项工作也将解决更大的炔+氧反应。第一部分的实验将在劳伦斯伯克利国家实验室的先进光源进行，第二部分的实验将在PI所在机构的实验室进行。这项研究将由学生参与。学生将获得当代物理化学前沿领域之一的知识和技能。因此，他们将为在学术界、工业界或国家实验室深造或就业做好准备。