State-Resolved and Bond-Selected Bimolecular Reactions in Gases and Liquids

气体和液体中的状态分辨和键选择双分子反应

• 批准号: 9985317
• 负责人: F. Fleming Crim
• 金额: $ 50.1万
• 依托单位: University of Wisconsin-Madison
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2000
• 资助国家: 美国
• 起止时间: 2000-05-01 至 2003-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=9985317&HistoricalAwards=false
• 关键词: State; Resolved; Bond; Selected; Bimolecular

Professor Fleming Crim of the University of Wisconsin is supported by the Experimental Physical Chemistry program to perform experimental studies on state-resolved bimolecular reactions in gases and liquids. Specific vibrations will be studied that lead to chemical reactions. This field has been active for some twenty years, and Professor Crim's work represents a transition in this field from gas phase to liquid phase studies. The most detailed information on vibrations in chemical reactions comes from studies of gases, but most industrial processes occur in the condensed phase. This proposal seeks to extend the principles about selective vibrational excitation chemistry learned from gas phase work to liquids. The PI proposes to study the reaction of cyanide with methanol, acetonitrile and propylene carbonate using femtosecond IR absorption spectroscopy, learning about rates and product states, and then to add vibrational excitation to drive the reaction. A successful outcome of this proposal would be demonstration of different liquid phase bimolecular reaction rates depending on the vibrational excitation imparted to the reactants -- and a mechanistic understanding of the differences. In addition, development of gas phase methodology for more complex molecules will be continued by adding new excitation and detection capabilities. Understanding how vibrations of molecules affect their chemistry will allow control of the course of chemical reactions. Successful control of chemical reactions using light could have exciting implications in industrial synthesis, reducing the need for toxic catalysts or solvents.

威斯康星州大学的弗莱明·克里姆教授得到实验物理化学计划的支持，对气体和液体中的状态分辨双分子反应进行实验研究。 将研究导致化学反应的特定振动。 这一领域已经活跃了大约二十年，Crim教授的工作代表了这一领域从气相到液相研究的过渡。 关于化学反应中振动的最详细的信息来自对气体的研究，但大多数工业过程都发生在凝聚相中。 该建议旨在将从气相工作学到的关于选择性振动激发化学的原理扩展到液体。 PI建议使用飞秒红外吸收光谱研究氰化物与甲醇，乙腈和碳酸丙烯酯的反应，了解速率和产物状态，然后添加振动激发来驱动反应。 这一建议的一个成功的结果将是不同的液相双分子反应速率取决于振动激发赋予反应物的演示-和差异的机械理解。 此外，将通过增加新的激发和检测能力，继续开发用于更复杂分子的气相方法。 了解分子的振动如何影响其化学性质将有助于控制化学反应的过程。 利用光成功控制化学反应可能对工业合成产生令人兴奋的影响，减少对有毒催化剂或溶剂的需求。