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

威斯康星大学的Fleming Crim教授在实验物理化学项目的支持下，对气体和液体中状态分解的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研究到液相研究的转变。关于化学反应中振动的最详细信息来自对气体的研究，但大多数工业过程发生在凝聚态。本提案旨在将从气相功学到的选择性振动激发化学原理扩展到液体。PI提出利用飞秒红外吸收光谱技术研究氰化物与甲醇、乙腈和碳酸丙烯的反应，了解反应速率和产物状态，然后加入振动激发来驱动反应。这一提议的一个成功结果将是展示不同的液相双分子反应速率，这取决于赋予反应物的振动激发——以及对差异的机理理解。此外，通过增加新的激发和检测能力，将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它们的化学性质，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。

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.