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

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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.