Ultrafast Kinetic Studies of Molecular Rearrangements

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With this renewal award, the Organic and Macromolecular Chemistry Program continues its support of the work of Professor Kevin S. Peters of the Department of Chemistry at the University of Colorado, Boulder, CO. The research will extend the PI's research using femtosecond, picosecond, and nanosecond transient absorption spectroscopy to study the real time dynamics of chemical reactions. Systems to be investigated include 1,2 and 1,3 hydride and deuteride shifts in carbocations, 1,2 alkyl shifts in carbocations, and the dynamics of proton/deuteron transfer in a variety of substituted benzophenones/N,N-diallylaniline radical ion pairs. The results of these kinetic studies will be analyzed within the context of adiabatic and non-adiabatic rearrangements in order to assess the validity of transition state theory for describing the dynamics of charge displacement reactions in the condensed phase.These studies of the dynamics of proton and hydride transfer are expected provide important fundamental information that will impact on theoretical and experimental treatments of such reactions in organic, physical, and biological chemistry.