Selective Evolution of Chemical Reactions on Excited Electronic Potential Energy Surfaces

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With this grant in Experimental Physical Chemistry, Dr. Butler will initiate a series of studies which focus on investigating the nonadiabatic interactions which dominate the evolution of chemical reactions on excited electronic potential energy surfaces. The work will utilize polarized emission spectroscopy, which measures the wavelength and polarization of photons emitted during molecular dissociation, in conjunction with state-selective laser excitation and product detection techniques. The studies are designed to elucidate how the branching between energetically allowed decomposition channels can be critically sensitive to the nature of the electronic surface accessed, and the subsequent intramolecular energy transfer processes and nonadiabatic interactions with other electroinc surfaces during dissociation. The significance of the work lies in the potential for controlling the products of chemical reactions via photoexcitation to particular electronic states. Numerous examples include photoinduced reactions of molecules adsorbed on surfaces, energy transfer in collisions of electronically excited or open shell atoms or molecules, and bimolecular or unimolecular reaction in the gas phase or in solution. As the work explores what molecular structural and dynamical factors allow one to photoinduce a selective chemical reaction which would not occur upon thermal excitation, the results could advance the development of new methods of synthetic chemistry.