Mechanistic and Exploratory Organic Photochemistry

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This project continues a variegated mechanistic organic research program that touches upon several aspects in the field. These include investigations of the chemistry of excited state organic molecules, where it remains to be determined if radiationless decay to alternative products or energy barriers on the excited state hypersurface govern the course of events. Methods used to probe these questions include quantum mechanical, theoretical, and experimental chemistry. A different endeavor involves the case where a reacting molecule is imbedded in a cavity of limited and irregular size. Conformational constraints then alter the otherwise observed course of the reaction. With this Award, the Organic and Macromolecular Chemistry Program continues support for the research of Professor Howard E. Zimmerman of the University of Wisconsin at Madison. Professor Zimmerman's research activities are in the area of mechanistic organic chemistry, which involves making close observations of chemical reactions under a variety of conditions in order to determine precisely how they occur. Since one cannot directly observe molecules as they react, one must devise other means of deducing these events. Particular emphasis in Professor Zimmerman's laboratories is given to reactions that are initiated by the absorption of light, and of molecules that are trapped within crystals.