With this new award, the Organic and Macromolecular Chemistry Program supports the research of Professor David M. Birney of the Department of Chemistry and Biochemistry at Texas Tech University, Lubbock, TX. The research will examine the potential energy surfaces for a variety of organic reactions using a combination of experimental and computational techniques. A major thrust of the experimental work will involve multiphoton infrared photolysis/thermolysis (MP-IR) investigations designed to identify new reaction pathways and intermediates. The advantages MP-IR include the ability to selectively excite reactant thereby avoiding product isomerization, the potential to observe higher energy reaction pathways, and the ability to drive endothermic reactions. Systems to be investigated include Diels-Alder reactions, carbene extrusions, and sigmatropic rearrangements. Possible symmetry constraints on vibrational energy relaxation in MP-IR induced reactions will also be studied. The research will include computational investigations of ionic and radical induced Bergman and related cyclizations as well as experiments designed to examine reactions whose potential energy surfaces contain sequential transition states in which different reaction paths can be followed. These investigations are expected provide important fundamental information that will facilitate attempts to achieve additional selectivity in organic reactions.
