With funding from the Organic Dynamics Program in the Chemistry Division, Professor John Baldwin of Syracuse University will study the characteristics of chemical reactions involving diradical intermediates or transition states. The stereochemistry of the isomerizations of several small, strained ring compounds will be determined using deuterium, or occasionally carbon-13, labels as stereochemical markers. The small systems proposed for study allow for high quality quantum mechanical computations of the appropriate hypersurfaces, which in turn allows a uniquely detailed comparison between theory and experiment for organic reactions. Understanding of the simplest, and the most straightforward appearing, chemical reactions at a level of great detail is a way to understand the very nature of chemical reactivity. This work provides the experimental foundation for eventual quantum mechanical understanding of simple thermal molecular rearrangements.
