Intramolecular Dynamics of Organic Reactions

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With the support of the Organic and Macromolecular Chemistry Program, Professor Barry K. Carpenter, of the Department of Chemistry and Chemical Biology at Cornell University, is studying the intramolecular dynamics of organic reactions. Through a combination of ab initio electronic structure theory, molecular dynamics simulations, and experimental organic chemistry, Professor Carpenter addresses the question of what factors control the behavior of reactive intermediates, including radical ions, carbenes, and biradicals, generated in thermal and photochemical reactions. Specific questions under investigation include what controls the behavior of molecules that encounter bifurcation points on their reaction paths; what controls the potential energy well depth in which an intermediate finds itself, and how does the reaction dynamics depend on the well depth; what theoretical methods can be developed to allow nonexperts to explore the dynamic issues of an organic reaction mechanism; and what kinds of experimental evidence provide the clearest distinction between traditional transition state theory (TST) behavior and behavior governed by non-TST dynamics.Development of a detailed, fundamental understanding of how organic reactions occur requires a combination of experimental and theoretical/calculational approaches, with theory suggesting important molecules for synthesis and study and with the study of various organic reactions in turn suggesting theoretical approaches and/or advances necessary to understand them. Professor Barry K. Carpenter, of the Deparment of Chemistry and Chemical Biology at Cornell University, carries out both synthetic and theoretical studies designed to address the reactivity of highly reactive intermediates, of only fleeting existence, generated in the course of chemical reactions. Through these studies, Professor Carpenter contributes to our fundamental understanding of how molecules react and provides calculational tools applicable by others in the continuing advancement of knowledge about organic chemical reactions.