This grant from the Organic Dynamics Program supports the work of Professor Charles F. Wilcox and Simon H. Bauer at Cornell University. The ability of the "temperature drift technique" to measure the concentrations and energetics of transition structures will be explored. Quantum and molecular mechanics calculations will provide the information needed to identify the vibrational bands produced by the transient species formed in the reaction. Fluxional interconversions involving degenerate sigmatropic rearrangements, for which a range of activation energies have been determined, will be examined. %%% Studies designed to directly observed molecules which are high in energy and structurally intermediate between starting materials and products will be conducted. Molecules which react thermally to form products will be subjected to very short duration high temperature pulses. The ability of the resultant activated material to absorb radiation as it drifts down in temperature will be monitored. This new previously unavailable data will greatly increase our ability to understand how molecules interconvert.
