Linear and Nonlinear Spectroscopy of Unimolecular Dynamics

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In this project supported by the Experimental Physical Chemistry Program of the Chemistry Division, Patrick Vaccaro of Yale University will study the unimolecular reaction dynamics of several small to medium-sized molecules using a variety of linear and nonlinear spectroscopic techniques. Earlier work on unimolecular transformations in S2O and on intramolecular hydrogen bonding and proton transfer in malonaldehyde will be extended, the structure unimolecular transformations in the cyanogen family will be examined in detail, and transformations between isomers in the cyanogen family, CNNC, CNCN, and CNNC will be studied. Experimental findings will be compared to calculations using new theoretical methods. Various degenerate four-wave mixing (DFWM) techniques will be developed and quantified, including Cavity Ring-Down Spectroscopy (CRDS). The proposed activities will advance the knowledge and the understanding of unimolecular dynamics and the interpretation of signals derived from linear and nonlinear optical measurements. The investigations undertaken in this project will help increase understanding of molecular behavior that plays a basic and important role in a variety of chemical and biological processes. For example, the sequence of bond reorganization events that occur during chemical syntheses can be elucidated, allowing chemists to devise more efficient routes to a desired product. The knowledge of structural preferences of molecules with bonds that can freely rotate impacts the understanding of protein folding in molecules of biological importance.