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High resolution infrared spectroscopy as a tool to measure chemical reaction dynamics

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Abstract

Both intra- and intermolecular interactions play an important role in determining the potential surface for a chemical reaction. Such interactions determine both physical structure and chemical reactivity. High resolution infrared spectroscopy has been used to probe both molecular structure and vibrationally induced chemistry. 2-fluorethanol is an example of a molecule in which the strong attractive interactions between F and the OH moity not only determine the lowest energy conformation of the molecule, but also the most efficient vibrational excitation for inducing conformational isomerization. An analogue of 2-fluoroethanol, 1,2-difluoroethane, although similar in structure, has quite different intramolecular interactions. These differences are apparent in both the isomerization dynamics and the spectroscopy. Spectra were measured using a color center laser with optothermal detection (resolution = 10-4 cm-1). The spectra of these molecules allow us to link vibrational mode-coupling to chemical reactivity.

© 1991 Optical Society of America

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