Abstract

One of the goals of condensed phase reaction dynamics is to contrast results from experiments in the gas phase with observations of similar reactions in liquids so as to elucidate the effects of solvation on the kinetics and energy partitioning of simple reactions. To date, there have been few experimental studies having the requisite spectral and temporal resolution to test current theories. Transient infrared spectroscopy has been useful in the study of a variety of unimolecular reactions [1] and recently in a bimolecular reaction that is not diffusion controlled [2]. The present work shows that for products with large reaction exoergicity and sufficient anharmonic shifts in the vibrational coordinate of interest, it is possible to observe highly excited modes in a variety of different reaction schemes, and to measure the nascent vibrational distributions. Such dynamical detail should allow tests of model potential energy surfaces for the condensed phase analogous to Monte Carlo studies of gas phase potential energy surfaces.

© 1994 Optical Society of America