State-to-state unimolecular reaction dynamics of highly vibrationally excited molecules

This article presents recent work investigating the unimolecular dissociation rates of quantum state-selected molecules. Such studies provide the most stringent test for quantitative models of unimolecular reactions and their assumptions. After briefly reviewing the various experimental and theoretical techniques for state-resolved unimolecular dissociation rates, we present results obtained in our laboratory using the method of double resonance overtone photofragment spectroscopy. We focus on the unimolecular dissociation of HOCl as a textbook case in which the dissociation rate is limited by slow intramolecular vibrational energy redistribution and give a simple model to treat this particular class of systems.


Published in:
CHEMICAL SOCIETY REVIEWS, 30, 4, 214-225
Year:
2001
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 Record created 2005-12-15, last modified 2018-03-17


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