Laser Chemistry

Laser Chemistry / 1995 / Article
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Molecular Energy Transfer and Reaction Dynamics in Japan: Part 1

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Volume 15 |Article ID 059696 | https://doi.org/10.1155/1995/59696

Kiyohiko Someda, Hiroki Nakamura, Frederick H. Mies, "Competition Between Intramolecular Vibrational Energy Re-Distribution and Unimolecular Dissociation: A Scattering Theoretical Point of View", Laser Chemistry, vol. 15, Article ID 059696, 12 pages, 1995. https://doi.org/10.1155/1995/59696

Competition Between Intramolecular Vibrational Energy Re-Distribution and Unimolecular Dissociation: A Scattering Theoretical Point of View

Received15 Mar 1994

Abstract

Systematic behavior of decay rates of resonances above dissociation threshold is investigated by using the theory of resonance scattering. The condition for the Rice-Ramsperger-Kassel-Marcus (RRKM) rate formula to be valid is clarified by analyzing the random model of unimolecular dissociation. The decay rate averaged over many resonances agrees with the RRKM rate when the mean spacing and the mean width of the resonance states coincide with each other. On the other hand, auto- and mutual-correlation functions of the non-stationary wave functions indicate a rather paradoxical and intriguing phenomenon: In the RRKM regime, insufficient time is left for intramolecular vibrational energy redistribution (IVR) before dissociation.

Copyright © 1995 Hindawi Publishing Corporation. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.


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