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RRKM and non-RRKM behavior in chemical activation and related studies

Marcus, R. A. and Hase, William L. and Swamy, Kandadai N. (1984) RRKM and non-RRKM behavior in chemical activation and related studies. Journal of Physical Chemistry, 88 (26). pp. 6717-6720. ISSN 0022-3654. doi:10.1021/j150670a040.

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An expression is derived for the pressure dependence of a chemical activation unimolecular rate constant at a fixed total energy and angular momentum in terms of the distribution of unimolecular lifetimes. This rate constant is shown to have a certain insensitivity at low pressures to the form of the lifetime distribution. A kinetic model is then introduced based on a finite rate of intramolecular vibrational energy redistribution. The model provides an analytical explanation of a recent finding in a trajectory calculation for a particular chemical activation system, that the chemical activation unimolecular rate constant at low pressures equals the 7 = 0 microcanonical value even though the unimolecular lifetime distribution is highly non-RRKM. A similar result is predicted for a class of such systems. Implications are described.

Item Type:Article
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Marcus, R. A.0000-0001-6547-1469
Additional Information:© 1984 American Chemical Society. Received July 3, 1984. This research is supported by the National Science Foundation. The collaborative research presented here was initiated at the NATO workshop on “Primary Photophysical Processes” held at Herrsching, FRG, in 1983.
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Caltech Arthur Amos Noyes Laboratory of Chemical Physics7056
Issue or Number:26
Record Number:CaltechAUTHORS:20150629-153003387
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Official Citation:Marcus, R. A., Hase, W. L., & Swamy, K. (1984). RRKM and non-RRKM behavior in chemical activation and related studies. The Journal of Physical Chemistry, 88(26), 6717-6720. doi: 10.1021/j150670a040
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:58685
Deposited By: Joanne McCole
Deposited On:29 Jun 2015 23:00
Last Modified:10 Nov 2021 22:09

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