RRKM and non-RRKM behavior in chemical activation and related studies
Abstract
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.
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.Additional details
- Eprint ID
- 58685
- Resolver ID
- CaltechAUTHORS:20150629-153003387
- NSF
- Created
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2015-06-29Created from EPrint's datestamp field
- Updated
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2021-11-10Created from EPrint's last_modified field
- Other Numbering System Name
- Caltech Arthur Amos Noyes Laboratory of Chemical Physics
- Other Numbering System Identifier
- 7056