CaltechAUTHORS
  A Caltech Library Service

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 . https://resolver.caltech.edu/CaltechAUTHORS:20150629-153003387

Full text is not posted in this repository. Consult Related URLs below.

Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20150629-153003387

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.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/j150670a040DOIArticle
http://pubs.acs.org/doi/abs/10.1021/j150670a040PublisherArticle
ORCID:
AuthorORCID
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.
Funders:
Funding AgencyGrant Number
NSFUNSPECIFIED
Other Numbering System:
Other Numbering System NameOther Numbering System ID
Caltech Arthur Amos Noyes Laboratory of Chemical Physics7056
Issue or Number:26
Record Number:CaltechAUTHORS:20150629-153003387
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20150629-153003387
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
Collection:CaltechAUTHORS
Deposited By: Joanne McCole
Deposited On:29 Jun 2015 23:00
Last Modified:22 Nov 2019 09:58

Repository Staff Only: item control page