Angular momentum coupling in simple-fission transition states

Karas, A.J. and Gilbert, R.G. (1992) Angular momentum coupling in simple-fission transition states. Journal of Physical Chemistry, 96 26: 10893-10898. doi:10.1021/j100205a053


Author Karas, A.J.
Gilbert, R.G.
Title Angular momentum coupling in simple-fission transition states
Journal name Journal of Physical Chemistry   Check publisher's open access policy
ISSN 0022-3654
1541-5740
Publication date 1992-12
Sub-type Article (original research)
DOI 10.1021/j100205a053
Volume 96
Issue 26
Start page 10893
End page 10898
Total pages 6
Place of publication Washington, DC, United States
Publisher American Chemical Society
Language eng
Abstract An efficient means is deduced for calculating RRKM microscopic reaction rates for simple-fission transition states by using a Hamiltonian consisting of the separate Hamiltonians for each moiety (A and B), hard-sphere interactions between A and B, and symmetric tops connected by a light rigid rod; the reaction coordinate is the breaking bond. This extension of the simple Gorin model takes exact account of the angular-momentum coupling between A and B and of the transition-state requirement that the density of states of the activated complex be evaluated with the reaction coordinate held fixed. Evaluation for typical systems shows that the simpler treatment where A and B are treated as independent rotors is both accurate and in accord with experiment, if both are small but breaks down when A and/or B are large. In the latter case, the variational calculation gives a rate coefficient that is highly sensitive to the assumed hard-sphere radii; although the model cannot then be used meaningfully for a priori prediction of experiment, it provides a useful means of fitting extant data to predict falloff behavior.
Keyword Potential-energy surfaces
Adiabatic channel model
Unimolecular processes
Recombination
Coordinate
Looseness
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Non-UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: School of Chemistry and Molecular Biosciences
Centre for Nutrition and Food Sciences Publications
 
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