Article (Scientific journals)
The Elimination of Redundant Constraints in Surprisal Analysis of Unimolecular Dissociation and Other Endothermic Processes
Remacle, Françoise; Levine, Raphaël David
2009In Journal of Physical Chemistry. A, 113 (16), p. 4658-4664
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Abstract :
[en] It is well understood that energy rich polyatomic molecules do not dissociate promptly because the number, P, of their energy states far exceeds the number, N, of the decay channels. In the simplest RRK theory, the fraction N/P is the probability of dissociation. We discuss the distribution of the decay rates of maximal entropy and conclude that it is governed by at most N linearly independent constraints, N < P, or, more typically, N << P. This mathematical requirement already severely restricts the number of constraints. Beyond it however, on physical grounds, one constraint, or at most a few, may be dominant. We discuss why just one constraint, or a few but less than N, can be sufficient to describe the product state distribution.
Disciplines :
Chemistry
Author, co-author :
Remacle, Françoise  ;  Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de chimie physique théorique
Levine, Raphaël David
Language :
English
Title :
The Elimination of Redundant Constraints in Surprisal Analysis of Unimolecular Dissociation and Other Endothermic Processes
Publication date :
2009
Journal title :
Journal of Physical Chemistry. A
ISSN :
1089-5639
eISSN :
1520-5215
Publisher :
American Chemical Society, Washington, United States - District of Columbia
Volume :
113
Issue :
16
Pages :
4658-4664
Peer reviewed :
Peer Reviewed verified by ORBi
Available on ORBi :
since 05 January 2010

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