Article (Scientific journals)
Role of angular momentum conservation in unimolecular translational energy release: Validity of the orbiting transition state theory
Gridelet, Evelyne; Lorquet, Jean-Claude; Leyh, Bernard
2005In Journal of Chemical Physics, 122 (9), p. 94106
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Abstract :
[en] The translational kinetic energy release distribution (KERD) for the halogen loss reaction of the bromobenzene and iodobenzene cations has been reinvestigated on the microsecond time scale. Two necessary conditions of validity of the orbiting transition state theory (OTST) for the calculation of kinetic energy release distributions (KERDs) have been formulated. One of them examines the central ion-induced dipole potential approximation. As a second criterion, an adiabatic parameter is derived. The lower the released translational energy and the total angular momentum, the larger the reduced mass, the rotational constant of the molecular fragment, and the polarizability of the released atom, the more valid is the OTST. Only the low-energy dissociation of the iodobenzene ion (E approximately 0.45 eV, where E is the internal energy above the reaction threshold) is found to fulfill the criteria of validity of the OTST. The constraints that act on the dissociation dynamics have been studied by the maximum entropy method. Calculations of entropy deficiencies (which measure the deviation from a microcanonical distribution) show that the pair of fragments does not sample the whole of the phase space that is compatible with the mere specification of the internal energy. The major constraint that results from conservation of angular momentum is related to a reduction of the dimensionality of the dynamics of the translational motion to a two-dimensional space. A second and minor constraint that affects the KERD leads to a suppression of small translational releases, i.e., accounts for threshold behavior. At high internal energies, the effects of curvature of the reaction path and of angular momentum conservation are intricately intermeddled and it is not possible to specify the share of each effect.
Disciplines :
Chemistry
Physics
Author, co-author :
Gridelet, Evelyne
Lorquet, Jean-Claude ;  Université de Liège - ULiège > Services généraux (Faculté des sciences) > Relations académiques et scientifiques (Sciences)
Leyh, Bernard  ;  Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de dynamique moléculaire
Language :
English
Title :
Role of angular momentum conservation in unimolecular translational energy release: Validity of the orbiting transition state theory
Publication date :
2005
Journal title :
Journal of Chemical Physics
ISSN :
0021-9606
eISSN :
1089-7690
Publisher :
Amer Inst Physics, Melville, United States - New York
Volume :
122
Issue :
9
Pages :
94106
Peer reviewed :
Peer Reviewed verified by ORBi
Available on ORBi :
since 16 May 2012

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