Reference : Role of angular momentum conservation in unimolecular translational energy release: Vali...
Scientific journals : Article
Physical, chemical, mathematical & earth Sciences : Chemistry
Physical, chemical, mathematical & earth Sciences : Physics
http://hdl.handle.net/2268/122081
Role of angular momentum conservation in unimolecular translational energy release: Validity of the orbiting transition state theory
English
Gridelet, Evelyne [> > > >]
Lorquet, Jean-Claude [Université de Liège - ULg > Services généraux (Faculté des sciences) > Relations académiques et scientifiques (Sciences) >]
Leyh, Bernard mailto [Université de Liège - ULg > Département de chimie (sciences) > Laboratoire de dynamique moléculaire >]
2005
Journal of Chemical Physics
Amer Inst Physics
122
9
94106
Yes (verified by ORBi)
International
0021-9606
Melville
[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.
http://hdl.handle.net/2268/122081

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