Reference : Wave packet dynamics along bifurcating reaction paths
Scientific journals : Article
Physical, chemical, mathematical & earth Sciences : Chemistry
Physical, chemical, mathematical & earth Sciences : Physics
http://hdl.handle.net/2268/30175
Wave packet dynamics along bifurcating reaction paths
English
Lasorne, Benjamin [> > > >]
Dive, Georges mailto [Université de Liège - ULg > > Centre d'ingénierie des protéines >]
Lauvergnat, David [> > > >]
Desouter, Michèle mailto [Université de Liège - ULg > Département de chimie (sciences) > Département de chimie (sciences) >]
1-Apr-2003
Journal of Chemical Physics
Amer Inst Physics
118
13
5831-5840
Yes (verified by ORBi)
International
0021-9606
Melville
[en] The problem of bifurcating reaction paths is revisited by wave packet (WP) dynamics. The pitchfork model connecting five stationary points-a reactive, two transition structures and two enantiomeric products-is characterized by a Valley Ridge inflection point (VRI) where WP could leave the standard intrinsic reaction path. We question the role of such a VRI point to determine whether the mechanism is sequential or concerted. WP simulations on two-dimensional minimum energy surfaces are carried out in the benchmark case of the methoxy radical isomerization H3CO-->H2COH. The ab initio potential energy surface (PES) is fitted to an analytical model which is bent to analyze the incidence of geometrical parameters on the WP behavior. For each of these generated PES, the WP width in the entrance valley is the main factor which conditions the behavior on the unstable ridge. The WP evolution is also analyzed in terms of nonadiabatic transitions among adiabatic channels along the reaction coordinate. Finally, the location of VRI points according to an invariant definition is discussed. (C) 2003 American Institute of Physics.
Researchers ; Professionals
http://hdl.handle.net/2268/30175

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