Wave packet dynamics along bifurcating reaction paths

[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.

Disciplines :

Chemistry
Physics

Author, co-author :

Lasorne, Benjamin

Dive, Georges ; Université de Liège - ULiège > Centre d'ingénierie des protéines

Lauvergnat, David

Desouter, Michèle ; Université de Liège - ULiège > Département de chimie (sciences) > Département de chimie (sciences)

Language :

English

Title :

Wave packet dynamics along bifurcating reaction paths

Publication date :

01 April 2003

Journal title :

Journal of Chemical Physics

ISSN :

0021-9606

eISSN :

1089-7690

Publisher :

Amer Inst Physics, Melville, United States - New York

Volume :

118

Issue :

Pages :

5831-5840

Peer reviewed :

Peer Reviewed verified by ORBi

Available on ORBi :

since 30 November 2009

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