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Adiabatic decoupling of the reaction coordinate
Lorquet, Jean-Claude
2008In International Journal of Quantum Chemistry, 108 (10), p. 1629-1636
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Keywords :
Adiabatic invariance; Ion-molecule reactions; Maximum entropy; Translational energy distributions; Reaction dynamics; Effective potentials; Dynamical constraints; Reaction coordinate (RC); Reaction paths
Abstract :
[en] When the dynamics is constrained by adiabatic invariance, a reactive process can be described as a one-dimensional motion along the reaction coordinate in an effective potential. This simplification is often valid for central potentials and for the curved harmonic valley studied in the reaction path Hamiltonian model. For an ionolecule reaction, the action integral < Pθ> = (1/2π){clockwise contour integral}P θdθ is an adiabatic invariant. The Poisson bracket of <Pθ>2 with Hamiltonians corresponding to a great variety of long-range electrostatic interactions is found to decrease with the separation coordinate r, faster than the corresponding potential. This indicates that the validity of the adiabatic approximation is not directly related to the shape of the potential energy surface. The leading role played by the translational momentum is accounted for by Jacobi's form of the least action principle. However, although the identification of adiabatic regions by this procedure is limited to a specific range of coordinate configurations, equivalent constraints must persist all along the reaction coordinate and must operate during the entire reaction, as a result of entropy conservation. The study of the translational kinetic energy released on the fragments is particularly appropriate to detect restrictions on energy exchange between the reaction coordinate and the bath of internal degrees of freedom. ©2008 Wiley Periodicals, Inc.
Disciplines :
Chemistry
Author, co-author :
Lorquet, Jean-Claude ;  Université de Liège > Relations académiques et scientifiques (Sciences)
Language :
English
Title :
Adiabatic decoupling of the reaction coordinate
Publication date :
2008
Event name :
33 ème Congrès des Chimistes Théoriciens d'Expression Latine (CHITEL33)
Event place :
La Habana, Cuba
Event date :
du 17 septembre 2007 au 21 septembre 2007
Audience :
International
Journal title :
International Journal of Quantum Chemistry
ISSN :
0020-7608
eISSN :
1097-461X
Publisher :
John Wiley & Sons, Hoboken, United States - New Jersey
Volume :
108
Issue :
10
Pages :
1629-1636
Peer reviewed :
Peer Reviewed verified by ORBi
Available on ORBi :
since 05 October 2015

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