Ab initio dynamic study of the reaction of Cl2LaR (R=H, CH3) with H2.
In this paper, a comparison between "static" and "dynamic" determination of the thermodynamic (DeltarF degrees) and kinetic data (DeltarF#) for the reaction of Cl2LaR (R=H, CH3) and H2 is given. A difference is obtained in the case of the reaction between Cl2LaH and H2 and can be attributed to a failure of the "static" approach based on the harmonic approximation. The influence of the zero point energy correction is also analyzed but does not explain the 30% difference between the two calculated activation energies. The influence of the flatness of the potential energy surface around the transition state is proved as no such an effect is observed for the reaction of Cl2LaCH3 and H2.
Raynaud
Christophe
C
Laboratoire de Physique Quantique (UMR 5626), IRSAMC, Université Paul Sabatier, 118 Route de Narbonne, 31062 Toulouse Cedex 4, France.
Daudey
Jean-Pierre
JP
Jolibois
Franck
F
Maron
Laurent
L
D003198:Computer Simulation; D006859:Hydrogen / Q000737:chemistry*; D007700:Kinetics; D028581:Lanthanoid Series Elements / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D011789:Quantum Theory; D013816:Thermodynamics
D028581:Lanthanoid Series Elements; D009942:Organometallic Compounds; D006859:Hydrogen