Quantum mechanical calculation of the rate constant for the reaction H+O[sub 2]→OH+O - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Journal of Chemical Physics Année : 1998

Quantum mechanical calculation of the rate constant for the reaction H+O[sub 2]→OH+O

Résumé

Quantum rate calculations for the H+O2→HO+OH+O2→HO+O combustion reaction, as well as for the reverse reaction, are reported. Using the DMBE IV potential energy surface, the cumulative reaction probability N0(E)N0(E) has been directly computed for total angular momentum J=0, by means of the Seideman, Manthe and Miller Lanczos-based absorbing boundary condition method [J. Chem. Phys. 96, 4412 (1992); 99, 3411 (1993)]. Special attention has been paid to the definition of the molecular basis set, and to the sensitivity of the results to the absorbing potentials used in the asymptotic regions. The N0(E) results show very good overall agreement with the coupled channel calculations of Pack et al. [J. Chem. Phys. 102, 5998 (1995)], although the highly oscillatory behavior just above threshold renders such a comparison difficult in that energy range. The behavior of the J≠0 cumulative reaction probability has been estimated from calculations using the Jz-conserving approximation for J values in the range 10–70. This allowed us to define which reference geometry should be used in the J-shifting approximation, in order to compute the cumulative reaction probability NJ(E) for any J value. By imposing conservation of the total energy within this approximation, the rate constants are shown to display better agreement with the experimental results.

Mots clés

Fichier principal
Vignette du fichier
Number01.pdf (241.74 Ko) Télécharger le fichier
Origine : Fichiers éditeurs autorisés sur une archive ouverte
Loading...

Dates et versions

hal-01117492 , version 1 (10-07-2017)

Identifiants

Citer

Alexandra Viel, Claude Leforestier, William H. Miller. Quantum mechanical calculation of the rate constant for the reaction H+O[sub 2]→OH+O. Journal of Chemical Physics, 1998, 108 (9), pp.3489-3497. ⟨10.1063/1.475776⟩. ⟨hal-01117492⟩
43 Consultations
81 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More