The H + CO ⇌ HCO reaction studied by ab ...
Type de document :
Compte-rendu et recension critique d'ouvrage
DOI :
PMID :
Titre :
The H + CO ⇌ HCO reaction studied by ab initio benchmark calculations.
Auteur(s) :
Peters, Phillip S [Auteur]
Institut de Planétologie et d'Astrophysique de Grenoble [IPAG ]
Physico-Chimie Moléculaire Théorique [PCMT]
Duflot, Denis [Auteur]
Physico-Chimie Moléculaire Théorique [PCMT]
Wiesenfeld, Laurent [Auteur]
Institut de Planétologie et d'Astrophysique de Grenoble [IPAG ]
Toubin, Céline [Auteur]
Physico-Chimie Moléculaire Théorique [PCMT]
Institut de Planétologie et d'Astrophysique de Grenoble [IPAG ]
Physico-Chimie Moléculaire Théorique [PCMT]
Duflot, Denis [Auteur]
Physico-Chimie Moléculaire Théorique [PCMT]
Wiesenfeld, Laurent [Auteur]
Institut de Planétologie et d'Astrophysique de Grenoble [IPAG ]
Toubin, Céline [Auteur]
Physico-Chimie Moléculaire Théorique [PCMT]
Titre de la revue :
The Journal of Chemical Physics
Pagination :
164310
Éditeur :
American Institute of Physics
Date de publication :
2013-10-28
ISSN :
0021-9606
Discipline(s) HAL :
Chimie/Chimie théorique et/ou physique
Résumé en anglais : [en]
: The title reaction has been calculated using complete active space self-consistent field and internally contracted multi-reference configuration interaction, including Davidson correction, calculations. Dunning's correlation ...
Lire la suite >: The title reaction has been calculated using complete active space self-consistent field and internally contracted multi-reference configuration interaction, including Davidson correction, calculations. Dunning's correlation consistent atomic basis sets, together with several complete basis set extrapolation schemes, were employed. Core-valence and scalar relativistic effects were also taken into account, as well as anharmonicity of the vibrational modes. Core-valence correlation appears to have a large impact on the calculated frequencies, spectroscopic constants, and on the energetics. In particular, the best estimate for the HCO (DCO) formation barrier height at 0 K, 4.54 ± 0.14 (4.43 ± 0.14) kcal mol(-1) is larger than previous theoretical works and well above the usually accepted value of 2.0 ± 0.4 kcal mol(-1), measured at room temperature. Inclusion of temperature and entropy at 298 K does not seem to be able to solve this discrepancy. The present theoretical barrier height is therefore the recommended value. The exo-ergicity of the HCO (DCO) dissociation reaction, predicted to be -13.36 ± 0.57 (-14.72 ± 0.57) kcal mol(-1), is slightly below the experimental value. Finally, all tested density functionals fail to reproduce accurately both the formation and dissociation barriers.Lire moins >
Lire la suite >: The title reaction has been calculated using complete active space self-consistent field and internally contracted multi-reference configuration interaction, including Davidson correction, calculations. Dunning's correlation consistent atomic basis sets, together with several complete basis set extrapolation schemes, were employed. Core-valence and scalar relativistic effects were also taken into account, as well as anharmonicity of the vibrational modes. Core-valence correlation appears to have a large impact on the calculated frequencies, spectroscopic constants, and on the energetics. In particular, the best estimate for the HCO (DCO) formation barrier height at 0 K, 4.54 ± 0.14 (4.43 ± 0.14) kcal mol(-1) is larger than previous theoretical works and well above the usually accepted value of 2.0 ± 0.4 kcal mol(-1), measured at room temperature. Inclusion of temperature and entropy at 298 K does not seem to be able to solve this discrepancy. The present theoretical barrier height is therefore the recommended value. The exo-ergicity of the HCO (DCO) dissociation reaction, predicted to be -13.36 ± 0.57 (-14.72 ± 0.57) kcal mol(-1), is slightly below the experimental value. Finally, all tested density functionals fail to reproduce accurately both the formation and dissociation barriers.Lire moins >
Langue :
Anglais
Vulgarisation :
Non
Source :