Extended ab initio calculations are carried out for the isolated ozone molecule, in its ground electronic state, and for its protonated adduct. For both systems, the corresponding nuclear geometries of lowest total energies are obtained by multidimensional optimization and different levels of basis set quality and correlation correction are examined in the two cases. The final results provide very good accord between gas-phase protonation energy data and calculated quantities. The extensive numerical experiments clearly underline the need for balanced correlation treatments in systems where both static and dynamic correlation effects are important. They further indicate that the existing kinetics experiments on the gas-phase proton affinity of O-3 are not likely to involve the electron transfer channel via a sampling of the conical intersection configuration space that exists in this system.
Gas-phase proton affinity of ozone : a computational test of the experimental mechanism / M. Ceotto, F.A. Gianturco. - In: JOURNAL OF MOLECULAR STRUCTURE. THEOCHEM. - ISSN 0166-1280. - 543(2001 Jun 22), pp. 115-122.
Gas-phase proton affinity of ozone : a computational test of the experimental mechanism
M. CeottoPrimo
;
2001
Abstract
Extended ab initio calculations are carried out for the isolated ozone molecule, in its ground electronic state, and for its protonated adduct. For both systems, the corresponding nuclear geometries of lowest total energies are obtained by multidimensional optimization and different levels of basis set quality and correlation correction are examined in the two cases. The final results provide very good accord between gas-phase protonation energy data and calculated quantities. The extensive numerical experiments clearly underline the need for balanced correlation treatments in systems where both static and dynamic correlation effects are important. They further indicate that the existing kinetics experiments on the gas-phase proton affinity of O-3 are not likely to involve the electron transfer channel via a sampling of the conical intersection configuration space that exists in this system.File | Dimensione | Formato | |
---|---|---|---|
1-s2.0-S0166128000008502-main.pdf
accesso riservato
Tipologia:
Publisher's version/PDF
Dimensione
101.05 kB
Formato
Adobe PDF
|
101.05 kB | Adobe PDF | Visualizza/Apri Richiedi una copia |
Pubblicazioni consigliate
I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.