We have performed fully correlated calculations using as a basis set the cc-pV5Z expansion with geometry optimization for the O3H+ moiety and have then calculated the partial cuts of the potential energy surfaces (PESs) for the first two roots using the cc-pDZP basis set expansion. Two electronically induced conical intersections (CIs) were found in the C-s-plane subspaces and one of them was accurately located by calculating the geometric phases for different path integrals. We also discuss the adiabatic versus nonadiabatic effects and suggest a kinetic mechanism for the dynamics of the gas-phase protonation of ozone which includes the role played by the present conical intersections. We also try to provide useful suggestions for the practical search of conical intersections based on a physically guided subspace factorization.
Charge-transfer effects in the gas-phase protonation of ozone: Locating the conical intersections / M. Ceotto, F.A. Gianturco. - In: THE JOURNAL OF CHEMICAL PHYSICS. - ISSN 0021-9606. - 112:13(2000 Apr 01), pp. 5820-5828.
Charge-transfer effects in the gas-phase protonation of ozone: Locating the conical intersections
M. CeottoPrimo
;
2000
Abstract
We have performed fully correlated calculations using as a basis set the cc-pV5Z expansion with geometry optimization for the O3H+ moiety and have then calculated the partial cuts of the potential energy surfaces (PESs) for the first two roots using the cc-pDZP basis set expansion. Two electronically induced conical intersections (CIs) were found in the C-s-plane subspaces and one of them was accurately located by calculating the geometric phases for different path integrals. We also discuss the adiabatic versus nonadiabatic effects and suggest a kinetic mechanism for the dynamics of the gas-phase protonation of ozone which includes the role played by the present conical intersections. We also try to provide useful suggestions for the practical search of conical intersections based on a physically guided subspace factorization.File | Dimensione | Formato | |
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