Naslov
Photodissociation pathways of acetone upon excitation into the 3s Rydberg state: adiabatic versus diabatic mechanism

Autori
Antol, Ivana ; Eckert-Maksić, Mirjana ; Ončák, Milan ; Slavíček, Petr ; Lischka, Hans

Izvornik
Collection of Czechoslovak chemical communications (0010-0765) 73 (2008), 11; 1475-1494

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
Ab initio calculations; acetone; conical intersections; deactivation mechanisms; photochemistry

Sažetak
Photolysis of acetone upon excitation to the 3s Rydberg excited state has been studied by means of high level ab initio methods. The calculations have been performed on multiconfigurational self consistent field (MCSCF) level with a subsequent addition of dynamical correlation both by perturbation theory (CASPT2) and via a configuration interaction expansion up to double excitations (MR-CISD). In addition to the major photoreaction that is well known Norrish type alfa-cleavage, the formation of hydrogen and acetonyl (1-methyloxy or 2-oxopropyl) radical has been discussed. The major question addressed is whether the dynamical processes occur adiabatically on the S_2 surface or diabatically, with non-adiabatic transitions taking place in the course of the reactions.

Izvorni jezik
Engleski

Znanstvena područja
Kemija

POVEZANOST RADA