Non-adiabatic dynamics of pyrrole: Dependence of deactivation mechanisms on the excitation energy

0347014 - ÚFCH JH 2011 RIV NL eng J - Článek v odborném periodiku
Barbatti, M. - Pittner, Jiří - Pederzoli, Marek - Werner, U. - Mitrić, R. - Bonačić-Koutecký, V. - Lischka, H.
Non-adiabatic dynamics of pyrrole: Dependence of deactivation mechanisms on the excitation energy.
Chemical Physics. Roč. 375, č. 1 (2010), s. 26-34. ISSN 0301-0104. E-ISSN 1873-4421
Grant CEP: GA AV ČR IAA400400810
Výzkumný záměr: CEZ:AV0Z40400503
Klíčová slova: non-adiabatic dynamics * ultrafast phenomena * pyrrole
Kód oboru RIV: CF - Fyzikální chemie a teoretická chemie
Impakt faktor: 2.017, rok: 2010

Non-adiabatic dynamics simulations were performed for pyrrole at time-dependent density functional theory level using the trajectory surface hopping approach. Initial conditions were prepared based on the UV-absorption spectrum so as to simulate monochromatic absorption in three distinct spectral regions. The results showed predominance of the NH-stretch mechanism for excited-state relaxation. With increasing initial energy, however, other mechanisms are activated as well, even though they still occurred for a minor fraction of the trajectories. Dynamics starting at the origin of the absorption spectrum exhibited internal conversion to the ground state with a time constant of 20 fs. In contrast, dynamics starting at higher energies gave rise to much longer time constants for internal conversion near 200 fs.
Trvalý link: http://hdl.handle.net/11104/0187890