TY - JOUR
T1 - Non-adiabatic dynamics of pyrrole
T2 - Dependence of deactivation mechanisms on the excitation energy
AU - Barbatti, Mario
AU - Pittner, Jiří
AU - Pederzoli, Marek
AU - Werner, Ute
AU - Mitrić, Roland
AU - Bonačić-Koutecký, Vlasta
AU - Lischka, Hans
N1 - Funding Information:
This work has been supported by the Austrian Science Fund within the framework of the Special Research Program F16 (Advanced Light Sources) and Project P18411-N19. The authors acknowledge support from the COST action D37. J.P. and M.P. acknowledge the support by the Granting Agency of Academy of Sciences of the Czech Republic (Project No. IAA400400810). This work was partially performed at the Vienna Scientific Cluster (Project No. 70019). U.W. and V.B.K. gratefully acknowledge the financial support by the Deutsche Forschungsgemeinschaft in the frame of SFB 450. R.M. acknowledges the financial support by the Deutsche Forschungsgemeinschaft in the frame of the Emmy-Noether-Programme.
PY - 2010/9/14
Y1 - 2010/9/14
N2 - 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.
AB - 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.
KW - Non-adiabatic dynamics
KW - Pyrrole
KW - Ultrafast phenomena
UR - http://www.scopus.com/inward/record.url?scp=78650646212&partnerID=8YFLogxK
U2 - 10.1016/j.chemphys.2010.07.014
DO - 10.1016/j.chemphys.2010.07.014
M3 - Article
AN - SCOPUS:78650646212
SN - 0301-0104
VL - 375
SP - 26
EP - 34
JO - Chemical Physics
JF - Chemical Physics
IS - 1
ER -