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

作者：Barbatti Mario^*; Pittner Jiri; Pederzoli Marek; Werner Ute; Mitric Roland; Bonacic Koutecky Vlasta; Lischka Hans

来源：Chemical Physics, 2010, 375(1): 26-34.

DOI：10.1016/j.chemphys.2010.07.014

• Non-adiabatic dynamics
• Ultrafast phenomena
• Pyrrole

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.

• 出版日期2010-9-14