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

Mario Barbatti, Jiří Pittner, Marek Pederzoli, Ute Werner, Roland Mitrić, Vlasta Bonačić-Koutecký, Hans Lischka

Research output: Contribution to journalArticlepeer-review

106 Scopus citations

Abstract

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.

Original languageEnglish
Pages (from-to)26-34
Number of pages9
JournalChemical Physics
Volume375
Issue number1
DOIs
StatePublished - Sep 14 2010

Keywords

  • Non-adiabatic dynamics
  • Pyrrole
  • Ultrafast phenomena

Fingerprint Dive into the research topics of 'Non-adiabatic dynamics of pyrrole: Dependence of deactivation mechanisms on the excitation energy'. Together they form a unique fingerprint.

Cite this