Dynamics starting at a conical intersection: Application to the photochemistry of pyrrole

0333457 - ÚOCHB 2010 RIV US eng J - Journal Article
Sellner, B. - Barbatti, M. - Lischka, Hans
Dynamics starting at a conical intersection: Application to the photochemistry of pyrrole.
Journal of Chemical Physics. Roč. 131, č. 2 (2009), 024312/1-024312/10. ISSN 0021-9606. E-ISSN 1089-7690
R&D Projects: GA MŠMT LC512
Institutional research plan: CEZ:AV0Z40550506
Keywords : on-the-fly ab initio dynamics * opening process in pyrrole * conical intersection
Subject RIV: CF - Physical ; Theoretical Chemistry
Impact factor: 3.093, year: 2009

The photochemical ring opening process in pyrrole has been investigated by means of on-the-fly dynamics using the MSCSC method for the computation of energies and energy gradients. As starting point for the dynamics the conical intersection corresponding to the ring-puckered ring-opened structure has been chosen. Within the simulation time of 1 ps, ring opening of pyrrole to the biradical NH=CH–CH•–CH=CH• chain followed by ring closure to a substituted cyclopropene structure (NH=CH–C3H3) is observed. The computed structural data correlate well with the experimentally observed dissociation products.
Permanent Link: http://hdl.handle.net/11104/0178431