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

Bernhard Sellner, Mario Barbatti, Hans Lischka

Research output: Contribution to journalArticlepeer-review

43 Scopus citations

Abstract

The photochemical ring opening process in pyrrole has been investigated by performing classical on-the-fly dynamics using the multiconfiguration self-consistent field 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, determined previously [Barbatti, J. Chem. Phys. 125, 164323 (2006)], has been chosen. Two sets of initial conditions for the nuclear velocities were constructed: (i) nuclear velocities in the branching (g,h) plane of the conical intersection and (ii) statistical distribution for all atoms. Both sets of initial conditions show very similar results. Reactive trajectories are only found in a very limited sector in the (g,h) plane and reaction products are very similar. 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- C3 H3) is observed. The computed structural data correlate well with the experimentally observed dissociation products.

Original languageEnglish
Article number024312
JournalJournal of Chemical Physics
Volume131
Issue number2
DOIs
StatePublished - 2009

Fingerprint Dive into the research topics of 'Dynamics starting at a conical intersection: Application to the photochemistry of pyrrole'. Together they form a unique fingerprint.

Cite this