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

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 et al., 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 center dot-CH=CH center dot 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. (C) 2009 American Institute of Physics. [DOI: 10.1063/1.3175799]