Dynamics of Pyrroles Excited to the 3s/πσ* State.

The available experimental data provided by ultrafast dynamics studies of pyrrole and its derivatives in excited states of mixed Rydberg/valence 3s/πσ* character are strongly affected by the interaction with the laser pulses. Understanding these data has constituted an endeavor for several groups during the past few years. Here we apply a simple theoretical model that, including the interaction with the laser pulses, allows one to clarify some aspects of the discrepancies between measurements monitoring different experimental observables. New experimental data on pyrrole, 2,4-dimethylpyrrole, and 2,5-dimethylpyrrole are also provided to check the validity of the model and to gain more insight into the excited state dynamics of pyrrole systems.