title: Revisiting the relaxation dynamics of isolated pyrrole.
abstract: Herein, the interpretation of the femtosecond-scale temporal evolution of the pyrrole ion signal, after excitation in the 267-217 nm interval, recently published by our group [R. Montero, A. Peralta Conde, V. Ovejas, M. Fernández-Fernández, F. Castaño, J. R. Vázquez de Aldana, and A. Longarte, J. Chem. Phys. 137, 064317 (2012)] is re-visited. The observation of a shift in the pyrrole(+) transient respect to zero delay reference, initially attributed to ultrafast dynamics on the πσ* type state (3s a1 ← π 1a2), is demonstrated to be caused by the existence of pump + probe populated states, along the ionization process. The influence of these resonances in pump-prone ionization experiments, when multi-photon probes are used, and the significance of a proper zero-time reference, is discussed. The possibility of preparing the πσ* state by direct excitation is investigated by collecting 1 + 1 photoelectron spectra, at excitation wavelengths ranging from 255 to 219 nm. No conclusive evidences of ionization through this state are found.
authors.affiliation: Departamento de Química Física, Universidad del País Vasco (UPV/EHU), Apart. 644, 48080 Bilbao, Spain.
authors.forename: Raúl
authors.initials: R
authors.lastname: Montero
authors.affiliation: Departamento de Química Física, Universidad del País Vasco (UPV/EHU), Apart. 644, 48080 Bilbao, Spain.
authors.forename: Virginia
authors.initials: V
authors.lastname: Ovejas
authors.affiliation: Departamento de Química Física, Universidad del País Vasco (UPV/EHU), Apart. 644, 48080 Bilbao, Spain.
authors.forename: Marta
authors.initials: M
authors.lastname: Fernández-Fernández
authors.affiliation: Centro de Láseres Pulsados (CLPU), Edificio M3, Parque Científico, 37185 Villamayor, Spain.
authors.forename: Álvaro
authors.initials: Á
authors.lastname: Peralta Conde
authors.affiliation: Departamento de Química Física, Universidad del País Vasco (UPV/EHU), Apart. 644, 48080 Bilbao, Spain.
authors.forename: Asier
authors.initials: A
authors.lastname: Longarte