RESUMO
The ultrafast relaxation dynamics of tetracene following UV excitation to the bright singlet state S6 has been studied with time-resolved photoelectron spectroscopy. With the help of high-level ab initio multireference perturbation theory calculations, we assign photoelectron signals to intermediate dark electronic states S3, S4, and S5 as well as to a low-lying electronic state S2. The energetic structure of these dark states has not been determined experimentally previously. The time-dependent photoelectron yields assigned to the states S6, S5, and S4 have been analyzed and reveal the depopulation of S6 within 60 fs, while S5 and S4 are populated with delays of about 50 and 80 fs. The dynamics of the lower-lying states S3 and S2 seem to agree with a delayed population coinciding with the depopulation of the higher-lying states S4-S6 but could not be elucidated in full detail due to the low signal levels of the corresponding two-photon ionization probe processes.
RESUMO
We present a compact design for a velocity-map imaging spectrometer for energetic electrons and ions. The standard geometry by Eppink and Parker [Rev. Sci. Instrum. 68, 3477 (1997)] is augmented by just two extended electrodes so as to realize an additional einzel lens. In this way, for a maximum electrode voltage of 7 kV, we experimentally demonstrate imaging of electrons with energies up to 65 eV. Simulations show that energy acceptances â²270 and â²1200 eV with an energy resolution ΔE∕Eâ²5% are achievable for electrode voltages ≤20 kV when using diameters of the position-sensitive detector of 42 and 78 mm, respectively.