Abstract
We have studied the dynamics of photoexcited tungsten cluster anions \(\mathrm{W}_{n}^{-}\) (n=3,4,…,14) by means of time-resolved two-photon photodetachment spectroscopy. At an excitation energy of hνpump=1.56 eV the photoinduced dynamics is mainly dominated by fast electronic relaxation processes. For the smallest clusters, i.e., \(\mathrm{W}_{3}^{-}\), \(\mathrm{W}_{4}^{-}\), and \(\mathrm{W}_{5}^{-}\), individual relaxation channels have been identified and resolved on a timescale well below 100 fs. The time constants for the decay of nascent and secondary electrons have been deduced from a Bloch model. Complete thermalization takes place for all clusters on a timescale of ∼1 ps.
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