Time-resolved photoelectron spectroscopy of $\mathrm{Al}₃\mathrm{O}₃^-$ : photoisomerization versus photofragmentation

In general, clusters are unstable and in many cases several metastable isomers exist even at low temperature. Therefore, a cluster may react with a dramatic geometry change to a small disturbance such as a weak field or to the absorption of a low-energy photon. Here, we study the response of \(\mathrm{Al}₃\mathrm{O}₃^-\) to photoexcitation using time-resolved photoelectron spectroscopy. Earlier experimental and theoretical studies suggested that this cluster anion undergoes a geometry change after photoexcitation. In contrast, our time-resolved spectra indicate that photoexcitation triggers ultra-fast fragmentation. This example demonstrates that ultra-fast processes in clusters are not well understood and that it is still difficult to gain reliable experimental data about such processes.