The photodissociation of Au3 is studied by time-resolved photoelectron spectroscopy using femtosecond laser pulses. The spectra show the time evolution of the electronic structure after photoabsorption. Absorption of a "pump" photon results in the formation of a metastable activated complex (Au3)*, which decays by dissociation into AuT + Au2 and, less favorably, into Au2 + Au 1. Photoelectron spectra recorded with the "probe" laser pulse at increasing delay time first show the spectrum of the intact Au3, then that of the activated complex (Au3)* and, finally, the spectra of the two charged dissociation products AuT and Au2. The lifetime of (Au~)* decreases dramatically with increasing energy of the "pump" photon. © 1998 Elsevier Science B.V.