Abstract
Photodissociation of the Au2Oanion following absorption of a 3.1 eV photon is studied using time-resolved photoelectron spectro- scopy. A new spectral feature appearing after 1 ps indicates the existence of a long-lived excited state with a geometry different from that of the ground state. With further increasing delay the pump-probe feature shifts to higher binding energy. At 7 ± 2 ps after excitation no further shift is observed, but now fragmentation into AuO � + Au and Au � + AuO starts with a time constant of 110 ± 3 ps. The dissociation process is accompanied by a decrease of the excited state feature. The spectra indicate that the delayed onset of fragmen- tation is caused by the time the system needs to reach a new minimum on the excited state potential surface. Hence, the time-resolved photoelectron spectra mirror part of the motion of the anion on the excited state potential surface.
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