Ultrafast nuclear dynamics induced by photodetachment of Ag2− and Ag2O2−: oxygen desorption from a molecular silver surface

Abstract

Femtosecond nuclear dynamics of mass-selected neutral Ag₂ and Ag₂O₂ clusters are investigated with the ‘negative ion–to neutral–to positive ion’ (NeNePo) technique. For the bare silver dimer, wave packet dynamics occurring in the neutral electronic ground state and in the first excited triplet state are observed after photodetachment from the anion with 3.05 eV photon energy. While the dynamics in the ground state lead to an oscillatory structure in the NeNePo-pump–probe spectra with a vibrational constant of 185 cm⁻¹, the dynamics in the triplet state are assigned to a bound–free transition leading to dissociation. Photodetachment from the Ag₂O₂⁻ complex results in the desorption of O₂. The experimental data clearly show the influence of the desorbing oxygen ligand on the nuclear dynamics of the silver dimer inducing a red shift in the vibrational frequency and an intensity enhancement of the oscillatory signal.