Photoabsorption of Ag(n)(N∼6-6000) nanoclusters formed in helium droplets: transition from compact to multicenter aggregation

Ag(N) clusters with up to thousands of atoms were grown in large He droplets and studied by optical spectroscopy. For N≲10(3) the spectra are dominated by a surface plasmon resonance near 3.8 eV and a broad feature in the UV, consistent with absorption by individual metallic particles. Larger clusters reveal unexpectedly strong broad absorption at low frequencies, extending down to ≈0.5 eV. This suggests a transition from single-center to multicenter formation, in agreement with estimates of cluster growth kinetics in He droplets. Moreover, the spectra of large clusters develop a characteristic dispersion profile at 3.5-4.5 eV, indicative of the coexistence of localized and delocalized electronic excitations in composite clusters, as predicted theoretically.