First-Principles Computational Visualization of Localized Surface Plasmon Resonance in Gold Nanoclusters

Cluster-size dependence of localized surface plasmon resonance (LSPR) for Aun nanoclusters (n = 54, 146, 308, 560, 922, 1414) is investigated by using our recently developed computational program of first-principles calculations for photoinduced electron dynamics in nanostructures. The size of Au-1414 (3.9 nm in diameter) is unprecedentedly large in comparison with those addressed in previous first-principles calculations of optical response in nanoclusters. These computations enable us to clearly see that LSPR gradually grows and the LSPR peaks red shift with increasing cluster size. The growth of LSPR is visualized in real space, demonstrating that electron charge distributions oscillate in a collective manner around the outermost surface region of the clusters. We further illustrate that the core d electrons screen the collective oscillation of the conduction-like s electrons.