Modeling and measuring plasmonic excitations in hollow spherical gold nanoparticles.

We investigate molecular plasmonic excitations sustained in hollow spherical gold nanoparticles using time-dependent density functional theory (TD-DFT). Specifically, we consider Au60 spherical, hollow molecules as a toy model for single-shell plasmonic molecules. To quantify the plasmonic character of the excitations obtained from TD-DFT, the energy-based plasmonicity index is generalized to the framework of DFT, validated on simple systems such as the sodium Na20 chain and the silver Ag20 compound, and subsequently successfully applied to more complex molecules. We also compare the quantum mechanical TD-DFT simulations to those obtained from a classical Mie theory that relies on macroscopic electrodynamics to model the light-matter interaction. This comparison allows us to distinguish those features that can be explained classically from those that require a quantum-mechanical treatment. Finally, a double-shell system obtained by placing a C60 buckyball inside the hollow spherical gold particle is further considered. It is found that the double-shell, while increasing the overall plasmonic character of the excitations, leads to significantly lowered absorption cross sections.

From single-particle-like to interaction-mediated plasmonic resonances in graphene nanoantennas.

Plasmonic nanostructures attract tremendous attention as they confine electromagnetic fields well below the diffraction limit while simultaneously sustaining extreme local field enhancements. To fully exploit these properties, the identification and classification of resonances in such nanostructures is crucial. Recently, a novel figure of merit for resonance classification has been proposed1 and its applicability was demonstrated mostly to toy model systems. This novel measure, the energy-based plasmonicity index (EPI), characterizes the nature of resonances in molecular nanostructures. The EPI distinguishes between either a single-particle-like or a plasmonic nature of resonances based on the energy space coherence dynamics of the excitation. To advance the further development of this newly established measure, we present here its exemplary application to characterize the resonances of graphene nanoantennas. In particular, we focus on resonances in a doped nanoantenna. The structure is of interest, as a consideration of the electron dynamics in real space might suggest a plasmonic nature of selected resonances in the low doping limit but our analysis reveals the opposite. We find that in the undoped and moderately doped nanoantenna, the EPI classifies all emerging resonances as predominantly single-particle-like and only after doping the structure heavily, the EPI observes plasmonic response.