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 Au$_{60}$ 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 Na$_{20}$ chain and the silver Ag$_{20}$ 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 C$_{60}$ 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.