Plasmons do not go that quantum

Abstract

We develop a theoretical model of the surface plasmon resonance of metallic nanospheres in the size range down to the single nanometer size. Within this model we explicitly show how different microscopic mechanisms, namely quantization due to size (QSE) and electron spill-out, affect the energy of the surface plasmon. We demonstrate, that electron spill-out effects, which can move the surface plasma energy both toward the red or the blue, can be comparable to or even stronger than QSE. Thus, depending on circumstances, QSE may only be observed for ultrasmall metal nanoparticles much closer to 1 nm in size than to 10 nm. Results presented herein are in quantitative agreement with recent published experimental results for Ag and Au.