Fingerprinting the Hidden Facets of Plasmonic Nanocavities.

The optical properties of nanogap plasmonic cavities formed by a NanoParticle-on-Mirror (NPoM, or patch antenna) are determined here, across a wide range of geometric parameters including the nanoparticle diameter, gap refractive index, gap thickness, facet size and shape. Full understanding of the confined optical modes allows these nanocavities to be utilized in a wide range of experiments across many fields. We show that the gap thickness t and refractive index n are spectroscopically indistinguishable, accounted for by a single gap parameter G = n/t 0.47. Simple tuning of mode resonant frequencies and strength is found for each quasi-normal mode, revealing a spectroscopic "fingerprint" for each facet shape, on both truncated spherical and rhombicuboctahedral nanoparticles. This is applied to determine the most likely nanoscale morphology of facets hidden below each NPoM in experiment, as well as to optimize the constructs for different applications. Simple scaling relations are demonstrated, and an online tool for general use is provided.