We show using time-dependent density functional theory (TDDFT) that light can be confined into slot waveguide modes residing between individual atomic layers of coinage metals, such as gold. As the top atomic monolayer lifts a few Å off the underlying bulk Au (111), ab initio electronic structure calculations show that for gaps >1.5 Å, visible light squeezes inside the empty slot underneath, giving optical field distributions 2 Å thick, less than the atomic diameter. Paradoxically classical electromagnetic models are also able to reproduce the resulting dispersion for these subatomic slot modes, where light reaches in-plane wavevectors ∼2 nm-1 and slows to <10-2c. We explain the success of these classical dispersion models for gaps ≥1.5 Å due to a quantum-well state forming in the lifted monolayer in the vicinity of the Fermi level. This extreme trapping of light may explain transient "flare" emission from plasmonic cavities where Raman scattering of metal electrons is greatly enhanced when subatomic slot confinement occurs. Such atomic restructuring of Au under illumination is relevant to many fields, from photocatalysis and molecular electronics to plasmonics and quantum optics.
Keywords: flare; nanocavity; nanoparticle; photoluminescence; plasmonics; quantum.