Effect of Nanogap Morphology on Plasmon Coupling.

Plasmon coupling is the fundamental principle by which the optical resonances in nanoparticle assemblies are tuned. Interactions of plasmons among nanoparticles in close proximity create plasmon coupling modes whose energies are sensitive to the nanogap parameters. Whereas many studies have focused on the gap distances, we herein probe the effect of gap morphology on plasmon coupling. Dimers that are prepared by adsorbing perfectly round ultrauniform Au nanospheres (AuNSs) onto the faces, edges, and vertices of Au nanocubes (AuNCs) present distinctly different nanogap morphologies. Dark-field single-particle scattering spectroscopy reveals that the longitudinal plasmon coupling mode shifts to lower energies as the AuNS forms a nanogap with parts of the AuNC with higher curvature. Simulation spectra are also consistent with this observation. Our calculations indicate that the much larger charge density at the vertex or edge of a AuNC lowers the plasmon coupling energy through the contribution of the Coulomb interaction when the AuNC combines with the AuNS. In comparison, the plasmon energies or anisotropic polarizability along the face, edge, and vertex directions of a AuNC differ only slightly and thus do not cause a shift in the plasmon coupling mode.