Binding Angle Robustness of Plasmonic Nanorod Dimer Resonances

Narrow gaps between coupled plasmonic nano‐particles show strong optical field enhancements and spectrally adjustable resonance positions, making them attractive for surface enhanced spectroscopies. Gold nanorod dimers formed from nanorod solutions with narrow size distributions are intensely investigated in this context. However, the binding angle of rods coupled at their end faces is usually not controllable. Surprisingly, it is observed that this has only little effect on field enhancement and resonance energies. In this work, gold nanorod dimers are investigated by mapping their plasmon resonances using electron energy‐loss spectroscopy in a scanning transmission electron microscope. For a wide range of dimer orientations, a negligible influence of the angle between the two rods on the bonding and antibonding longitudinal dipole resonances is confirmed, in good agreement with numerical simulations. The results are interpreted via the predominant end‐coupling of the individual nanorod's plasmonic modes, as illustrated by an analytical charge coupling model. In addition, the simulations emphasize that conclusions from experimental data on the gap morphology on the size range of one nanometer can be ambiguous. In any case, the full understanding of the angle‐invariant resonances of nano‐rod dimers can further promote their controlled application in surface enhanced spectroscopy or ‐sensing. Narrow gaps between gold nanorods show strong optical field enhancement at spectrally adjustable plasmon resonances. The hardly controllable binding angle has little effect on the resonances. Electron energy‐loss spectroscopy in a transmission electron microscopy (TEM) and numerical simulations are applied here to explain this phenomenon. The results suggest the application of the dimers for reproducible surface enhanced spectroscopy.