Ideal Dimers of Gold Nanospheres for Precision Plasmonics: Synthesis and Characterization at the Single‐Particle Level for Identification of Higher Order Modes

Abstract Ideal dimers comprising gold nanoparticles with a smooth surface and high sphericity are synthesized by a substrate‐based assembly strategy with efficient cetyltrimethylammonium bromide removal. An unprecedented structural and plasmonic uniformity at the single‐particle level is observed since inhomogeneities resulting from variations in gap morphology are eliminated. Single ideal dimers are analyzed by polarization‐resolved dark‐field scattering spectroscopy. Contributions from transverse as well as quadrupolar and octupolar longitudinal plasmon coupling modes can be discriminated because of their orthogonal polarization behavior. The assignment of these higher order coupling modes is supported by computer simulations.