Tailoring Plasmon Coupling in Self-Assembled One-Dimensional Au Nanoparticle Chains through Simultaneous Control of Size and Gap Separation.

We investigated the near- and far-field response of one-dimensional chains of Au nanoparticles (NPs) fabricated with high structural control through template guided self-assembly. We demonstrate that the density of polyethylene glycol (PEG) ligands grafted onto the NP surface, in combination with the buffer conditions, facilitate a systematic variation of the average gap width (g) at short separations of g<1.1nm. The overall size (n) of the cluster was controlled through the template. The ability to independently vary n and g allowed for a rational tuning of the spectral response in individual NP clusters over a broad spectral range. We used this structural control for a systematic investigation of the electromagnetic coupling underlying the superradiant cluster mode. Independent of the chain length, plasmon coupling is dominated by direct neighbor interactions. A decrease in coupling strength at separations ≲0.5nm indicates the presence of non-local and/or quantum mechanical coupling mechanisms.