Spectral signatures of charge transfer in assemblies of molecularly-linked plasmonic nanoparticles.

Self-assembly of functionalized nanoparticles (NPs) provides a unique class of nanomaterials for exploring and utilizing quantum-plasmonic effects that occur if the interparticle separation between NPs approaches a few nanometers and below. We review recent theoretical and experimental studies of plasmon coupling in self-assembled NP structures that contain molecular linkers between the NPs. Charge transfer through the interparticle gap of an NP dimer results in a significant blue-shift of the bonding dipolar plasmon (BDP) mode relative to classical electromagnetic predictions, and gives rise to new coupled plasmon modes, the so-called charge transfer plasmon (CTP) modes. The blue-shift of the plasmon spectrum is accompanied by a weakening of the electromagnetic field in the gap of the NPs. Due to an optical far-field signature that is sensitive to charge transfer across the gap, plasmonic molecules represent a sensor platform for detecting and characterizing gap conductivity in an optical fashion and for characterizing the role of molecules in facilitating the charge transfer across the gap.