Particle Size-Dependent Onset of the Tunneling Regime in Ideal Dimers of Gold Nanospheres

We report on the nanoparticle-size-dependent onset of quantum tunneling of electrons across the subnanometer gaps in three different sizes (30, 50, and 80 nm) of highly uniform gold nanosphere (AuNS) dimers. For precision plasmonics, the gap distance is systematically controlled at the level of single C-C bonds via a series of alkanedithiol linkers (C₂-C₁₆). Parallax-corrected high-resolution transmission electron microscope (HRTEM) imaging and subsequent tomographic reconstruction are employed to resolve the nm to subnm interparticle gap distances in AuNS dimers. Single-particle scattering experiments on three different sizes of AuNS dimers reveal that for the larger dimers the onset of quantum tunneling regime occurs at larger gap distances: 0.96 ± 0.04 nm (C₆) for 80 nm, 0.83 ± 0.03 nm (C₅) for 50 nm, and 0.72 ± 0.02 nm (C₄) for 30 nm dimers. 2D nonlocal and quantum-corrected model (QCM) calculations qualitatively explain the physical origin for this experimental observation: the lower curvature of the larger particles leads to a higher tunneling current due to a larger effective conductivity volume in the gap. Our results have possible implications in scenarios where precise geometrical control over plasmonic properties is crucial such as in hybrid (molecule-metal) and/or quantum plasmonic devices. More importantly, this study constitutes the closest experimental results to the theory for a 3D sphere dimer system and offers a reference data set for comparison with theory/simulations.