Light Extinction by Agglomerates of Gold Nanoparticles: A Plasmon Ruler for Sub-10 nm Interparticle Distances

Plasmon rulers relate the shift of resonance wavelength, λ_l, of gold agglomerates to the average distance, s, between their constituent nanoparticles. These rulers are essential for monitoring the dynamics of biomolecules (e.g., proteins and DNA) by determining their small (<10 nm) coating thickness. However, existing rulers for dimers and chains estimate coating thicknesses smaller than 10 nm with rather large errors (more than 200%). Here, the light extinction of dimers, 7- and 15-mers of gold nanoparticles with diameter d_p = 20-80 nm and s = 1-50 nm is simulated. Such agglomerates shift λ_l up to 680 nm due to plasmonic coupling, in excellent agreement with experimental data by microscopy, dynamic light scattering, analytical centrifugation, and UV-visible spectroscopy. Subsequently, a new plasmon ruler is derived for gold nanoagglomerates that enables the accurate determination of sub-10 nm coating thicknesses, in excellent agreement also with tedious microscopy measurements.