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Linear arrays of very small Ag nanoparticles (diameter ~10 nm, spacing 0–4 nm) were fabricated in sodalime glass using an ion irradiation technique. Optical extinction spectroscopy of the arrays reveals a large polarization-dependent splitting of the collective plasmon extinction band. Depending on the preparation condition, a redshift of the longitudinal resonance as large as 1.5 eV is observed. Simulations of the three-dimensional electromagnetic field evolution are used to determine the resonance energy of idealized nanoparticle arrays with different interparticle spacings and array lengths. Using these data, the experimentally observed redshift is attributed to collective plasmon coupling in touching particles and/or in long arrays of strongly coupled particles. The simulations also indicate that for closely coupled nanoparticles (1–2 nm spacing) the electromagnetic field is concentrated in nanoscale regions (10 dB radius: 3 nm) between the particles, with a 5000-fold local field intensity enhancement. In arrays of 1-nm-spaced particles the dipolar particle interaction extends to over 10 particles, while for larger spacing the interaction length decreases. Spatial images of the local field distribution in 12-particle arrays of touching particles reveal a particlelike coupled mode with a resonance at 1.8 eV and a wirelike mode at 0.4 eV.

Highly confined electromagnetic fields in arrays of strongly coupled Ag nanoparticles