Light-induced release of DNA from gold nanoparticles: nanoshells and nanorods.

Plasmon-resonant nanoparticle complexes show highly promising potential for light-triggered, remote-controlled delivery of oligonucleotides on demand, for research and therapeutic purposes. Here we investigate the light-triggered release of DNA from two types of nanoparticle substrates: Au nanoshells and Au nanorods. Both light-triggered and thermally induced release are distinctly observable from nanoshell-based complexes, with light-triggered release occurring at an ambient solution temperature well below the DNA melting temperature. Surprisingly, no analogous measurable release was observable from nanorod-based complexes below the DNA melting temperature. These results suggest that a nonthermal mechanism may play a role in plasmon resonant, light-triggered DNA release.

On the energy shift between near-field and far-field peak intensities in localized plasmon systems.

The localized plasmons of metallic nanoparticles and nanostructures are known to display an interesting and apparently universal phenomenon: upon optical excitation, the maximum near-field enhancements occur at lower energies than the maximum of the corresponding far-field spectrum. Here we present an explanation for this behavior, showing that it results directly from the physics of a driven and damped harmonic oscillator. We show that the magnitude of the shift between the near- and far-field peak intensities depends directly on the total damping of the system, whether it is intrinsic damping within the metal of the nanoparticle or radiative damping of the localized plasmon.

Quantum plasmonics: optical properties and tunability of metallic nanorods.

The plasmon resonances in metallic nanorods are investigated using fully quantum mechanical time-dependent density functional theory. The computed optical absorption curves display well-defined longitudinal and transverse plasmon resonances whose energies depend on the aspect ratio of the rods, in excellent agreement with classical electromagnetic modeling. The field enhancements obtained from the quantum mechanical calculations, however, differ significantly from classical predictions for distances shorter than 0.5 nm from the nanoparticle surfaces. These deviations can be understood as arising from the nonlocal screening properties of the conduction electrons at the nanoparticle surface.

Quantum description of the plasmon resonances of a nanoparticle dimer.

Using time-dependent density functional theory, we present a fully quantum mechanical investigation of the plasmon resonances in a nanoparticle dimer as a function of interparticle separation. We show that for dimer separations below 1 nm quantum mechanical effects, such as electron tunneling across the dimer junction and screening, significantly modify the optical response and drastically reduce the electromagnetic field enhancements relative to classical predictions. For larger separations, the dimer plasmons are well described by classical electromagnetic theory.