Robust subnanometric plasmon ruler by rescaling of the nonlocal optical response.

We present the optical response of two interacting metallic nanowires calculated for separation distances down to angstrom range. State-of-the-art local and nonlocal approaches are compared with full quantum time-dependent density functional theory calculations that give an exact account of nonlocal and tunneling effects. We find that the quantum results are equivalent to those from classical approaches when the nanoparticle separation is defined as the separation between centroids of the screening charges. This establishes a universal plasmon ruler for subnanometric distances. Such a ruler not only impacts the basis of many applications of plasmonics, but also provides a robust rule for subnanometric metrology.

Quantum plasmonics: nonlinear effects in the field enhancement of a plasmonic nanoparticle dimer.

A fully quantum mechanical investigation using time-dependent density functional theory reveals that the field enhancement in a coupled nanoparticle dimer can be strongly affected by nonlinear effects. We show that both classical as well as linear quantum mechanical descriptions of the system fail even for moderate incident light intensities. An interparticle current resulting from the strong field photoemission tends to neutralize the plasmon-induced surface charge densities on the opposite sides of the nanoparticle junction. Thus, the coupling between the two nanoparticles and the field enhancement is reduced as compared to linear theory. A substantial nonlinear effect is revealed already at incident powers of 10(9) W/cm(2) for interparticle separation distances as large as 1 nm and down to the touching limit.

Bethe-hole polarization analyser for the magnetic vector of light.

The nature of light as an electromagnetic wave with transverse components has been confirmed using optical polarizers, which are sensitive to the orientation of the electric field. Recent advances in nanoscale optical technologies demand their magnetic counterpart, which can sense the orientation of the optical magnetic field. Here we report that subwavelength metallic apertures on infinite plane predominantly sense the magnetic field of light, establishing the orientation of the magnetic component of light as a separate entity from its electric counterpart. A subwavelength aperture combined with a tapered optical fibre probe can also serve as a nanoscale polarization analyser for the optical magnetic field, analogous to a nanoparticle sensing the local electric polarization. As proof of its functionality, we demonstrate the measurement of a magnetic field orientation that is parallel to the electric field, as well as a circularly polarized magnetic field in the presence of a linearly polarized electric field.

Quantum plexcitonics: strongly interacting plasmons and excitons.

We present a fully quantum mechanical approach to describe the coupling between plasmons and excitonic systems such as molecules or quantum dots. The formalism relies on Zubarev's Green functions, which allow us to go beyond the perturbative regime within the internal evolution of a plasmonic nanostructure and to fully account for quantum aspects of the optical response and Fano resonances in plasmon-excition (plexcitonic) systems. We illustrate this method with two examples consisting of an exciton-supporting quantum emitter placed either in the vicinity of a single metal nanoparticle or in the gap of a nanoparticle dimer. The optical absorption of the combined emitter-dimer structure is shown to undergo dramatic changes when the emitter excitation level is tuned across the gap-plasmon resonance. Our work opens a new avenue to deal with strongly interacting plasmon-excition hybrid systems.

Optical spectroscopy of conductive junctions in plasmonic cavities.

The optical properties of a nanoparticle dimer bridged by a conductive junction depend strongly on the junction conductivity. As the conductivity increases, the bonding dimer plasmon blueshifts and broadens. For large conductance, a low energy charge transfer plasmon also appears in the spectra with a line width that decreases with increasing conductance. A simple physical model for the understanding of the spectral feature is presented. Our finding of a strong influence of junction conductivity on the optical spectrum suggests that plasmonic cavities might serve as probes of molecular conductance at elevated frequencies not accessible through electrical measurements.

Plasmons in the metallic nanoparticle-film system as a tunable impurity problem.

We show that the plasmon resonances of a metallic nanoparticle interacting with the surface plasmons of a metallic film is an electromagnetic analogue of the spinless Anderson-Fano model. This is the same model used to describe the interaction of a localized electronic state with a continuous band of electronic states. The three characteristic regimes of this model are realized here, where the energy of the nanoparticle plasmon resonance lies above, within, or below the energy band of surface plasmon states. These three interaction regimes are controlled by film thickness. The latter regime is experimentally observed and identified.

Finite-difference time-domain studies of the optical properties of nanoshell dimers.

The optical properties of metallic nanoshell dimers are investigated using the finite difference time domain (FDTD) method. We discuss issues of numerical convergence specific for the dimer system. We present results for both homodimers and heterodimers. The results show that retardation effects must be taken into account for an accurate description of realistic size nanoparticle dimers. The optical properties of the nanoshell dimer are found to be strongly polarization dependent. Maximal coupling between the nanoshells in a dimer occurs when the electric field of the incident pulse is aligned parallel to the dimer axis. The wavelengths of the peaks in the extinction cross section of the dimer are shown to vary by more than 100 nm, depending on the incident electric field polarization. The calculations show that electric field enhancements in the dimer junctions depend strongly on dimer separation. The maximum field enhancements occur in the dimer junction and at the expense of a reduced electric field enhancement in other regions of space. We investigate the usefulness of nanoshell dimers substrates for SERS by integrating the fourth power of the electric field enhancements around the surfaces of the nanoparticles as a function of dimer separation and wavelength. The SERS efficiency is shown to depend strongly on dimer separation but much weaker than the fourth power of the maximum electric field enhancement at a particular point. The SERS efficiency is also found to depend strongly on the wavelength of the incident light. Maximum SERS efficiency occurs for resonant excitation of the dimer plasmons.

First principles resonance widths for Li near an Al(001) surface: predictions of scattered ion neutralization probabilities.

By combining a first-principles periodic density functional theory calculation of adsorbate resonance widths with a many-body dynamical theory of charge transfer, we assess charge-transfer rates for ions scattering off metal surfaces. This goes beyond previous approaches, which have been limited to modeling the surfaces with either static potentials or finite clusters. Here we consider Li(+) scattering from an Al(001) surface. We show how the Li 2s orbital hybridizes with metal valence bands, near the surface, increasing the width of the 2s energy level. This in turn affects the charge-transfer rates between the ion and the metal surface. Our predictions for Li(+)-Al(001) scattering yield the correct angular dependence of the fraction of neutral Li atoms formed when compared to experiment.

Plasmon hybridization in spherical nanoparticles.

We show that the plasmon resonances in single metallic nanoshells and multiple concentric metallic shell particles can be understood in terms of interaction between the bare plasmon modes of the individual surfaces of the metallic shells. The interaction of these elementary plasmons results in hybridized plasmons whose energy can be tuned over a wide range of optical and infrared wavelengths. The approach can easily be generalized to more complex systems, such as dimers and small nanoparticle aggregates.

A hybridization model for the plasmon response of complex nanostructures.

We present a simple and intuitive picture, an electromagnetic analog of molecular orbital theory, that describes the plasmon response of complex nanostructures of arbitrary shape. Our model can be understood as the interaction or "hybridization" of elementary plasmons supported by nanostructures of elementary geometries. As an example, the approach is applied to the important case of a four-layer concentric nanoshell, where the hybridization of the plasmons of the inner and outer nanoshells determines the resonant frequencies of the multilayer nanostructure.

The effect of water on the Fe(3+)/Fe(2+) reduction potential of heme.

Hemeproteins can act as catalysts, oxygen carriers or electron conductors. The ferric/ferrous reduction potential E(m7) of iron in the center of the prosthetic group ranges from negative values for peroxidases to an extreme positive value for cytochrome a(3) with Hb and Mb in the middle [1]. Proteins exercise their influence on E(m7) in several ways: via substituents at the periphery of the chelate structure, via the proximal ligand, and via interaction with the surrounding medium, amino acid side chains, or polar solvents. Work on recombined proteins and 2,4-substituted free hemes documented that the first two effects are additive [2]. For the third effect, models of the dielectric media on a molecular level have been successfully applied [3-5]. E(m7) has also been empirically correlated to the degree of heme exposure to water [6-8]. The apoprotein/porphyrin and water/porphyrin interfaces are complementary since water molecules fill any empty space in the crevice and surround any pertinent part of heme outside the protein boundary. The present work links to this idea by a combination of statistical mechanics simulations and quantum mechanical calculations comparing heme in water with heme in an apolar environment. Our results show that polarization of the porphyrin pi-electron cloud by the field from water dipoles influences E(m7). The dominant effect of this and other determinates of iron electron availability is perturbations of delocalized electron density in the porphyrin chelate, reproduced by a model where the prosthetic group is treated as a disc of uniform electron density. The present work is also of interest since the interfacial energy constitutes the main barrier for heme-protein separation [9-11].

Ionization of xenon Rydberg atoms at a metal surface.

Experiments in which a thermal-energy beam of xenon Rydberg atoms is directed at near grazing incidence onto a flat Au(111) surface are described that provide new insight into charge transfer and electron tunneling during atom/surface interactions. Analysis of the data shows that for the present range of principal quantum number n, 13 < or = n < or = 20, ionization occurs at an atom/surface separation Z(i) = (4.5+/-0.9)n2a0, where n2a0 is the Bohr radius of the atom. This result is in good agreement with the value Z(i) approximately 3.8n2a0 predicted by ab initio hydrogenic theory.

Unraveling nanotubes: field emission from an atomic wire.

Field emission of electrons from individually mounted carbon nanotubes has been found to be dramatically enhanced when the nanotube tips are opened by laser evaporation or oxidative etching. Emission currents of 0.1 to 1 microampere were readily obtained at room temperature with bias voltages of less than 80 volts. The emitting structures are concluded to be linear chains of carbon atoms, Cn, (n = 10 to 100), pulled out from the open edges of the graphene wall layers of the nanotube by the force of the electric field, in a process that resembles unraveling the sleeve of a sweater.