Close encounters between two nanoshells.

Plasmonic nanoparticle pairs known as "dimers" embody a simple system for generating intense nanoscale fields for surface enhanced spectroscopies and for developing an understanding of coupled plasmons. Individual nanoshell dimers in directly adjacent pairs and touching geometries show dramatically different plasmonic properties. At close distances, hybridized plasmon modes appear whose energies depend extremely sensitively on the presence of a small number of molecules in the interparticle junction.

Simultaneous measurements of electronic conduction and Raman response in molecular junctions.

Electronic conduction through single molecules is affected by the molecular electronic structure as well as by other information that is extremely difficult to assess, such as bonding geometry and chemical environment. The lack of an independent diagnostic technique has long hampered single-molecule conductance studies. We report simultaneous measurement of the conductance and the Raman spectra of nanoscale junctions used for single-molecule electronic experiments.

Plasmonic nanoclusters: a path towards negative-index metafluids.

We introduce the concept of metafluids-liquid metamaterials based on clusters of metallic nanoparticles which we will term Artificial Plasmonic Molecules (APMs). APMs comprising four nanoparticles in a tetrahedral arrangement have isotropic electric and magnetic responses and are analyzed using the plasmon hybridization (PH) method, an electrostatic eigenvalue equation, and vectorial finite element frequency domain (FEFD) electromagnetic simulations. With the aid of group theory, we identify the resonances that provide the strongest electric and magnetic response and study them as a function of separation between spherical nanoparticles.

Nanoparticle-mediated coupling of light into a nanowire.

We show that a nanoparticle can serve as an efficient antenna for coupling of visible light into propagating plasmons of an Ag nanowire. For long wires, the coupling is maximal for incident light polarized perpendicular to the nanowire. For sub-10-mum nanowires, the polarization corresponding to maximum emission from the ends of the nanowire was found to be strongly dependent on the nanowire geometry and position of the vicinal nanoparticle.

Plasmon modes of curvilinear metallic core/shell particles.

The plasmon hybridization method is generalized to calculate the plasmon modes and optical properties of solid and dielectric-core/metallic-shell particles of geometrical structures that can be described using separable curvilinear coordinates. The authors present a detailed discussion of the plasmonic properties of hollow metallic nanowires with dielectric cores and core/shell structures of oblate and prolate spheroidal shapes. They show that the plasmon frequencies of these particles can be expressed in a common form and that the plasmon modes of the core/shell structures can be viewed as resulting from the hybridization of the solid particle plasmons associated with the outer surface of the shell and of the cavity plasmons associated with the inner surface.

Electromigrated nanoscale gaps for surface-enhanced Raman spectroscopy.

Single-molecule detection with chemical specificity is a powerful and much desired tool for biology, chemistry, physics, and sensing technologies. Surface-enhanced spectroscopies enable single-molecule studies, yet reliable substrates of adequate sensitivity are in short supply. We present a simple, scaleable substrate for surface-enhanced Raman spectroscopy (SERS) incorporating nanometer-scale electromigrated gaps between extended electrodes.

Plasmon resonances of a gold nanostar.

Using the finite-difference time-domain method, we show that the plasmons of a nanostar result from hybridization of plasmons of the core and tips of the nanoparticle. The nanostar core serves as a nanoscale antenna, dramatically increasing the excitation cross section and the electromagnetic field enhancements of the tip plasmons. Our analysis demonstrates that the plasmon hybridization picture can be combined with numerical approaches to interpret the physical origin of the plasmons of highly complex nanostructures.

Plasmonic nanostructures: artificial molecules.

This Account describes a new paradigm for the relationship between the geometry of metallic nanostructures and their optical properties. While the interaction of light with metallic nanoparticles is determined by their collective electronic or plasmon response, a compelling analogy exists between plasmon resonances of metallic nanoparticles and wave functions of simple atoms and molecules. Based on this insight, an entire family of plasmonic nanostructures, artificial molecules, has been developed whose optical properties can be understood within this picture: nanoparticles (nanoshells, nanoeggs, nanomatryushkas, nanorice), multi-nanoparticle assemblies (dimers, trimers, quadrumers), and a nanoparticle-over-metallic film, an electromagnetic analog of the spinless Anderson model.

Plasmon hybridization in nanoshells with a nonconcentric core.

We apply the plasmon hybridization method to a nanoshell with a nonconcentric (offset) core and investigate how the energy and excitation cross section of the plasmon modes depend on the offset distance D of the inner core from the nanoshell center. A two-center spherical coordinate system is used for mathematical convenience. It is shown that the presence of an offset core shifts the plasmon energies and makes higher multipolar nanoshell plasmons dipole active and visible in the optical spectrum.

Controlled texturing modifies the surface topography and plasmonic properties of Au nanoshells.

We report a facile and controllable method for the postfabrication texturing of the surface topography of Au nanoshells based on site-selective chemical etching of the polycrystalline Au nanoshell surface by a bifunctional alkanethiol molecule, cysteamine. This nanoscale surface texturing process systematically introduces dramatic changes to the plasmonic properties of the Au nanoshells. The modification of the plasmon resonant properties of nanoshells as a function of increased surface roughness was examined experimentally and modeled theoretically using three-dimensional finite difference time domain (FDTD) simulations.

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.

Symmetry breaking in individual plasmonic nanoparticles.

The plasmon resonances of a concentric metallic nanoshell arise from the hybridization of primitive plasmon modes of the same angular momentum on its inner and outer surfaces. For a nanoshell with an offset core, the reduction in symmetry relaxes these selection rules, allowing for an admixture of dipolar components in all plasmon modes of the particle. This metallodielectric nanostructure with reduced symmetry exhibits a core offset-dependent multipeaked spectrum, seen in single-particle spectroscopic measurements, and exhibits significantly larger local-field enhancements on its external surface than the equivalent concentric spherical nanostructure.

Plasmon modes of nanosphere trimers and quadrumers.

Using the plasmon hybridization method, we investigate the plasmon frequencies and optical absorption spectra of symmetric configurations of nanosphere trimers and quadrumers. Plasmon hybridization allows us to express the fundamental plasmon modes of these multinanosphere systems as linear combinations of the plasmons of individual nanospheres in a manner analogous to molecular orbital theory. We show how group theory may be used to interpret the plasmon modes of each multiparticle system as specific structure-dependent symmetric combinations of the plasmon modes of the individual nanoparticles.

Nanorice: a hybrid plasmonic nanostructure.

We have designed and fabricated a new hybrid nanoparticle that combines the intense local fields of nanorods with the highly tunable plasmon resonances of nanoshells. This dielectric core-metallic shell prolate spheroid nanoparticle bears a remarkable resemblance to a grain of rice, inspiring the name "nanorice". This geometry possesses far greater structural tunability than either a nanorod or a nanoshell, along with much larger local field intensity enhancements and far greater sensitivity as a surface plasmon resonance (SPR) nanosensor than any dielectric-metal nanostructures reported previously.

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.

Surface-enhanced Raman scattering from individual au nanoparticles and nanoparticle dimer substrates.

Surface-enhanced Raman scattering (SERS) intensities for individual Au nanospheres, nanoshells, and nanosphere and nanoshell dimers coated with nonresonant molecules are measured, where the precise nanoscale geometry of each monomer and dimer is identified through in situ atomic force microscopy. The observed intensities correlate with the integrated quartic local electromagnetic field calculated for each specific nanostructure geometry. In this study, we find that suitably fabricated nanoshells can provide SERS enhancements comparable to nanosphere dimers.

Plasmon hybridization in nanoshell dimers.

We extend the plasmon hybridization method to investigate the plasmon modes of metallic nanoshell dimers. The formalism is also generalized to include the effects of dielectric backgrounds. It is shown that the presence of dielectrics shifts the plasmon resonances of the individual nanoparticles to lower energies and screens their interaction in the dimer configuration.

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.

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.

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.

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.