Surface plasmons are waves that propagate along the surface of a conductor. By altering the structure of a metal's surface, the properties of surface plasmons--in particular their interaction with light--can be tailored, which offers the potential for developing new types of photonic device. This could lead to miniaturized photonic circuits with length scales that are much smaller than those currently achieved. Surface plasmons are being explored for their potential in subwavelength optics, data storage, light generation, microscopy and bio-photonics.

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Surface plasmon subwavelength optics

This article reviews the current status of lattice-dynamical calculations in crystals, using density-functional perturbation theory, with emphasis on the plane-wave pseudopotential method. Several specialized topics are treated, including the implementation for metals, the calculation of the response to macroscopic electric fields and their relevance to long-wavelength vibrations in polar materials, the response to strain deformations, and higher-order responses. The success of this methodology is demonstrated with a number of applications existing in the literature.

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Phonons and related crystal properties from density-functional perturbation theory

In 1978 it was discovered, largely through the work of Fleischmann, Van Duyne, Creighton, and their coworkers that molecules adsorbed on specially prepared silver surfaces produce a Raman spectrum that is at times a millionfold more intense than expected. This effect was dubbed surface-enhanced Raman scattering (SERS). Since then the effect has been demonstrated with many molecules and with a number of metals, including Cu, Ag, Au, Li, Na, K, In, Pt, and Rh. In addition, related phenomena such as surface-enhanced second-harmonic generation, four-wave mixing, absorption, and fluorescence have been observed. Although not all fine points of the enhancement mechanism have been clarified, the majority view is that the largest contributor to the intensity amplification results from the electric field enhancement that occurs in the vicinity of small, interacting metal particles that are illuminated with light resonant or near resonant with the localized surface-plasmon frequency of the metal structure. Small in this context is gauged in relation to the wavelength of light. The special preparations required to produce the effect, which include among other techniques electrochemical oxidation-reduction cycling, deposition of metal on very cold substrates, and the generation of metal-island films and colloids, is now understood to be necessary as a means of producing surfaces with appropriate electromagnetic resonances that may couple to electromagnetic fields either by generating rough films (as in the case of the former two examples) or by placing small metal particles in close proximity to one another (as in the case of the latter two). For molecules chemisorbed on SERS-active surface there exists a "chemical enhancement" in addition to the electromagnetic effect. Although difficult to measure accurately, the magnitude of this effect rarely exceeds a factor of 10 and is best thought to arise from the modification of the Raman polarizability tensor of the adsorbate resulting from the formation of a complex between the adsorbate and the metal. Rather than an enhancement mechanism, the chemical effect is more logically to be regarded as a change in the nature and identity of the adsorbate.

Surface-enhanced spectroscopy

Over the past several years, cerium oxide and CeO2-containing materials have come under intense scrutiny as catalysts and as structural and electronic promoters of heterogeneous catalytic reactions. Recent developments regarding the characterization of ceria and CeO2-containing catalysts are critically reviewed with a special focus towards catalyst interaction with small molecules such as hydrogen, carbon monoxide, oxygen, and nitric oxide. Relevant catalytic and technological applications such as the use of ceria in automotive exhaust emission control and in the formulation of SO x reduction catalysts is described. A survey of the use of CeO2-containing materials as oxidation and reduction catalysts is also presented.

Catalytic Properties of Ceria and CeO2-Containing Materials

Traditional analysis of reactions catalyzed by supported metals involves the structure of the metallic particles. However, we report here that for the class of nanostructured gold- or platinum-cerium oxide catalysts, which are active for the water-gas shift reaction, metal nanoparticles do not participate in the reaction. Nonmetallic gold or platinum species strongly associated with surface cerium-oxygen groups are responsible for the activity.

http://science.sciencemag.org/content/sci/301/5635/935.full.pdf

Active Nonmetallic Au and Pt Species on Ceria-Based Water-Gas Shift Catalysts

Powdered samples of the type Ce1−xRExO2−y, where RE=La, Pr, Nd, Eu, Gd, and Tb, are synthesized over the range 0≤x≤0.5 starting from nitrate solutions of the rare earths. X‐ray diffraction and Raman scattering are used to analyze the samples. These compounds, at least in the low doping regime and for strictly trivalent dopants, form solid solutions that maintain the fluorite structure of CeO2 with a change in lattice constant that is approximately proportional to the dopant ionic radius. The single allowed Raman mode, which occurs at 465 cm−1 in pure CeO2, is observed to shift to lower frequency with increasing doping level for all the rare earths. However, after correcting for the Gruneisen shift from the lattice expansion, the frequency shift is actually positive for all the strictly trivalent ions. In addition, the Raman line broadens and becomes asymmetric with a low frequency tail, and a new broad feature appears in the spectrum at ∼570 cm−1. These changes in the Raman spectrum are attributed to O va...

Raman and x‐ray studies of Ce1−xRExO2−y, where RE=La, Pr, Nd, Eu, Gd, and Tb

Polarized Raman-scattering spectra are obtained from oriented single crystals of ${\mathrm{CeO}}_{2}$. Second-order features are assigned to phonon overtones from the X and L points on the Brillouin-zone boundary on the basis of selection rules and by analogy to another fluorite structure compound, ${\mathrm{BaF}}_{2}$, in which the phonon dispersion curves are known. Complete selection rules for second-order scattering from these high-symmetry points are determined. A rigid-ion model is constructed for the phonon dispersion curves by fitting several of these features and the known zone-center optical modes. The ${\mathit{F}}_{2\mathit{g}}$ Raman-active mode at 465 ${\mathrm{cm}}^{\mathrm{\ensuremath{-}}1}$ in ${\mathrm{CeO}}_{2}$ shifts and broadens with decreased particle size [G. W. Graham, W. H. Weber, C. R. Peters, and R. Usmen, J. Catalysis 130, 310 (1991)]. It is shown using the calculated dispersion curves that this particle-size effect cannot be explained with the spatial-correlation model.

Raman study of CeO2: Second-order scattering, lattice dynamics, and particle-size effects.

Luminescent greenhouse collector for solar radiation.

The probability for direct energy transfer from a dye molecule to the surface plasmons (SP) on a nearby metal is calculated using the classical Sommerfeld model. For 600-nm emission from a dipole-oriented ⊥ to an Ag surface, the peak SP coupling probability is 93% at a distance of 120 nm from the metal. The coupling is demonstrated in experiments with an Ag film between a rhodamine–methanol solution and a high-index prism. The SP-coupled radiation produces an intense cone of radiation in the prism, each frequency component of which satisfies the SP dispersion relation.

Willes H. Weber

Papers

Raman and x‐ray studies of Ce1−xRExO2−y, where RE=La, Pr, Nd, Eu, Gd, and Tb

Raman study of CeO2: Second-order scattering, lattice dynamics, and particle-size effects.

Luminescent greenhouse collector for solar radiation.

Energy transfer from an excited dye molecule to the surface plasmons of an adjacent metal.

Empirical method for determining CeO2-particle size in catalysts by raman spectroscopy