The authors review the development of extended x-ray absorption fine structure (EXAFS) within the last decade. Advances in experimental techniques have been largely stimulated by the availability of synchrotron radiation. The theory of EXAFS has also matured to the point where quantitative comparison with experiments can be made. The authors review in some detail the analysis of EXAFS data, starting from the treatment of raw data to the extraction of distances and amplitude information, and they also discuss selected examples of applications of EXAFS chosen to illustrate both the strength and limitations of EXAFS as a structural tool.

Extended x-ray absorption fine structure—its strengths and limitations as a structural tool

Size dependence of nanostructures: Impact of bond order deficiency

Excitations of the $2p$ subshell in the $3d$ transition metals and their oxides have been studied by inelastic scattering of 75-keV electrons. The ${L}_{23}$ "white lines" which arise from dipole transitions to unoccupied $d$ states have been investigated in terms of their threshold energies, widths, and intensity ratios. Shifts in the ${L}_{3}$ threshold energy between the metal and oxide are different from the chemical shifts measured by x-ray photoemission spectroscopy and this suggests the importance of relaxation effects. Single-particle calculations for the ${L}_{3}$ spectra are also discussed. Measured ${L}_{3}$ linewidths are generally larger than those predicted by suitably broadened theory. A variation from the statistical ${L}_{3}$-to-${L}_{2}$ white-line intensity ratio of 2:1 has been observed across the $3d$ transition row, with values ranging between 0.8:1 for Ti to 5:1 for FeO. This behavior appears to be associated with the white lines since Cu with a filled $3d$ band exhibits the statistical results. It is suggested that the anomalous ratios may be explained by a breakdown of $j\ensuremath{-}j$ coupling caused by an exchange mechanism. Finally, the extended x-ray absorption fine-structure-type structure extending several hundred eV above the white lines is analyzed for Cr to provide the radial distribution function.

Study of the L 23 edges in the 3 d transition metals and their oxides by electron-energy-loss spectroscopy with comparisons to theory

Core-level binding-energy shifts at surfaces and in solids

Properties of materials determined by their size are indeed fascinating and form the basis of the emerging area of nanoscience. In this article, we examine the size dependent electronic structure and properties of nanocrystals of semiconductors and metals to illustrate this aspect. We then discuss the chemical reactivity of metal nanocrystals which is strongly dependent on the size not only because of the large surface area but also a result of the significantly different electronic structure of the small nanocrystals. Nanoscale catalysis of gold exemplifies this feature. Size also plays a role in the assembly of nanocrystals into crystalline arrays. While we owe the beginnings of size-dependent chemistry to the early studies of colloids, recent findings have added a new dimension to the subject.

Size‐Dependent Chemistry: Properties of Nanocrystals

Extended x-ray-absorption fine-structure measurements have been made on metal clusters of Cu and Ni which were formed by vapor deposition on amorphous carbon substrates. Small clusters of both elements show a substantial contraction of the nearest-neighbor metal-metal distance and an increase in binding energy for the onset of the $K$ absorption edge. The results are explained by the increasing surface-to-volume ratio as the cluster size decreases resulting in a more free-atom---like configuration of the metal atoms.

Extended X-Ray—Absorption Fine Structure of Small Cu and Ni Clusters: Binding-Energy and Bond-Length Changes with Cluster Size

Samarium clusters exhibit mixed-valence behavior which is sensitive to particle size. XPS and UPS data show samarium to be primarily divalent (4f{sup 6} ) at small particle size. The trivalent state (4f{sup 5} ) becomes progressively more abundant with increasing s1ze, becoming the dominant state for the bulk metal. These results are interpreted using a model in which band narrowing, due to reduced surface coordination, is more dominant than surface tension effects in establishing the valence of small samarium clusters.

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Particle-Size-Induced Valence Changes in Samarium Clusters

Absorption measurements above the K edges of the low-Z atoms, C, N, O, and F, are discussed, which utilize 250–1000-eV synchrotron radiation. The paper emphasizes experimental procedures of soft x-ray absorption and extended absorption fine structure (EXAFS) measurements as well as applications and future prospects of such studies. In particular, we discuss such applications as surface EXAFS, surface absorption fine structure, and ion yield EXAFS measurements.

Extended absorption fine structure studies above the carbon, nitrogen, oxygen, and fluorine K absorption edges.

Extended x-ray absorption fine structure (EXAFS) and photoemission measurements have been carried out on clusters ranging from isolated atoms to aggregates large enough to acquire bulk metal properties. EXAFS studies of copper show a substantial contraction of the nearest-neighbor Cu-Cu distance for small clusters. In addition, the onset of the K absorption edge shifts toward higher energy as the cluster size decreases. Variable energy photoemission spectra of gold clusters show the evolution of band structure with increasing cluster size.

G. Apai

Papers

Extended X-Ray—Absorption Fine Structure of Small Cu and Ni Clusters: Binding-Energy and Bond-Length Changes with Cluster Size

Particle-Size-Induced Valence Changes in Samarium Clusters

Extended absorption fine structure studies above the carbon, nitrogen, oxygen, and fluorine K absorption edges.

Binding Energies, Bond-Length Changes, and Band Structure Formation in Small Clusters