X-ray absorption fine structure EXAFS

Figure 8.34 Experimental method for extended X-ray absorption fine structure (EXAFS)...

Figure 8.38 Curve fitting of Mo extended X-ray absorption fine structure (EXAFS) for Mo(SC6H4NH)3, taking into account (a) sulphur and (b) sulphur and nitrogen atoms as near neighbours. (Reproduced, with permission, trom Winnick, H. and Doniach, S. (Eds), Synchrotron Radiation Research, p. 436, Plenum, New York, 1980)...

Extended X-Ray Absorption Fine Structure, EXAFS 214 Surface Extended X-Ray Absorption Fine Structure and Near Et e X-Ray Absorption Fine Structure, SEXAFS/NEXAFS 227 X-Ray Photoelectron and Auger Diffraction,... 

This chapter contains articles on six techniques that provide structural information on surfaces, interfeces, and thin films. They use X rays (X-ray diffraction, XRD, and Extended X-ray Absorption Fine-Structure, EXAFS), electrons (Low-Energy Electron Diffraction, LEED, and Reflection High-Energy Electron Diffraction, RHEED), or X rays in and electrons out (Surfece Extended X-ray Absorption Fine Structure, SEXAFS, and X-ray Photoelectron Diffraction, XPD). In their usual form, XRD and EXAFS are bulk methods, since X rays probe many microns deep, whereas the other techniques are surfece sensitive. There are, however, ways to make XRD and EXAFS much more surfece sensitive. For EXAFS this converts the technique into SEXAFS, which can have submonolayer sensitivity. 

Alternatives to XRD include transmission electron microscopy (TEM) and diffraction, Low-Energy and Reflection High-Energy Electron Diffraction (LEED and RHEED), extended X-ray Absorption Fine Structure (EXAFS), and neutron diffraction. LEED and RHEED are limited to surfaces and do not probe the bulk of thin films. The elemental sensitivity in neutron diffraction is quite different from XRD, but neutron sources are much weaker than X-ray sources. Neutrons are, however, sensitive to magnetic moments. If adequately large specimens are available, neutron diffraction is a good alternative for low-Z materials and for materials where the magnetic structure is of interest. 

The discovery of the phenomenon that is now known as extended X-ray absorption fine structure (EXAFS) was made in the 1920s, however, it wasn t until the 1970s that two developments set the foundation for the theory and practice of EXAFS measurements. The first was the demonstration of mathematical algorithms for the analysis of EXAFS data. The second was the advent of intense synchrotron radiation of X-ray wavelengths that immensely facilitated the acquisition of these data. During the past two decades, the use of EXAFS has become firmly established as a practical and powerfiil analytical capability for structure determination. ... 

A detailed investigation of the structure of amorphous PcRu by large-angle X-ray scattering (LAXS)269 showed that in the solid state dimeric species exist with a Ru-Ru distance in the magnitude of a double bond. Current experiments using the extended X-ray absorption fine structure (EXAFS) method confirm these results.279... 

Extended X-ray absorption fine structure (EXAFS) measurements based on the photoeffect caused by collision of an inner shell electron with an X-ray photon of sufficient energy may also be used. The spectrum, starting from the absorption edge, exhibits a sinusoidal fine structure caused by interferences between the outgoing and the backscattered waves of the photoelectron which is the product of the collision. Since the intensity of the backscattering decreases rapidly over the distances to the next neighbor atoms, information about the chemical surroundings of the excited atom can be deduced. 

X-Ray Absorption Spectroscopy, X-Ray Absorption Edge Spectroscopy and Extended X-Ray Absorption Fine Structure (EXAFS) 247,280,469,980,1090,1619, 1691... 

Fe-S and Fe-Fe distances in [2Fe-2S], [3Fe-4S], and [4Fe-4S] clusters are all very similar 2.3 and 2.7 A, respectively. In the [6Fe-6S] prismane model cluster, however, there is an additional Fe-Fe distance at 3.7 A (Fig. 2). If a [6Fe-6S] cluster were present in the Fepr protein, then this longer Fe-Fe distance should he visible with extended X-ray absorption fine structure (EXAFS). As a consequence, EXAFS studies were carried out at the CCLRC Synchrotron Radiation facility in Daresbury, UK. The two Fepr proteins (those of D. vulgaris and D. desulfuricans), as well as a synthetic [6Fe-6S] cluster, were subjected to an EXAFS study. Low-temperature EXAFS... 

Time-resolved X-ray absorption is a very different class of experiments [5-7]. Chemical reactions are triggered by an ultrafast laser pulse, but the laser-induced change in geometry is observed by absorption rather than diffraction. This technique permits one to monitor local rather than global changes in the system. What one measures in practice is the extended X-ray absorption fine structure (EXAFS), and the X-ray extended nearedge strucmre (XANES). 

Extended X-ray absorption fine structure (EXAFS) studies have been very useful for obtaining structural information on bimetallic cluster catalysts. The application to bimetallic systems is a particularly good one for illustrating the various factors which have an influence on EXAFS. Moreover, the applicability of EXAFS to this area has been very timely, in view of the enormous interest in bimetallic systems in both catalytic science and technology. 

X-ray absorption spectroscopy combining x-ray absorption near edge fine structure (XANES) and extended x-ray absorption fine structure (EXAFS) was used to extensively characterize Pt on Cabosll catalysts. XANES Is the result of electron transitions to bound states of the absorbing atom and thereby maps the symmetry - selected empty manifold of electron states. It Is sensitive to the electronic configuration of the absorbing atom. When the photoelectron has sufficient kinetic energy to be ejected from the atom It can be backscattered by neighboring atoms. The quantum Interference of the Initial... 

These conclusions from the infrared reflectance spectra recorded with Pt and Pt-Ru bulk alloys were confirmed in electrocatalysis studies on small bimetallic particles dispersed on high surface area carbon powders.Concerning the structure of bimetallic Pt-Ru particles, in situ Extended X-Ray Absorption Fine Structure (EXAFS>XANES experiments showed that the particle is a true alloy. For practical application, it is very important to determine the optimum composition of the R-Ru alloys. Even if there are still some discrepancies, several recent studies have concluded that an optimum composition about 15 to 20 at.% in ruthenium gives the best results for the oxidation of methanol. This composition is different from that for the oxidation of dissolved CO (about 50 at.% Ru), confirming a different spatial distribution of the adsorbed species. 

In the present study, we synthesized in zeolite cavities Co-Mo binary sulfide clusters by using Co and Mo carbonyls and characterized the clusters by extended X-ray absorption fine structure (EXAFS), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), and high resolution electron microscopy (HREM). The mechanism of catalytic synergy generation in HDS is discussed. 

Intermediates were also observed in the synthesis of a neutral cluster, Ir4(CO)i2, from Ir(CO)2(acac) in the cages of zeohte NaY these were characterized by IR and extended X-ray absorption fine structure (EXAFS) spectroscopies, the latter being a technique ideally suited to investigation of small, highly dispersed species present in small amoimts in sohds. The spectra indicated dimeric intermediates, possibly Ir2(CO)8 [ 16], when the reaction was carried out in the near absence of water in the zeohte in contrast, the reaction in the dehydrated zeolite was faster, and no evidence of intermediates was observed [16]. 

Fig. 3 Ir4 cluster supported at the six-ring of zeolite NaX as represented by density functional theory samples were characterized by Extended X-ray absorption fine structure (EXAFS) spectroscopy and other techniques [32]...

Extended X-ray absorption fine structure (EXAFS) and photoemission measurements carried out on the clusters ranging from isolated atoms to aggregates large enough to acquire bulk metal properties, is also could be a measure for the electronic properties [40]. Copper shows a... 

Extended X-ray Absorption Fine Structure (EXAFS) the measurements were mostly made at the Gilda Italian Beamline (equipped with a bending magnet) at the European Synchrotron Radiation Facility in Grenoble (France). 

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