Synchrotron Absorption Fine Structure

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)...

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. ... 

Figure 2 Molybdenum K-edge X-ray absorption spectrum, ln(i /i ) versus X-ray energy (eV), for molybdenum metal foil (25- jjn thick), obtained by transmission at 77 K with synchrotron radiation. The energy-dependent constructive and destructive interference of outgoing and backscattered photoelectrons at molybdenum produces the EXAFS peaks and valleys, respectively. The preedge and edge structures marked here are known together as X-ray absorption near edge structure, XANES and EXAFS are provided in a new compilation of literature entitled X-rsy Absorption Fine Structure (S.S. Hasain, ed.) Ellis Norwood, New York, 1991.

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... 

Y. Iwasawa, X-Ray Absorption Fine Structure for Catalysts and Surfaces, World Scientific Series on Synchrotron Radiation Techniques and Applications, Vol. 2, World Scientific, Singapore, 1996. 

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). 

The most prevalent technique exploiting synchrotron radiation is X-ray absorption spectroscopy (XAS, also called X-ray absorption fine structure, XAFS). Two related types of experiments are conducted X-ray absorption near-edge spectroscopy (XANES), which probes the initial absorption edge and related nearby structure, and... 

EXAFS (Extended X-ray Absorption Fine Structure) measurements using synchrotron radiation have been successfully applied to the determination of structural details of SCO systems and have been particularly useful when it has not been possible to obtain suitable crystals for X-ray diffraction studies. Perhaps the most significant application has been in elucidating important aspects of the structure of the iron(II) SCO linear polymers derived from 1,2,4-triazoles [56]. EXAFS has also been applied to probe the dimensions of LIESST-generated metastable high spin states [57]. It has even been used to generate a spin transition curve from multi-temperature measurements [58]. 

Inner electrons are usually excited by X-rays. Atoms give characteristic X-ray absorption and emission spectra, due to a variety of ionization and possible inter-shell transitions. Two relevant refined X-ray absorption techniques, that use synchrotron radiation, are the so-called Absorption Edge Fine Structure (AEFS) and Extended X-ray Absorption Fine Structure (EXAFS). These techniques are very useful in the investigation of local structures in solids. On the other hand, X-Ray Fluorescence (XRF) is an important analytical technique. 

Extended X-ray absorption fine structure (EXAFS) A technique for observing the local structure around a metal centre, using X-rays from a synchrotron source. The atom of interest absorbs photons at a characteristic wavelength and the emitted electrons, undergoing constructive or destructive interference as they are scattered by the surrounding atoms, modulate the absorption spectrum. The modulation frequency corresponds directly to the distance of the surrounding atoms while the amplitude is related to the type and number of atoms. In particular, bond lengths and coordination numbers may be derived. 

Although a number of secondary minerals have been predicted to form in weathered CCB materials, few have been positively identified by physical characterization methods. Secondary phases in CCB materials may be difficult or impossible to characterize due to their low abundance and small particle size. Conventional mineral identification methods such as X-ray diffraction (XRD) analysis fail to identify secondary phases that are less than 1-5% by weight of the CCB or are X-ray amorphous. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM), coupled with energy dispersive spectroscopy (EDS), can often identify phases not seen by XRD. Additional analytical methods used to characterize trace secondary phases include infrared (IR) spectroscopy, electron microprobe (EMP) analysis, differential thermal analysis (DTA), and various synchrotron radiation techniques (e.g., micro-XRD, X-ray absorption near-eidge spectroscopy [XANES], X-ray absorption fine-structure [XAFSJ). 

EXAFS (Extended X-Ray Absorption Fine Structure). Characterization of the surface of metal nanoparticles had been limited to chemical methods, e.g., chemisorption of hydrogen and carbon monoxide. In 1970s, the situation was surprisingly changed due to the advances in x-ray absorption spectroscopy, especially extended x-ray absorption fine structure (EXAFS), Advances in this method have been achieved with the use of synchrotron radiation, which runs effectively at Tsukuba (Japan), Grenoble (France), etc. Now it is one of the most valuable tools to get structural information on bimetallic nanoparticles. 

Mineral-liquid or mineral-gas interfaces under reactive conditions cannot be studied easily using standard UHV surface science methods. To overcome the pressure gap between ex situ UHV measurements and the in situ reactivity of surfaces under atmospheric pressure or in contact with a liquid, new approaches are required, some of which have only been introduced in the last 20 years, including scanning tunneling microscopy [28,29], atomic force microscopy [30,31], non-linear optical methods [32,33], synchrotron-based surface scattering [34—38], synchrotron-based X-ray absorption fine structure spectroscopy [39,40], X-ray standing wave... 

In 2006, Lobinski et al.1 reported on the imaging and speciation analysis of trace elements to study the element distribution, oxidation state, metal site and metal structure in biological environments using mass spectrometric techniques (LA-ICP-MS, SIMS, MALDI-MS) and non-mass-spectrometric techniques such as micro-PIXE (proton induced X-ray emission), XANES (X-ray absorption near edge structure) and EXAFS (extended X-ray absorption fine structure) -the latter two techniques are very sensitive due the use of a more intense synchrotron beam.1... 

Recently, carbon (Is) near-edge X-ray absorption fine structure (C (Is) NEXAFS) spectroscopy using synchrotron radiation has been applied to carbon (C) speciation and to investigate source apportionment of combustion derived particulate matter, as well as to predict a possible decay path for carboxylic groups in soot by photo-... 

A non exhaustive description of the history of X-ray Absorption Spectroscopy (XAS) can be found in Ref. 1. The modem EXAFS (Extended X-ray Absorption Fine Structure) technique began in the early seventies of the last century. It corresponds to the concomitance of both theoretical and experimental developments. Between 1969 and 1975, Stem, Sayers and Lytle succeeded in interpreting theoretically the X-ray Absorption Structures observed above an absorption edge [2], while during the same period, the advent of synchrotron radiation (SR) sources reduced drastically the acquisition time of a spectrum if compared to data obtained with conventional X-ray tubes. XAS provides essential information about the local atomic geometry and the electronic and chemical state of a specific atom, for almost any element of the periodic table (Z>5). This prime tool for... 

Synchrotron Radiation Extended X-Ray Absorption Fine Structure... 

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