X-ray, absorption structure

Applications EXAFS spectroscopy is obviously well suited to speciate and quantify the state of heavy metals, e.g. in soils [310]. Similarly, it allows differentiation of ZnO and Zn stearate on the basis of the X-ray absorption structure of zinc. 

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... 

EXAFS Extended X-ray absorption fine structure spectroscopy. A spectroscopic technique which can determine interatomic distances very precisely. 

EXAFS Extended x-ray absorption fine structure [177, 178] Variation of x-ray absorption as a function of x-ray energy beyond an absorption edge the probability is affected by backscattering of the emitted electron from adjacent atoms Number and interatomic distance of surface atoms... 

At a surface, not only can the atomic structure differ from the bulk, but electronic energy levels are present that do not exist in the bulk band structure. These are referred to as surface states . If the states are occupied, they can easily be measured with photoelectron spectroscopy (described in section A 1.7.5.1 and section Bl.25.2). If the states are unoccupied, a teclmique such as inverse photoemission or x-ray absorption is required [22, 23]. Also, note that STM has been used to measure surface states by monitoring the tunnelling current as a fiinction of the bias voltage [24] (see section BT20). This is sometimes called scamiing tuimelling spectroscopy (STS). 

For bulk structural detemiination (see chapter B 1.9). the main teclmique used has been x-ray diffraction (XRD). Several other teclmiques are also available for more specialized applications, including electron diffraction (ED) for thin film structures and gas-phase molecules neutron diffraction (ND) and nuclear magnetic resonance (NMR) for magnetic studies (see chapter B1.12 and chapter B1.13) x-ray absorption fine structure (XAFS) for local structures in small or unstable samples and other spectroscopies to examine local structures in molecules. Electron microscopy also plays an important role, primarily tlirough unaging (see chapter B1.17). 

Lee P A, Citrin P H, Eisenberger P and Kincaid B M 1981 Extended x-ray absorption fine structure—its strengths and limitations as a structural tool Rev. Mod. Rhys. 53 769-806... 

Iwasawa Y (ed) 1996 X-Ray Absorption Fine Structure for Cataiysis and Surfaces (Singapore World Scientific)... 

Stdhr J, Kollin E B, Fischer D A, Flastings J B, Zaera F and Sette F 1985 Surface extended x-ray-absorption fine structure of low-Z adsorbates studied with fluorescence detection Rhys. Rev. Lett. 55 1468-71... 

Zaera F, Fischer D A, Carr R G and Gland J L 1988 Determination of chemisorption geometries for complex molecules by using near-edge X-ray absorption fine structure ethylene on Ni(IOO) J. Chem. Rhys. 89 5335-41... 

Ingalls R, Crozier E D, Whitmore J E, Seary A J and Tranquada J M 1980 Extended x-ray absorption fine structure of sodium bromide and germanium at high pressure J. Appl. Phys. 51 3158... 

Fischer D, Marti A and Hahner G 1997 Orientation and order in microcontact-printed, seif-assembied monoiayers of aikanethiois on goid investigated with near edge x-ray absorption fine structure spectroscopy J. Vac. Sc/. Technol. A 15 (4) 2173-80... 

Wu S, Lipkowski J, Tyiiszczak T and Hitchcock A P 1997 Eariy stages of copper eiectrocrystaiiization eiectrochemicai and in situ x-ray absorption fine structure studies of coadsorption of copper and chioride at the Au(111) eiectrode surface J.Phys. Chem. B 101 10 310-22... 

Rehr J J, Mustre de Leon J, Zabinski S I and Albers R C 1991 Theoretical x-ray absorption fine structure standards J. Am. Chem. Soc. 113 5135-40... 

Rehr J J, Albers R C and Zabinski S I 1992 High order multiple scattering calculation of x-ray absorption fine structure Phys. Rev. Lett. 69 3397-400... 

Figure 8.33 Formation of an absorption edge and pre-edge structure in X-ray absorption...

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)...

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