X-ray edge spectroscopy

Zaera F, Fischer D A, Shen S and Gland J L 1998 Fluorescence yield near-edge X-ray absorption spectroscopy under atmospheric conditions CO and FI2 coadsorption on Ni(IOO) at pressures between 10 and 0.1 Torr Surf. Sc/. 194 205-16... 

X-Ray Absorption Spectroscopy. As the excitation energy incident on a sample is increased, sharp rises in absorption occur at the K, L,..., absorption edges where the energy just matches that required for ionization by ejection of an electron from the K, L,. .., sheUs. These energies are characteristic for each element. The absorption foUows Beer s law (eq. 1), which in this region is usually written as A( A) = )px where p is the density,... 

Near edge x-ray absorption fine stmcture spectroscopy (nexafs) and x-ray photoelectron spectroscopy (xps) have been used to study SAMs of OTS, octadecyltrimethoxysilane (OTMS), CH2(CH2) ySi(OCH2)3, and (17-aminoheptadecyl)-trimethoxysilane (AHTMS), H2N(CH2) ySi(OCH3)3 (149). A number of important observations have been reported. First, the chains in OTS SAMs are practicaUy perpendicular to the substrate surface (tilt angle... 

EXAFS is part of the field of X-ray absorption spectroscopy (XAS), in which a number of acronyms abound. An X-ray absorption spectrum contains EXAFS data as well as the X-ray absorption near-edge structure, XANES (alternatively called the near-edge X-ray absorption fine structure, NEXAFS). The combination of XANES (NEXAFS) and EXAFS is commonly referred to as X-ray absorption fine structure, or XAFS. In applications of EXAFS to surface science, the acronym SEXAFS, for surface-EXAFS, is used. The principles and analysis of EXAFS and SEXAFS are the same. See the article following this one for a discussion of SEXAFS and NEXAFS. 

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

The prepared catalysts were characterized by x-ray diffraction (XRD), N2 adsorption and CO chemisorption. Also, X-ray absorption spectroscopy (XAS) at the Ni K edge (8.333 keV) of reference and catalyst samples was carried out in the energy range 8.233 to 9.283 keV at beamline X18B of the... 

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... 

Analytical electron microscopy (AEM) can use several signals from the specimen to analyze volumes of catalyst material about a thousand times smaller than conventional techniques. X-ray emission spectroscopy (XES) is the most quantitative mode of chemical analyse in the AEM and is now also useful as a high resolution elemental mapping technique. Electron energy loss spectroscopy (EELS) vftiile not as well developed for quantitative analysis gives additional chemical information in the fine structure of the elemental absorption edges. EELS avoids the problem of spurious x-rays generated from areas of the spectrum remote from the analysis area. 

Evidence for the first reason was demonstrated in X-ray photoelectron spectroscopy (XPS) or X-Ray Absorption Near Edge Structure (XANES) studies, as well as by many voltammetric studies. ... 

The reaction on the catalyst surface was followed by in situ i.r. spectroscopy using a Bruker IFS88 FTIR spectrometer for the characterisation of sorbed species and mass spectroscopy for the analysis of gas phase. The state of Pt was further investigated by in situ X-ray absorption spectroscopy (Daresbury, UK, beamline 9.1, transmission mode, Si(220) monochromator, Pt-Lj, edge). Details of catalyst characterisation techniques are reported elsewhere [13,14]. 

In general, several spectroscopic techniques have been applied to the study of NO, removal. X-ray photoelectron spectroscopy (XPS), electron paramagnetic resonance (EPR), nuclear magnetic resonance (NMR), extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) are currently used to determine the surface composition of the catalysts, with the aim to identify the cationic active sites, as well as their coordinative environment. 

Figure 5.13 X-ray Absorption Spectroscopy complex. The calculated spectra were (XAS) spectra (top) and XMCD spectra (bot- obtained from ligand-field multiplet calcula-tom) for Dy3+ at the M45 edges (A) and tions. (Reprinted with permission from [47].

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... 

XPS has typically been regarded primarily as a surface characterization technique. Indeed, angle-resolved XPS studies can be very informative in revealing the surface structure of solids, as demonstrated for the oxidation of Hf(Sio.sAso.5)As. However, with proper sample preparation, the electronic structure of the bulk solid can be obtained. A useful adjunct to XPS is X-ray absorption spectroscopy, which probes the bulk of the solid. If trends in the XPS BEs parallel those in absorption energies, then we can be reasonably confident that they represent the intrinsic properties of the solid. Features in XANES spectra such as pre-edge and absorption edge intensities can also provide qualitative information about the occupation of electronic states. 

The applications of polarized x-ray absorption spectroscopy (PXAS) for structure determination in inorganic and bioinorganic systems are discussed. PXAS studies of oriented samples add angular detail to the information obtained from x-ray absorption edges and from EXAFS. In some cases, PXAS can be used to determine molecular orientation. In other cases, PXAS can be used to infer the details of electronic structure or of chemical bonding. Some of the potential future applications of PXAS are discussed. 

In this chapter, we briefly discuss the theoretical background of polarized x-ray absorption spectroscopy (PXAS). Many of the recent applications of synchrotron radiation to polarized absorption edge structure and to EXAFS are discussed, with particular emphasis being given to the study of discrete molecular systems. We present here some indication of the potential applications of PXAS to systems of chemical and biological interest. 

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