Theoretical Aspects and Hardware

X-ray diffraction from crystalline samples can result in a complete three-dimensional crystal structure of a molecule, but requires a single crystal suit- 

The XAS spectrometer is similar to a UV-visible system in that it consists of a source, a monochromator, and a detector. The most favorable XAS source, synchrotron radiation, is tunable to different wavelengths of desirable high intensity. A laboratory instrument for analysis of solids and concentrated solutions may use a rotating anode source (further described in Section 3.3). The monochromator for X-ray radiation usually consists of silicon single crystals. The crystals can be rotated so that the wavelength ( i) of the X-rays produced depends of the angle of incidence (0) with a Bragg lattice plane of 

Detectors for quantitative measurement of X-ray absorption spectra must measure the flux (photons s of the X-ray beam. Ionization chambers consisting of X-ray transparent windows on each end of a chamber holding an inert gas work well as transmission detectors for concentrated samples. For transmission detectors, ln(/o//) is proportional to the absorption coefficient of the absorbing atom, p (/o = incident X-ray photon intensity, /= transmitted intensity), according to Beer s Law  

Fluorescence excitation techniques provide a more sensitive detection system in which fluorescent X-ray photons (a fraction of the ionized absorbing atoms relax by emission of a fluorescent X-ray photon) are counted as the photon energy is scanned. The signal generated is proportional to the absorption coefficient, p, of the absorbing atom. 

The data collected are subjected to Fourier transformation yielding a peak at the frequency of each sine wave component in the EXAFS. The sine wave frequencies are proportional to the absorber-scatterer (a-s) distance i as- Each peak in the display represents a particular shell of atoms. To answer the question of how many of what kind of atom, one must do curve fitting. This requires a reliance on chemical intuition, experience, and adherence to reasonable chemical bond distances expected for the molecule under study. In practice, two methods are used to determine what the back-scattered EXAFS data for a given system should look like. The first, an empirical method, compares the unknown system to known models the second, a theoretical method, calculates the expected behavior of the a-s pair. The empirical method depends on having information on a suitable model, whereas the theoretical method is dependent on having good wave function descriptions of both absorber and scatterer. 

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