Centre for Radiation Chemical

Chemical Hazards and Poisons Division, Centre for Radiation, Chemical and Environmental Hazards, Health Protection Agency, Chilton, Didcot, Oxfordshire, 0X11 ORQ, UK... 

Identification of crystalline substance and crystalline phases in a specimen is achieved by comparing the specimen diffraction spectrum with spectra of known crystalline substances. X-ray diffraction data from a known substance are recorded as a powder diffractionfile (PDF). Most PDFs are obtained with CuKa radiation. Standard diffraction data have been published by the International Centre for Diffraction Data (ICDD), and they are updated and expanded from time to time. For one crystalline substance, there may be more than one file. The most recently updated file is recommended for phase identification. The early PDFs may contain errors in data obtained experimentally. More recently published PDFs are either obtained by more accurate experimental measurements or by theoretical calculation. A specimen to be identified should be in a powder form for most accurate matching. When we need to identify the crystal structure of a specimen that cannot be prepared as powder, matches of peak positions and relative intensities might be less than perfect. In this case, other information about the specimen such as chemical composition should be used to make a judgment. 

From a chemist s viewpoint, the most important act of ionizing radiation (usually X-rays, y-rays or high energy electrons) is electron ejection. Initially the ejected electrons have sufficient energy to eject further electrons on interaction with other molecules, but the electrons ultimately become thermalised and then are able to interact "chemically". We consider first various reaction pathways for these electrons, and then consider the fate of the "hole" centres created by electron ejection. [We refer to electron-gain and electron-loss centres rather than to radical-anions and -cations since, of course, the substrate may comprise ions rather than neutral molecules. 

X-ray absorption spectroscopy is an exciting new tool, ideally suited to probing the immediate environment of a specific atom type in a physical, chemical or biological system. The advent of synchrotron radiation has transformed this technique from a topic of relatively minor interest to one of major scientific importance and activity " . A major attraction of the technique is the possibility it provides of probing a reaction centre in a wide range of materials ranging from an industrial catalyst to an enzyme the technique is not limited by the physical state of the sample. In this review, suitability of this technique for biochemical systems is discussed. 

Considerable interest centres on the Mantle constituting, as it does, more than half of the Earth by volume and by weight. Attention has been focussed on several problems, including the chemical composition, mineralogy, phase transitions and element partitioning in the Mantle, and the geophysical properties of seismicity, heat transfer by radiation, electrical conductivity and magnetism in the Earth. Many of these properties of the Earth s interior are influenced by the electronic structures of transition metal ions in Mantle minerals at elevated temperatures and pressures. Such effects are amenable to interpretation by crystal field theory based on optical spectral data for minerals measured at elevated temperatures and pressures. 

Figure B2.3.8. Energy-level schemes describing various optical methods for state-selectively detecting chemical reaction products left-hand side, laser-induced fluorescence (LIF) centre, resonance-enhanced multiphoton ionization (REMPI) and right-hand side, coherent anti-Stokes Raman spectroscopy (CARS). The ionization continuum is denoted by a shaded area. The dashed lines indicate virtual electronic states. Straight arrows indicate coherent radiation, while a wavy arrow denotes spontaneous emission.

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