Diffraction and Other X-Ray Methods

A beam of X-ray (i.e. electromagnetic radiation with a wavelength between A, = 0.01 and 10 nm) interacts with matter in three different ways  

X-rays are basically scattered or absorbed by all atoms in their path, thus they are not inherently surface sensitive. Depending on the type of interaction employed in a given method, various approaches are possible to confer this surface sensitivity when desired, as outlined below. 

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X-ray diffraction uses X-rays of known wavelengths to determine the lattice spacing in crystalline structures and therefore directly identify chemical compounds. This is in contrast to the other X-ray methods discussed in this chapter (XRF, electron microprobe analysis, PIXE) which determine concentrations of constituent elements in artifacts. Powder XRD, the simplest of the range of XRD methods, is the most widely applied method for structural identification of inorganic materials, and, in some cases, can also provide information about mechanical and thermal treatments during artifact manufacture. Cullity (1978) provides a detailed account of the method. 

X-Ray Methods. In x-ray fluorescence the sample containing mercury is exposed to a high iatensity x-ray beam which causes the mercury and other elements ia the sample to emit characteristic x-rays. The iatensity of the emitted beam is directly proportional to the elemental concentration ia the sample (22). Mercury content below 1 ppm can be detected by this method. X-ray diffraction analysis is ordinarily used for the quaUtative but not the quantitative determination of mercury. 

This chapter contains articles on six techniques that provide structural information on surfaces, interfeces, and thin films. They use X rays (X-ray diffraction, XRD, and Extended X-ray Absorption Fine-Structure, EXAFS), electrons (Low-Energy Electron Diffraction, LEED, and Reflection High-Energy Electron Diffraction, RHEED), or X rays in and electrons out (Surfece Extended X-ray Absorption Fine Structure, SEXAFS, and X-ray Photoelectron Diffraction, XPD). In their usual form, XRD and EXAFS are bulk methods, since X rays probe many microns deep, whereas the other techniques are surfece sensitive. There are, however, ways to make XRD and EXAFS much more surfece sensitive. For EXAFS this converts the technique into SEXAFS, which can have submonolayer sensitivity. 

Once a suitable crystal is obtained and the X-ray diffraction data are collected, the calculation of the electron density map from the data has to overcome a hurdle inherent to X-ray analysis. The X-rays scattered by the electrons in the protein crystal are defined by their amplitudes and phases, but only the amplitude can be calculated from the intensity of the diffraction spot. Different methods have been developed in order to obtain the phase information. Two approaches, commonly applied in protein crystallography, should be mentioned here. In case the structure of a homologous protein or of a major component in a protein complex is already known, the phases can be obtained by molecular replacement. The other possibility requires further experimentation, since crystals and diffraction data of heavy atom derivatives of the native crystals are also needed. Heavy atoms may be introduced by covalent attachment to cystein residues of the protein prior to crystallization, by soaking of heavy metal salts into the crystal, or by incorporation of heavy atoms in amino acids (e.g., Se-methionine) prior to bacterial synthesis of the recombinant protein. Determination of the phases corresponding to the strongly scattering heavy atoms allows successive determination of all phases. This method is called isomorphous replacement. 

The development of electron diffraction and microscopy was parallel but separate. Although there are many obvious similarities between the theories, they are usually expressed in different notations and it is common that workers trained in the one have little knowledge of the other. This is particularly unfortunate in that the techniques are almost always complementary, and many investigations will benefit by the use of both electron and X-ray (or neutron) methods. The emphasis in this book is on the X-ray methods. Electron techniques have been amply covered in a number of excellent publications we have not... 

Elemental composition Ni 78.58%, O 21.42%. Nickel may be analyzed in a diluted solution of the oxide in nitric acid by AA, ICP and other instrumental methods. The oxide may be identified from its physical properties and by x-ray diffraction. 

The section Analysis starts with elemental composition of the compound. Thus the composition of any compound can be determined from its elemental analysis, particularly the metal content. For practically all metal salts, atomic absorption and emission spectrophotometric methods are favored in this text for measuring metal content. Also, some other instrumental techniques such as x-ray fluorescence, x-ray diffraction, and neutron activation analyses are suggested. Many refractory substances and also a number of salts can be characterized nondestructively by x-ray methods. Anions can be measured in aqueous solutions by ion chromatography, ion-selective electrodes, titration, and colorimetric reactions. Water of crystallization can be measured by simple gravimetry or thermogravimetric analysis. 

The five years since last considering specifically recent developments in X-ray and neutron diffraction methods for zeolites [1] have witnessed substantial progress. Some techniques, such as high resolution powder X-ray diffraction using synchrotron X-rays, have blossomed from earliest demonstrations of feasibility to widespread and productive application. Others, such as neutron powder diffraction, have shown steady progress. For still others, notably microcrystal diffraction, a variety of circumstances have contributed to extended gestation periods. Additionally, opportunities scarcely considered earlier (such as single crystal Laue diffraction, and certain developments in computer simulations that complement diffraction work) now command broad attention and warrant the commitment of substantial further investment. 

Use of X-ray diffraction patterns or identification. Even when complete structure determination is not possible, however, much valuable information of a less detailed character may be obtained by X-ray methods. In the first place, the diffracted beams produced when X-rays pass through crystals may be recorded on photographic films or plates, and the patterns thus formed may be used quite empirically, without any attempt at interpretation, to identify crystalline substances, in much the same way as we use optical emission spectra to identify elements, or infra-red absorption spectra to identify molecules. Each crystalline substance gives its own characteristic pattern, which is different from the patterns of all other substances and the pattern is of such complexity (that is, it presents so many measurable quantities) that in most cases it constitutes by far the most certain physical criterion for identification. The X-ray method of identification is of greatest value in cases where microscopic methodsare inadequate for instance, when the crystals are opaque or are too small to be seen as individuals under the microscope. The X-ray diffraction patterns of different substances generally differ so much from each other that visual comparison... 

Conclusion. This book is concerned with optical and X-ray methods but there are of course other methods of studying the structures of crystals and molecules. The diffraction of electrons and of neutrons depends on the same general principles as that of X-rays or visible light but there are important theoretical differences, and the expert mental arrangements are very different. It is not proposed to deal with either of these subjects here, but a few remarks will be made on their relation to the X-ray diffraction method. 

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