Electron-Diffraction Measurements

The mechanisms of lead corrosion in sulfuric acid have been studied and good reviews of the Hterature are available (27—30). The main techniques used in lead corrosion studies have been electrochemical measurements, x-ray diffraction, and electron microscopy. More recendy, laser Raman spectroscopy and photoelectrochemistry have been used to gain new insight into the corrosion process (30,31). 

Structural data of a diaziridine come from gas phase electron diffraction measurements (74CC397). The N—N bond of 3-methyldiaziridine (24) is longer than in hydrazine (1.449 A) the C—N bond distances in (24) and in diazirine are nearly equal (1.479 versus 1.482 A),... 

The simplest diffraction measurement is the determination of the surface or overlayer unit mesh size and shape. This can be performed by inspection of the diffraction pattern at any energy of the incident beam (see Figure 4). The determination is simplest if the electron beam is incident normal to the surface, because the symmetry of the pattern is then preserved. The diffraction pattern determines only the size and shape of the unit mesh. The positions of atoms in the surface cannot be determined from visual inspection of the diffraction pattern, but must be obtained from an analysis of the intensities of the diffracted beams. Generally, the intensity in a diffracted beam is measured as a fimction of the incident-beam energy at several diffraction geometries. These intensity-versus-energy curves are then compared to model calculations. ... 

The allyl radical would be expected to be planar in order to maximize n delocalization. Molecular structure parameters have been obtained from EPR, IR, and electron diffraction measurements and confirm that the radical is planar. ... 

The hydrogen treatment procedures, tensile, compression and torsion tests at fixed temperatures, transmission electron or optical microscopy at room temperature as well as X-ray diffraction measurements were detailed elsewhere All experiments were performed so as to compare properties of the same alloy, but modified using different treatment procedures. 

In theory, electron diffraction measurements on gaseous molecules are somewhat sensitive to the thermal motions of the atoms,... 

To ensure quality control material suppliers and developers routinely measure such complex properties as molecular weight and its distribution, crystallinity and crystalline lattice geometry, and detailed fracture characteristics (Chapter 6). They use complex, specialized tests such as gel permeation chromatography (2, 3), wide- and narrow-angle X-ray diffraction, scanning electron microscopy, and high-temperature pressurized solvent reaction tests to develop new polymers and plastics applications. 

X-Ray and electron diffraction measurements have been most usually used to characterize the phases present in any reactant mixture, and provide a means of identification of solid reactants, intermediates and products. In addition to such qualitative analyses, the method can also be used quantitatively, with suitable systems, to determine the amounts of particular solids present [111], changes in lattice parameters during reaction, topotactical relationships between reactants and products, the presence of finely divided or strained material, crystallographic transformations, etc. 

Indications are that a C—D bond is slightly shorter than a corresponding C—H bond. Thus, electron-diffraction measurements of C2H6 and showed a C—H bond distance of 1.1122 0.0012 A and a C—D distance of 1.1071 0.0012... 

Another seven-membered ring that shows some aromatic character is tropone (44). This molecule would have an aromatic sextet if the two C=0 electrons stayed away from the ring and resided near the electronegative oxygen atom. In fact, tropones are stable compounds, and tropolones (45) are found in nature. However, analyses of dipole moments, NMR spectra, and X-ray diffraction measurements show that tropones and tropolones display appreciable bond alternations. ... 

In the matrix of PLA/ polycaprilactone (PCL)/OMMT nano-composites, the silicate layers of the organoclay were intercalated and randomly distributed (Zhenyang et at, 2007). The PLA/PCL blend significantly improved the tensile and other mechanical properties by addition of OMMT. Thermal stability of PLA/PCL blends was also explicitly improved when the OMMT content is less than 5%wt. Preparation of PLA/thermoplastic starch/MMT nano-composites have been investigated and the products have been characterized using X-Ray diffraction, transmission electron microscopy and tensile measurements. The results show improvement in the tensile and modulus, and reduction in fracture toughness (Arroyo et ah, 2010). 

Ge) for the electron diffraction measurements was carried out by thermal reaction of silicon (1200°C, 1 Torr) or germanium (620-660°C, 1 Torr) with the corresponding tetrahalides MX4 or hexahalides M2X6 (Shultz et al., 1979 Schultz et al., 1982 Hargittai et al., 1983). 

It is therefore clear that MaxEnt redistribution of all electrons, using a uniform prior prejudice and carried out in the absence of very high-resolution diffraction measurements, cannot be expected to reproduce a physically acceptable picture of atomic cores. The reconstruction of total electron densities from limited-resolution diffraction measurements amounts to a misuse of the MaxEnt method, especially when the prior prejudice is uniform. 

For simple monovalent metals, the pseudopotential interaction between ion cores and electrons is weak, leading to a uniform density for the conduction electrons in the interior, as would obtain if there were no point ions, but rather a uniform positive background. The arrangement of ions is determined by the ion-electron and interionic forces, but the former have no effect if the electrons are uniformly distributed. As the interionic forces are mainly coulombic, it is not surprising that the alkali metals crystallize in a body-centered cubic lattice, which is the lattice with the smallest Madelung energy for a given density.46 Diffraction measurements... 

Thus, although the initial X-ray study of Cotton, Dollase and Wood (21) was interpreted (22) in terms of a uniform C—C distance and an overall D6h symmetry, Jellinek (23, 24) concluded from his crystallographic data that the benzenoid rings showed alternating C—C bond lengths, with an effective symmetry no higher thanZ)3d. Finally however more accurate low temperature crystal data due to Keulen and Jellinek (25), and electron diffraction measurements by Haoland (26) showed conclusively that bis-benzenechromium has in fact sixfold, D6h, symmetry in both crystal and the gas phase. 

The characterization of evaporated alloy films can be carried out at widely different levels of sophistication. At the very least, it is necessary to determine the bulk composition, probably after the film has been used for an adsorption or catalytic experiment. Then various techniques can be applied, e.g., X-ray diffraction, electron diffraction, and electron microscopy, to investigate the homogeneity or morphology of the film. The measurement of surface area by chemisorption presents special problems compared with the pure metals. Finally, there is the question of the surface composition (as distinct from the bulk or overall composition), and a brief account is given of techniques such as Auger electron spectroscopy which might be applied to alloy films. 

The good agreement between electrochemical and UHV data, documented in Figure 4, is a very important result, because it proves for the first time that the microscopic information which one obtains with surface science techniques in the simulation studies is indeed very relevant to interfacial electrochemistry. As an example of such microscopic information, Figure 5 shows a structural model of the inner layer for bromide specific adsorption at a halide coverage of 0.25 on Ag 110 which has been deduced from thermal desorption and low energy electron diffraction measurements /12/. Qualitatively similar models have been obtained for H2O / Br / Cu( 110) /18/and also for H2O/CI /Ag 110. ... 

As noted earlier, the diffraction of X-rays, unlike the diffraction of neutrons, is primarily sensitive to the distribution of 00 separations. Although many of the early studies 9> of amorphous solid water included electron or X-ray diffraction measurements, the nature of the samples prepared and the restricted angular range of the measurements reported combine to prevent extraction of detailed structural information. The most complete of the early X-ray studies is by Bon-dot 26>. Only scanty description is given of the conditions of deposition but it appears likely his sample of amorphous solid water had little or no contamination with crystalline ice. He found a liquid-like distribution of 00 separations at 83 K, with the first neighbor peak centered at 2.77 A. If the pair correlation function is decomposed into a superposition of Gaussian peaks, the area of the near neighbor peak is found to correspond to 4.23 molecules, and to have a root mean square width of 0.50 A. 

The application of electron diffraction may be hindered, however, by the lack of knowledge of the vapor composition or by the insufficient concentration of the species to be investigated. The solution to this problem is the simultaneous mass ectrometric and electron diffraction measurements. In this combined experiment the vapor composition and the optimal experimental conditions are determined prior to and during the diffraction experiment. We have employed this combined technique in the Budapest laboratory and are aware of similar attempts at the University of Oslo and The University of Texas at Austin. 

They also treated 71 electron diffraction measurements involving both bonds and nonbonded interactions in the distance range 1.217 5.618 A and established... 

The object of this paper is to discuss some of these problems. We start with the evidence for the new system of ionic radii. X-rays are diffracted by electrons in principle therefore X-ray diffraction should always locate the few outer electrons involved in bonding, but in fact this requires sophisticated treatment of meticulous measurements on crystals of high symmetry [6—9). But it has long been clear that some ionic crystals show round each ion an electron density which is approximately spherical but falls away to a very low background the following Table shows a typical example. 

---