Rock-salt crystal structure

Fig. 1.2 Crystal structures of the major sulfides (metal atoms are shown as smaller or black spheres) (A) galena (PbS) structure (rock salt) (B) sphalerite (ZnS) structure (zinc blende) (C) wurtzite (ZnS) strucmre (D) pyrite structure and the linkage of metal-sulfur octahedra along the c-axis direction in (/) pyrite (FeSa) and (//) marcasite (FeSa) (E) niccolite (NiAs) structure (F) coveUite (CuS) structure (layered). (Adapted from Vaughan DJ (2005) Sulphides. In Selley RC, Robin L, Cocks M, Plimer IR (eds.) Encyclopedia of Geology, MINERALS, Elsevier p 574 (doi 10.1016/B0-12-369396-9/00276-8))...

As Pauling took up the technique, only 10 years after its discovery, laboratories in Europe were already describing the atomic architecture of dozens of crystals, from rock salt to diamonds. They were confirming some old theories— finding, as predicted, that carbon atoms often join to make three-sided pyramids called tetrahedra—but throwing out others. Hard data about structure at the atomic level could now, for the first time in human history, be used to test chemists ideas. 

The simplest model, of course, is a free cluster. This is merely a finite, mostly rather small part of the crystal, used without any modification. In most cases, such a cluster consists of an array of mxnxp atoms or imit cells, where m, n, and p denote the niunber of atoms or imit cells in the three Cartesian directions or along the crystallographic axes. Other cluster designs are also used occasionally. Figure 1 shows two examples The first one in Fig. la is a small NiO cluster containing two layers of nine atoms each, i.e., a 3x3x2 cluster in the above notation. Clusters of this kind have been used frequently to represent the (100) surface plane of crystals with rock salt structure (see below). The second example in Fig. lb is a cluster which is part of the wurtzite structure... 

All the alkali metal halides except CsCl, CsBr and Csl form cubic crystals with rock-salt structure, where each metal cation is surrounded by six halide anions, and each anion surrounded by six cations at the comers of an octahedron. See Fig. 5.3. Consultation of a textbook on elementary inorganic or physical chemistry should make it clear that the energy of one mole of the crystalline material relative to the separated, neutral atoms is given by... 

Table 5.2. Coordination numbers, C, Madelung constants, M, and calculated bond distance ratios, R R, for gaseous, monomeric alkali metal halides MX, gaseous square dimers M2X2, for cubic tetramers M4X4 and for MX crystals with rock-salt structures.

The formation of a surface by separating a crystal with rock salt structure is straightforward, because a cut perpendicular to the (100) crystal direction results always in the formation of two equivalent rock salt (100) surfaces, exhibiting the same surface structure and number of ions. However, the situation becomes more difficult for oxide structures with a more complex stacking sequence. In Figure 15.4b, we show three possibilities to separate a crystal with rutile stmcture... 

Calculations of this type are carried out for fee, bcc, rock salt, and hep crystal structures and applied to precursor decay in single-crystal copper, tungsten, NaCl, and LiF [17]. The calculations show that the initial mobile dislocation densities necessary to obtain the measured rapid precursor decay in all cases are two or three orders of magnitude greater than initially present in the crystals. Herrmann et al. [18] show how dislocation multiplication combined with nonlinear elastic response can give some explanation for this effect. 

X-ray structural studies have played a major role in transforming chemistry from a descriptive science at the beginning of the twentieth century to one in which the properties of novel compounds can be predicted on theoretical grounds. When W.L. Bragg solved the very first crystal structure, that of rock salt, NaCl, the results completely changed prevalent concepts of bonding forces in ionic compounds. 

The compound Li4Nb04F crystallizes in cubic syngony, with a cell parameter of 4.192 A and a Rock Salt (NaCl) structure. The compound s X-ray diffraction pattern and cell parameter are very similar to those of nickel oxide, NiO. 

In the case of lithium orthoniobate, Li3Nb04, no meta-stable phase was found that had a rock-salt crystal structure with disordered cation distribution [268]. Nevertheless, solid solutions Li2+xTii-4xNb3x03, where 0 < x < 0.22, have a monoclinic structure at low temperatures and undergo transformation to a disordered NaCl type structure at high temperatures [274]. 

In all cases, broad diffuse reflections are observed in the high interface distance range of X-ray powder diffraction patterns. The presence of such diffuse reflection is related to a high-order distortion in the crystal structure. The intensity of the diffuse reflections drops, the closer the valencies of the cations contained in the compound are. Such compounds characterizing by similar type of crystal structure also have approximately the same type of IR absorption spectra [261]. Compounds with rock-salt-type structures with disordered ion distributions display a practically continuous absorption in the range of 900-400 cm 1 (see Fig. 44, curves 1 - 4). However, the transition into a tetragonal phase or cubic modification, characterized by the entry of the ions into certain positions in the compound, generates discrete bands in the IR absorption spectra (see Fig. 44, curves 5 - 8). 

Thus, in cubic oxyfluorides of niobium and tantalum with rock-salt (NaCl) crystal structures, the formation and extinction of spontaneous polarization occurs due to polar ordering or disordering of Li+ - Nb5+(Ta5+) dipoles. 

The rock-salt structure is a common ionic structure that takes its name from the mineral form of sodium chloride. In it, the Cl- ions lie at the corners and in the centers of the faces of a cube, forming a face-centered cube (Fig. 5.39). This arrangement is like an expanded ccp arrangement the expansion keeps the anions out of contact with one another, thereby reducing their repulsion, and opens up holes that are big enough to accommodate the Na+ ions. These ions fit into the octahedral holes between the Cl ions. There is one octahedral hole for each anion in the close-packed array, and so all the octahedral holes are occupied. If we look carefully at the structure, we can see that each cation is surrounded by six anions and each anion is surrounded by six cations. The pattern repeats over and over, with each ion surrounded by six other ions of the opposite charge (Fig. 5.40). A crystal of sodium chloride is a three-dimensional array of a vast number of these little cubes. 

The saline hydrides are white, high-melting-point solids with crystal structures that resemble those of the corresponding halides. The alkali metal hydrides, for instance, have the rock-salt structure (Fig. 5.39). 

Madelung constant (A) A number that appears in the expression for the lattice energy and depends on the type of crystal lattice. Example A = 1.748 for the rock-salt structure. 

The monosulfides of the alkaline earth metals crystallize in the rock salt (MgS, CaS, SrS, BaS) and zinc blende (BeS) structures. BaS is insoluble in water, while the other monosulfides are sparingly soluble but hydrolyzed on warming (except MgS that is completely hydrolyzed). The monoselenides are isomorphous to the sulfides. The monotellurides CaTe, SrTe, BaTe adopt the rock salt stmcture, while BeTe has the zinc blende and MgTe the wurtzite structure. Alkaline earth polysulfides may be prepared by boiling a solution or suspension of the metal hydroxide with sulfur, e.g.,... 

Most monochalcogenides of the Group 3 metals adopt the rock salt (NaCl) structure. Note that the crystal chemistry of divalent europium is very similar to that of the alkaline earths, particularly strontium, as the radius of Eu is almost the same as that of Sr ". For the Yb compounds, the cell dimensions are practically identical with those of the Ca compounds. 

All the 12 monochalcogenides of the IIB metals crystallize in the tetrahedral zinc blende (ZB) or wurtzite (W) structures, as shown in the table below, with the exception of HgS that exists also in a distorted rock salt (RS) form. 

FIGURE7.4 The rock salt or sodium chloride crystal structure. 

The fourth and final crystal structure type common in binary semiconductors is the rock salt structure, named after NaCl but occurring in many divalent metal oxides, sulfides, selenides, and tellurides. It consists of two atom types forming separate face-centered cubic lattices. The trend from WZ or ZB structures to the rock salt structure takes place as covalent bonds become increasingly ionic [24]. 

A ternary reciprocal system is a system containing four components, but where these components are related through a reciprocal reaction. One example is the system LiCl-LiF-KCl-KF. Solid LiCl, LiF, KC1 and KF are highly ionic materials and take the rock salt crystal structure, in which the cations and anions are located on separate sub-lattices. It is therefore convenient to introduce ionic fractions (Xj) for each sub-lattice as discussed briefly in Section 3.1. The ionic fractions of the anions and cations are not independent since electron neutrality must be fulfilled ... 

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