Spheres, closest packing

Figure 3.35. Position of the holes in closest packing. Unit cell projections are shown for the cubic and hexagonal sphere closest packing. Coordinates of the spheres and of the tetrahedral and octahedral holes are given. The values indicated inside the drawing correspond to the third coordinate (along the vertical axis) when two values are given, these correspond to two positions along the same vertical line.

Closest packed structures contain twice as many tetrahedral holes as packed spheres. Closest packed structures contain the same number of octahedral holes as packed spheres. 

By now, you should have some appreciation for the different types of crystalline lattices and have some idea of the difficulty in predicting the exact structure that a compound will form. There are a variety of factors involved in the process of crystallization, including (but not limited to) closest packing of spheres, closest packing of polyhedra, electrostatic interactions, hydrogen bonding, hybridization, crystal field effects, and the degree of polarization. When it comes to the solid state, simple stoichiometries do not necessarily imply simple structures. 

Unit Cells Packing Spheres Closest Packing... 

The C, values for Sb faces are noticeably lower than those for Bi. Just as for Bi, the closest-packed faces show the lowest values of C, [except Bi(lll) and Sb(lll)].28,152,153 This result is in good agreement with the theory428,429 based on the jellium model for the metal and the simple hard sphere model for the electrolyte solution. The adsorption of organic compounds at Sb and Bi single-crystal face electrodes28,152,726 shows that the surface activity of Bi(lll) and Sb(lll) is lower than for the other planes. Thus the anomalous position of Sb(lll) as well as Bi(lll) is probably caused by a more pronounced influence of the capacitance of the metal phase compared with other Sb and Bi faces28... 

Back reflection of translational and rotational velocity is rather reasonable, but the extremum in the free-path time distribution was never found when collisional statistics were checked by computer simulation. Even in the hard-sphere solid the statistics only deviate slightly from Pois-sonian at the highest free-paths [74] in contrast to the prediction of free volume theories. The collisional statistics have recently been investigated by MD simulation of 108 hard spheres at reduced density n/ o = 0.65 (where no is the density of closest packing) [75], The obtained ratio t2/l2 = 2.07 was very close to 2, which is indirect evidence for uniform... 

Fig. 1.—The arrangement of 45 spheres in icosahedral closest packing. At the left there is shown a single sphere, which constitutes the inner core. Next there is shown the layer of 12 spheres, at the corners of a regular icosahedron. The third model shows the core of 13 spheres with 20 added in the outer layer, each in a triangular pocket corresponding to a face of the icosahedron these 20 spheres lie at the corners of a pentagonal dodecahedron. The third layer is completed, as shown in the model at the right, by adding 12 spheres at corners of a large icosahedron the 32 spheres of the third layer lie at the corners of a rhombic triaconta-hedron. The fourth layer (not shown) contains 72 spheres.

We may use this example of triangular closest packing to derive an expression for the distribution of spheres in successive layers. The form of the expression (number of spheres proportional to the cube of a length, the radius) reflects the assumption of constancy of effective volume per sphere. The expression is... 

The general geometrical problem of the packing of spheres has not been solved. An example of closest packing of atoms with some variation in effective radius is the icosahedral packing found (13) in the intermetallic compound Mg3B(Al,Zn) (Fig. 1). The successive layers in this structure contain 1, 12, 32, and 117 spheres. These numbers are reproduced (to within 1) by the empirical equation (12)... 

Tc or c cubic closest-packing of spheres Th or h hexagonal closest-packing of spheres Ts stacking sequence AA... of hexagonal layers Qs stacking sequence AA... of square layers... 

The structure of iodine at four different pressures. The outlined face-centered unit cell in the 30-Gpa figure corresponds to that of a (distorted) cubic closest-packing of spheres. At 24.6 GPa four unit cells of the face-centered approximant structure are shown the structure is incommensurately modulated, the atomic positions follow a sine wave with a wave length of 3.89 x c. The amplitude of the wave is exaggerated by a factor of two. Lower left Dependence of the twelve interatomic contact distances on pressure... 

In crystalline C60 the molecules have a face-centered cubic arrangement, i.e. they are packed as in a cubic closest-packing of spheres as they are nearly spherical, the molecules spin in the crystal. The crystals are as soft as graphite. Similar to the intercalation com-... 

In a-B12 the icosahedra are arranged as in a cubic closest-packing of spheres (Fig. 11.16). In one layer of icosahedra every icosahedron is surrounded by six other icosahedra that are linked by three-center two-electron bonds. Every boron atom involved contributes an average of electrons to these bonds, which amounts to -6 = 4 electrons per icosahedron. Every icosahedron is surrounded additionally by six icosahedra of the two adjacent layers, to which it is bonded by normal B-B bonds this requires 6 electrons per icosahedron. In total, this adds up exactly to the above-mentioned 10 electrons for the inter-icosahedron bonds. 

Germanium forms the same kinds of modifications as silicon at similar conditions (Fig. 12.4). Tin, however, does not exhibit this diversity )3-tin transforms to a body-centered cubic packing of spheres at 45 GPa. Lead already adopts a cubic closest-packing of spheres at ambient pressure. 

The cluster condensation can be carried on the chains of octahedra sharing edges can be joined to double-strands and finally to layers of octahedra (Fig. 13.18). Every layer consists of metal atoms in two planes arranged in the same way as two adjacent layers of atoms in a closest-packing of spheres. This is simply a section from a metal structure. The X atoms occupy positions between the metal layers and act as insulating layers. Substances like ZrCl that have this structure have metallic properties in two dimensions. 

Unit cells for hexagonal (left) and cubic closest-packing of spheres. Top row projections in the stacking direction. 

The space filling in the body-centered cubic packing of spheres is less than in the closest packings, but the difference is moderate. The fraction of space filled amounts to ns/3 = 0.6802 or 68.02 %. The reduction of the coordination number from 12 to 8 seems to be more serious however, the difference is actually not so serious because in addition to the 8 directly adjacent spheres every sphere has 6 further neighbors that are only 15.5 % more distant (Fig. 14.3). The coordination number can be designated by 8 + 6. 

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