CHAPTER 6 SPHERE AND CYLINDER PACKINGS In this chapter and the next we discuss periodic three-dimensional siuctutes. This extends the diseussion from finite polyhedra, citele packings, and two-dimensional 01, t0 infinite polyhedsa, sphere and cylinder packings, and three-dimensional nets. Now we sre approsching the real world of crystal structures and examples of them will be met more frequently. In many crystal structures one oF several kinds of tom ae in positions corresponding to the centers of spheres in a sphere packing, and other atoms are in positions corresponding to interstices ofthat packing. [is common (especially for mathematiciaas) to cefer to such interstices as “holes,” but that word has been appropriated to have a special meaning (teferring to an electronic defect in Solid state scence, so we avoid it. We generally just refer to “sites.” Inthe same vein, the word “vacancy” has the meaning ofa site that shoud be aceupied but at some particular point in areal crystal isnot (ea special kind of atomic defect). We recommend using “vacancy” onfy in the context of defect thermodynamics and Kinetics (and then with great care), and at other times using ferm such as “unoccupied site” instead Il is essential at the outset to recognize that we are here only concerned with the geometry of certain patlems of points which are of common occurrence in crystal structures, It is convenient to consider such patterns as arising from packings of spheres, but as they can also aise in several other contexts itis important notte get a mental image of exystals as assembled from 2 packing of hard sphere “atoms” as is sometimes seen iMlustrated (we do this ourselves in § 6.1 and 6.2, but nowhere else). We shall see, for example, that in several simple and farlir crystal sieutuces of binary compounds AB the arrays of both the A and the B atoms are the same as the centers of spheres in closest Packing. Unless the spheres representing A and those represeating B iaterpeneiate substantially thee cannot be simultaneous A~A and B-B contacts, (One reason for discussing sphere packings is that tis hard to read the literature of cxystal chemistry without some knowledge of the subject and is associated terminology, The most compelling reason is, however, that the tople intzoduees patterns that are biguitous in crystal struccures; indeed itis hard to invent a simple symmetrical sphere packing that doesnot occur in nature. Our organization is by coordination number, staring ‘With the densest packing of spheres; however, this is for convenience only: we could ‘equally have chosen one of a mumber of other scheanes. 6.1 The densest packing of spheres We consider first the elassieal problem of packing equal-sized spies in space as densely as possible (closest packing). I should be appazent that this isthe same problem as ‘mat of arranging pours ofan inte aray with given Gensity (eumer per unit volume) 50 Sphere and Cylinder Packings 209 ‘thatthe shores distance between them isa maximum; stated this way, the problem is an extension of Tammes" problem (§ 5.1.9) which referred to arranging points (with fixed ‘umber per unit area) onthe surface ofa spkere such thatthe minimum distance beteen them was a maximam. Another preblem with the same solution isto ask for ways of acranging points in space so that every point has twelve equidistant nearest neighbors. Yet ‘nother problem, again with the sime solution, i to ak forthe arrangement of vertices in ‘space-fling packings of regular octabedra and tewaedra with equal edges. "Thus the same geometscal arrangement arses in very different contexts. only one of ‘which involves spheres in contact. When we want to emphasize such considerations we Use the term eutany to mean “an arrangement coresponding tothe centers of spheres in Closest packing” and describe such arrays as eusactic. Generally though, we follow ‘established usage indicated by bold face abbreviations in the next paragraph Tf wo restrict ourselves to arrangements in which the points (or the centers of the spheres) fall ona atce, ther is just one solution to the above problem. The rrengement is ‘commonly referred to as cubic closest packing (ecp), but we also use the term cubic ‘euraryl Ifthe restriction to points on a latice i Uifted, we finda second arrangemeat of ‘equivalent (symmetry-related) points known as “hexagonal closest packing” (hep) or hexagonal extaxy. There is an infinity of other serangements with the same density, but ‘with more than one kind (in the rystallographic sense) of point as we wil see. We refer to these generically as ep of as eutzctic. We consider only periodic pattems and stat results mostly without proof? The construction of models with a dozen or so polystyrene balls, and yoothpcks to bold them togedber wl be found invaluable 6.1 Stacking of close-packed layers Fig 61, Par of yer of clone pakot spheres A marks the comers faut ‘Thee sed as sab ose packing (ep) ao for rangement ony approxima the Meal srargenes. “some obvious” resus are remakay fie wo prove na way aceptabls to mathematins Foe ovmmens om the fot (by W. Hig) that closet yanking” s jst chat se N Mk, Marre 388, 113 tom,210. Chapter 6 Conceptually the simplest way to generate these pattems is to start with a layer of spheres lying on a flat surface ina closest-packed way.! Their centers will be on the vertices of 836 net (a ep layer, just as inthe densest circle packing. Fig. 6.1 shows four such spheres with centers atthe corners of a hexagonal unit cell of 36. inthe figure the letters “A are at these comers Now we add a second close-packed layer on top ofthe fest. To have maximam density ‘we want the spheres ofthe second layer to nestle in the depressions of the frst... over the points marked "8" or “C.” (It shouldbe clea tha B aad C are too close for spaeres of the sevond layer co be simultaneously over both of these positions). Accordingly there sre "ito possibilities for the two-layer structure: AB or AC. These are of course ideptical sangements (remember the layers are infinite inthe pine) For the sake of subsequent slscussion let the arangement chasea be AB forthe moment ig, 6:2, Pa eo layers ofclose-packa spheres. Th ler ain the se plea Fi. 6 A small fragment ofthe two-layer packing is shown in Fig. 6.2. It should be clear from ‘hat figure that if we aow add third layer in a similar way, the centers ofthe spheres i the thine layer must fie over ether A or C so we have two distinct three-layer sequences: ABA ‘and ABC. These differ in that in the first case the layers below and above the midele one ‘are ia same (4) positions, and inthe second case the layers below and above the axiddle ‘one are indifferent positions (A and ©) For unit diameter spheres in contac, the peependicular distance between layers will be (2/3) = 0.8165 (this is the height of a regulac tetrahedron of unit edge, ofp. 133). gs sn we poe sees re a, tr expe, poled stance | | { Sphere and Cylinder Packings 211 Fig. 6.3 shows pars of the two different three-layer sequences. At the top the spheres are pucked ABC and atthe botiom te sequence is ABA. The two simplest infinite packings ‘would be obtained by repeating these sequences indefinitely: ABCABC... and ABAB. Fle, 63. Spheres packed inthe seguznce ABC (top fa and ABA (oto ba. ‘The centers of the spheres in a sab of two layers divide the sab into regula tetrahedra and octahedra. Fig. 64 shows how a ttrahedron and ga octabedron are so defined by foar and six sphere centers respectively. The eutactc arrangements of points thus also arise 2s ‘he position ofthe vertices when regular tetrahedra and octahedea are packed to fll space, and this is possibly the real reason forthe common accarrence of eutxy as the aztagement of cations andor anions in so many compounds in which there is 4 and/or 6-fold coordination (see Notes § 68.3). Figure 655 illustrates the arrangement of octahedra and tetrahedra in a two-layer slab ‘Bach octahedron sares edges with six other octahedra, The tetrahedra can be divided into two groups (see Fig. 6.5): those “pointing down” and those “poiating up.” Tetrahedra of ‘el ype share only verces wids eas oer, Dut e8ch “up” rettanedon snares three edges212 Chapier hom eraede inthe tae layer and ce versa liogetber pss i and ice vera, Altogetir pace dvde into al aumber of vthedr, "ip" teeasmandsdowaetcearas : VS Fig. 64. A tahedion and =n ontario formed by spheres in contac Wig, 5: Mite: th costs of 26 ptr rsa by isi do by ccs) nde ne of cls pking ‘showing the octabedral interstices. Top: the same points, bat now sl “ Tented Bono asa vow owing he "Son rss Baton ‘the same points showing the “wp” tetrahedra. mine Fig. G6. A roombobedeoncomposo! ofa ethan and two taeda ompare Fi, 6.5) Sphere and Cylinder Packings 213 ‘The reader is urged to asseroble auch « layer with polyhedra. When that is done it wi surely be noticed that two tetrahedra may be combined with an octahedron to form a 60" shombohedroa as shown in Fig. 6.6. Cleary chs polyhedron fills space and contains one ‘each ofan “up” tetcahedeon, “down” tetrahedron and an octahedron. We will ee that itis ‘unit cell of eep. It should be clear that each two-layer slab can be divided into such ‘hombohedea, so all ep arrays are made up of octahedra, “up” tetrahedra, and “down” tetrahedra in equal amounts (one each per ep sphere) 6.1.2 Hexagonal eutaxy (hep) We diseuss the case AB... first. We could equally label she sequence AC..., BC. ‘which would describe exactly the seme packing but witha different choice of origin. Inf itis a the origin ofa hexagonal cel itis useful now to describe the two-layer repeat as BC... We can then get a convenient description in crystallographic terms of a hexagonal ‘unit coll with sphere centers at 1/3 2,14 and 2/3,13,34. Ifthe spheres are uit diameter, ‘ail be 1.0 (see Fig. 6.1) and ¢ wil be 2Y(2/3) = V(8/3) = 1.6330. The z coordinates are chosen a5 1/4 and 3/4 (eather than e.g. 0 and 1/2) because we then have the origin of, coordinates at a center of symmetry. The space group is PSs/mmc. The arrangement of Sphere center points is nota lattice, a a vector from the center of a sphere tothe center of a ‘contiguous sphere in an adjacent layer is nota lattice vector. The spheres are related by symmetry though; ther centers are in the special positions 2c of Pésimme. in hep, the planes normal to © and containing the centers of the spheres are mircor planes, It follows therefore, tat the octahedra i successive layers share comimon faces ant form face-sharing colurnns (parallel to ¢). The eeaters ofthe octahedra are at 00,0 and (0,0,1/2 inthe unt cell (2 a of P63/mmc). On the other hand the tetrahedra wil form pairs (one “up” and one “down” with a common face. Recall thatthe “up” set of tetrahedca ave bly common vertices (are eoener-sharing) as do the “down” set. The centers of the tetrahedra are in 4 f-M13,203.2 : 223,13, 1/24e) with z= -1/8, 6.1.3 Cubie eutaxy (cep) “The chombotidron of Fis. 6.6 with points atthe vertices can be considered ss the unit cell ofa structore withthe points coinciding with a atic. The 60° rhombohedcon i, in fact, a primitive cell of the face-centored cubic latice (see § 4.4), Fig. 6.7 shows 14 sphicees with theic centers a the lattice points ofa face-centered cubic cel. As can be seen from the figure tke ceaters of the spre lie in close-packed (111] plans. "The structare we are describing is cublc eutaxy or “cubic close packing” (cep). Discussed in terms of @ stacking of close-packed layers the sequence is ABC... The simplest way to se this is to use the description ofa rhombohedral lattice in terms of a ‘entered hexagonal cell, Thus if the ehombohectl cell (Fig 6.7) has a = 1, o°= 60" then the hexagonal cel has a = 1,¢= 32/3) = 6 = 2.449... and te latie points are at 00,0 (A) 28,13,13 (2); and 18,28.28 (©) “The face-conterod cubic ell containe four lattice points (at 40.0 = 171/20; 172.0112