Manual of Cubic Unit Cells Model Kit

Introduction

The outstanding macroscopic properties of crystalline solids are rigidity, incompressibility and
characteristic shape. All crystalline solids are composed of orderly arrangements of atoms, ions,
or molecules. The macroscopic result of the microscopic arrangements of the atoms, ions or
molecules is exhibited in the symmetrical shapes of the crystalline solids.

Solids are either amorphous, without form, or crystalline. In crystalline solids the array of
particles are well ordered. Crystalline solids have definite, rigid shapes with clearly defined
faces. The arrangement of the atoms, ions or molecules are very ordered and repeat in 3-
dimensions. A fundamental concept in the description of crystalline solids is that of a “Bravais
lattice”. A Bravais lattice is an infinite arrangement of points (to which are attached atoms or
molecules or ions) in space that has the following property:

 The lattice looks exactly the same when viewed from any lattice point
 A primitive cell of a Bravais lattice is the smallest region which when translated by all
different lattice vectors can “tile” or “cover” the entire lattice without overlapping

It is very cumbersome to draw entire lattices in 3D so some small portion of the lattice, having
full symmetry of the lattice, is usually drawn. This small portion when repeated can generate
the whole lattice and is called the “unit cell” and it could be larger than the primitive cell. There
are 14 different Bravais lattices in 3D that are classified into 7 different crystal systems .The unit
cell shape for each crystal system can be described by the relative lengths of the unit vectors
and the angles between them.

In 3D, there are 7 crystal systems:

 Triclinic
 Monoclinic
 Orthorhombic
 Trigonal (Rhombohedral)
 Hexagonal
 Tetragonal
 Simple cubic

The templates of the above crystal systems are available with us.

With the help of this kit, we will explore the cubic unit cells in detail to understand the structure of
most metals and a wide range of ionic compounds.
Main Features of the Cubic Unit Cells Model Kit
1. 8-slit balls at the corners , faces or centre of cubic unit cells shows the contribution of
atoms clearly per unit cell.
2. Planar sheets help in visualization of different planes in cubic unit cells.
3. Tetrahedra helps in visualization of tetrahedral holes . But it is cautioned that the
boundaries of the void space are spherical sections, not tetrahedra. The tetrahedron is
just an imaginary construction whose four corners point to the centers of the four
atoms that are in contact.
4. The model kit helps in visualization of octahedral holes in an explicit manner.
5. 4 and 8 tetrahedra enclosing ball and stick tetrahedron placed at alternate small cubes
formed and at all small cubes of the cubic unit cell show clearly the ZnS and CaF2
structures clearly.
6. The model kit also helps in understanding AB, AB,….. and ABC, ABC,……. Packing and
visualization of FCC from ABC, ABC, …. Packing.

List of items:

1. 8-slit balls 18 ( 16 of one colour and 2 of another colour)

2. Planar sheet 20
3. Tetrahedra 8
4. Four-prong atom 8
5. Linkers 32
6. Small connectors 20
7. Manual 1
8. Box 1
Exploration

First of all let us construct AB, AB, ………..Packing by joining the balls with the help of small
connectors . First let us make the first layer as
The second layer is
We can put the third layer as the same as first layer to get AB, Ab,……Packing. To get ABC , ABC
packing we have to put the third layer so that the balls are not above that of first layer. In fact
this ABC, ABC … packing is cubic close packing or Face Centered cubic which can be viewed by
tilting through 45 degree as below

By tilting through 45 degree , we get FCC

In the cubic crystal system three types of arrangements (3 Bravais lattices) are found;

 Simple cubic
 Body-centered cubic
 Face-centered cubic

Cubic lattices are of interest since a large number of materials have a cubic lattice. There are
only three cubic Bravais lattices. All other cubic crystal structures (for instance
the diamond lattice) can be formed by adding an appropriate base at each lattice point to one
of those three lattices. The three cubic Bravais lattices are the simple cubic lattice, the body
centered cubic lattice and the face centered cubic lattice. The reduction of possible lattice types
into primitive Bravais lattices, has nothing to do with “space available” or “hindrance”. It is
purely a mathematical property having to do with the symmetry of the lattices. Then a question
arises why is the base-centered cubic lattice is not a Bravais lattice. The base-centered cubic
lattice is not a Bravais lattice, because it is equivalent to a simple tetragonal lattice as shown
below:
Now we would like to peep into the structures of ionic crystals which are composed of charged
species and the ions of the compound have different sizes. The NaCl structure which is common
to LiCl, KBr, RbI, MgO, CaO and AgCl can be viewed in two different ways: face-centered cubic
in chloride ions with sodium ions in every octahedral hole, or as two interpenetrating face-
centered cubic structures.The CsCl structure has a simple cubic arrangement of chlorides ions
with the cesium ion in the body-centered hole (cubic hole). ZnS, or zinc blende, has a face-
centered cubic arrangement of sulfide ions with zinc ions in every other tetrahedral hole.

Calcium fluoride has a face-centered structure of calcium ions with fluoride ions in every
tetrahedral hole.

Tetrahedral holes

If we direct our attention to a region in the diagram where a single

atom is in contact with the three atoms in the layers directly below
it, the void space is known as a tetrahedral hole. A similar space will
be be found between this single atom and the three atoms (not
shown) that would lie on top of it in an extended lattice. Any
interstitial atom that might occupy this site will interact with the
four atoms surrounding it, so this is also called a four-coordinate interstitial space.
Don't be misled by this name; the boundaries of the void space are spherical sections, not
tetrahedra. The tetrahedron is just an imaginary construction whose four corners point to the
centers of the four atoms that are in contact

Octahedral holes

Similarly, when two sets of three trigonally-

oriented spheres are in close-packed contact,
they will be oriented 60° apart and the centers
of the spheres will define the six corners of an
imaginary octahedron centered in the void
space between the two layers, so we call these
octahedral holes or six-coordinate interstitial
sites. Octahedral sites are larger than tetrahedral sites.

An octahedron has six corners and eight sides. We usually draw octahedra as a double square
pyramid standing on one corner (left), but in order to visualize the octahedral shape in a close-
packed lattice, it is better to think of the octahedron as lying on one of its faces (right).
Each sphere in a close-packed lattice is associated with one octahedral site, whereas there are
only half as many tetrahedral sites. This can be seen in this diagram that shows the central
atom in the B layer in alignment with the hollows in the C and A layers above and below

Construction
1. Join the balls with the help of small connectors so as to form a tetrahedral arrangement
and octahedral arrangement.
2. Join the balls with the help of small connectors so as to form close-packed arrangement
of six balls with one ball in the centre to see it as first layer.
3. Join three balls to see it second layer
4. Similarly third layer can be constructed.
Now we study each of the cubic unit cells.

1. Simple Cubic unit cell

The simple cubic unit cell has eight atoms at the corners, which mark the actual cube. These are
corner atoms, so each one only contributes one eighth of an atom to the unit cell, thus giving us
only one net atom.

• 8 particles, one at each corner of a cube

• 1/8th of each particle lies in the unit cell, each particle part of 8 cells and 1 particle in each
unit cell, so 8 corners x 1/8th of each atom equals one atom per unit cell
• coordination number of 6 .

Construction

1. Take 8-slit ball and insert the planar sheets into the slits such that each slit is occupied
to form 8 small cubes . Buid the structure such that there are 8 balls at the corner of the
cube.
2. Now consider only the inside of the big cube. You will notice that at each corner of the
cube 1/8 portion of each ball is inside the cube. Thus total ball inside the cube is 8X1/8=
1 ball i.e. total no of atoms contributed by a simple cubic unit cell is one. Neglect the
central ball for the moment.
3. In order to view octahedral holes, one is in the center and other ones can be viewed
through arrangement around one of the balls in the center of the edge of the cube.
4. Tetrahedral holes and their geometry can be viewd by placing tetrahedra at the
appropriate places in the center of the smaller cubes.
 2.Body-centered cubic unit cell

This unit cell uses nine atoms, eight of which are corner atoms (forming the cube) and one
more in the center of the cube. The corners contribute only one net atom and the center atom
contributes another for a total of two net atoms. Since the center atom is in contact with eight
other atoms, we say that it has a coordination number of eight.

9 particles, one at each corner of a cube+ one in center

• 1/8th of each corner particle lies in the unit cell
– 2 particles in each unit cell
• 8 corners x 1/8 + 1 center
• coordination number of 8

Construction

1. Proceed as step 1 in A, but now consider the ball in the center of big cube.
2. Now you see that one full ball + portion of balls at the corner contribute to the cube
making two atoms per unit cell.
 3. Face-centered cubic unit cell

This unit cell uses 14 atoms, eight of which are corner atoms (forming the cube) with
the other six in the center of each of the faces. Since the face atoms are shared by two
cubes, they only contribute three net atoms to the unit cell. These three atoms plus the
one from the corners yield the observed four net atoms in the unit cell. Please, notice
that once more, the corner atoms do not touch one another, touching instead through
the diagonal of the face. Look at the structure carefully and corroborate that we have a
coordination number of 12.

Construction

1. Proceed as step 1 above, but now insert balls at the centre of each face.
2. Now count the portion of the balls inside the cube. You will notice that at each face
center, half of the ball is inside the cube. There are 6 faces contributing 3 atoms per unit
cell + one atom at the corner making 4 atoms per unit cell.
3. Octahedral holes and tetrahedral holes are as in simple cubic unit cell.
The face-centered cubic unit cell contains a single octahedral hole within itself, but octahedral
holes shared with adjacent cells exist at the centers of each edge.

Each of these twelve edge-located sites is shared with four adjacent cells, and thus contributes
(12 × ¼) = 3 atoms to the cell. Added to the single hole contained in the middle of the cell, this
makes a total of 4 octahedral sites per unit cell. This is the same as the number we calculated
above for the number of atoms in the cell.

It can be shown from elementary trigonometry that an atom will fit exactly into an octahedral
site if its radius is 0.414 as great as that of the host atoms. The corresponding figure for the
smaller tetrahedral holes is 0.225.
Many pure metals and compounds form face-centered cubic (cubic close- packed) structures.
The existence of tetrahedral and octahedral holes in these lattices presents an opportunity for
"foreign" atoms to occupy some or all of these interstitial sites. In order to retain close-packing,
the interstitial atoms must be small enough to fit into these holes without disrupting the host
CCP lattice. When these atoms are too large, which is commonly the case in ionic compounds,
the atoms in the interstitial sites will push the host atoms apart so that the face-centered cubic
lattice is somewhat opened up and loses its close-packing character. In the face centered cubic
(fcc) cell there is more than one type of 'hole'. If the octahedral holes are filled, the structure
above results, with a one:one count for the two types of ions in the salt. If the terahedral holes
are filled, a diffrerent structure exists, that with twice as many of one type of ion as the other.
In the figure below, The left shows the structure of NaCl and the right that of CaF 2.
Some salts want to use the tetrahedral holes because of the relative sizes of the positive and
negative ions, but don't fill all of them to maintain stoichiometry, This is the case for ZnSe, the
middle panel below. Other relative ion sizes, like CsCl, left below, are filled simple cubic cells
(not fcc).

The rock-salt structure

Alkali halides that crystallize with the "rock-salt" structure exemplified by sodium chloride can
be regarded either as a FCC structure of one kind of ion in which the octahedral holes are
occupied by ions of opposite charge, or as two interpenetrating FCC lattices made up of the two
kinds of ions. The two shaded octahedra illustrate the identical coordination of the two kinds of
ions; each atom or ion of a given kind is surrounded by six of the opposite kind, resulting in a
coordination expressed as (6:6). Compare this figure with the model you construted.

How many NaCl units are contained in the unit cell? If we ignore the atoms that were placed
outside the cell in order to construct the octahedra, you should be able to count fourteen
"orange" atoms and thirteen "blue" ones. But many of these are shared with adjacent unit cells.

An atom at the corner of the cube is shared by eight adjacent cubes, and thus makes a 1/8
contribution to any one cell. Similarly, the center of an edge is common to four other cells, and
an atom centered in a face is shared with two cells. Taking all this into consideration, you
should be able to confirm the following tally showing that there are four AB units in a unit cell
of this kind.

Orange Blue
8 at corners: 8 x 1/8 = 1 12 at edge centers: 12 x ¼ = 3
6 at face centers: 6 x ½ = 3 1 at body center = 1

total: 4 total: 4

If we take into consideration the actual sizes of the ions (Na+ = 116 pm, Cl– = 167 pm), it is
apparent that neither ion will fit into the octahedral holes with a CCP lattice composed of the
other ion, so the actual structure of NaCl is somewhat expanded beyond the close-packed
model.

Now let us consider the structure of specific compounds which can be visualized with the
model kit.
1. The zinc-blende structure: using some tetrahedral holes

Since there are two tetrahedral sites for every atom in a close-
packed lattice, we can have binary compounds of 1:1 or 1:2
stoichiometry depending on whether half or all of the
tetrahedral holes are occupied.
Zinc-blende is the mineralogical name for zinc sulfide, ZnS. This structure consists essentially of
a FCC (CCP) lattice of sulfur atoms (orange) (equivalent to the lattice of chloride ions in NaCl) in
which zinc ions (green) occupy half of the tetrahedral sites. As with any FCC lattice, there are
four atoms of sulfur per unit cell, and the the four zinc atoms are totally contained in the unit
cell.

Each atom in this structure has four nearest neighbors, and is thus tetrahedrally coordinated.

It is interesting to note that if all the atoms are replaced with carbon, this would correspond to
the diamond structure.

2. The fluorite structure: all tetrahedral sites occupied

Fluorite, CaF2, having twice as many ions of fluoride as of calcium, makes use of all eight
tetrahedral holes in the CPP lattice of calcium ions (orange) depicted here. To help you
understand this structure, we have shown some of the octahedral sites in the next cell on the
right; you can see that the calcium ion at A is surrounded by eight fluoride ions, and this is of
course the case for all of the calcium sites. Since each fluoride ion has four nearest-neighbor
calcium ions, the coordination in this structure is described as (8:4).

Although the radii of the two ions (F–= 117 pm, Ca2+ = 126 pm does not allow true close packing,
they are similar enough that one could just as well describe the structure as a FCC lattice of
fluoride ions with calcium ions in the octahedral holes.
Constrution

1. Construct the structure as in a. Now take the four prong atom and put the
connectors on to its prongs.
2. Fold the tetrahedron and place the above tetrahedral arrangement in this
tetrahedron. Similarly make other tetrahedron.
3. Place the tetrahedron in the small cubes as per the requirement of the
structur i.e. at alternate small cubes for ZnS structure and in all the eight
small cubes for CaF2 structures.
4. Care should be taken so as to point the connectors to the balls at the
corners and face centre.
Simple- and body-centered cubic structures

The simplest of the three cubic lattice types, the simple cubic lattice,
lacks the hexagonally-arranged layers that are required for close
packing. But as shown in this exploded view, the void space between
the two square-packed layers of this cell constitutes an octahedral hole
that can accommodate another atom, yielding a packing arrangement
that in favorable cases can approximate true close-packing. Each
second-layer B atom (blue) resides within the unit cell defined the A
layers above and below it.

The A and B atoms can be of the same kind or they can be different. If
they are the same, we have a body-centered cubic lattice. If they are different, and especially if
they are oppositely-charged ions (as in the CsCl structure), there are size restrictions: if the B
atom is too large to fit into the interstitial space, or if it is so small that the A layers (which all
carry the same electric charge) come into contact without sufficient A-B coulombic attractions,
this structural arrangement may not be stable.

The cesium chloride structure

CsCl is the common model for the BCC structure. As with so many other structures involving
two different atoms or ions, we can regard the same basic structure in different ways. Thus if
we look beyond a single unit cell, we see that CsCl can be represented as two interpenetrating
simple cubic lattices in which each atom occupies an
octahedral hole within the cubes of the other
lattice.
Concept Map