Crystals

Crystals are solids with a long range order, periodicity. The atoms in a crystal are in a regular
repeating pattern called the crystalline lattice. A crystal is a repeating array. In describing this
structure we must distinguish between the pattern of repetition (the lattice type) and what is
repeated (the unit cell). The properties of the crystal thus can be related to the property of its unit
cell.
The most fundamental property of a crystal lattice is its symmetry. Symmetry restricts unit cells
to certain shapes, such that all space can be covered without gaps and overlaps. In 2 dimensions,
for examples, pentagons can not sutisfy that,

but squares, rectangels and hexagons can.
In 3 dimensions, the idea is similar - unit cells stack like boxes, filling the space, making the
crystal. There are seven usually identified types of crystal latices:

Triclinic
a >< b >< c
o >< | ><
Monoclinic
a >< b >< c
o = | = t/2 ><
Orthorhombic
a >< b >< c
o = | = = t/2
Tetragonal
a = b >< c
o = | = = t/2
Trigonal
a = b = c
o = | < 2t/3; >< t/2
Hexagonal
a = b >< c
o = | = t/2; = 2t/3
Cubic
a = b = c
o = | = = t/2
Crystals form because of the attraction between atoms. Due to their attraction, it is favorable to
have many neighbors and unfavorable - to have a lot of empty space. Thus, the coordination
number, or number of adjacent atoms, is important.
In 2 dimensions. For a square lattice as shown on the left, the
coordination number is 4 (the number of circles touching any
individual). The coordination geometry is square, as shown
below. The empty spaces between the atoms are interstitial
sites. Since each atom is touched by 4 circles, the interstitial
sites are also 4-coordinate, and the geometry is also square. In
this example there are the same number of interstitial sites as
circles.

Because the atoms attract one another, there is a tendency to minimize empty space. The
packing efficiency (PE) is the fraction of the crystal (or unit cell) actually occupied by the
atoms. It must always be less than 100% because it is impossible to pack spheres (atoms are
usually spherical) without having some empty space between them.
P.E. = (area of circles within the unit cell) / (area of unit cell)
Regarding the square lattice of circles, we can calculate the packing efficiency (PE) for this
particular lattice as follows:
P.E. = t r
2
/ (2r)
2
= t/4 = 78.54%.
The interstitial sites must occupy 100% - 78.54% = 21.46%.
For hexagonal lattice :
atomic coordination number is 6, but interstitial coordination
number is 3
atomic coordination geometry hexagonal but interstitial
coordination geometry is triangular
packing efficiency is 90.69%
You can see that in this packing there are twice as many of
these 3-coordinate interstitial sites as circles - for each circle
there is one pointing left and another pointing right. Thus,
these sites are much smaller than those in the square lattice.
The larger coordination number (more bonds) and greater
packing efficiency suggest that this would be a more stable lattice than the square one.
In 3 dimensions we have more choices.
Simple cubic (sc) is the simplest and often is observed for metals where too close packing
encounters greater repulsion of cations. Here are two ways to draw a unit cell for the simple
cubic structure. In the unit cell on the left, the atoms at the corners are cut because only a portion
(in this case 1/8) belongs to that cell. The rest of the atom belongs to neighboring cells, as shown
in the stacking below. (I took the pictures from the Structure of Crystals ) The picture on the
right emphasizes that effectively there is one atom per unit cell.

In 3-D the packing efficiency is given by:
P.E. = (volume of spheres within the unit cell) / (volume of cell)
For a simple cubic lattice, this is: P.E. = (1/8 x 8)(4/3 t r
3
) / (2r)
3
= t /6 = 52.35%.
This low value is not suprising. Remember that a 2-D square lattice uses space inefficiently. A
simple cubic lattice is its 3-D analog, and also contains much empty space. Speaking of which,
each unit cell contains one large interstitial site in its center (47.65% of the volume). There are
8 atoms touching this space, so the interstitial coordination number is 8, and its geometry is
cubic (a cube has 8 corners).

Since each unit cell contains (8 x 1/8 =) 1 atom and 1 interstitial site, the number of atoms and
interstitial sites is the same. The arrangement about any single atom in the simple cubic lattice
is given by 6 neighboring atoms, so the atomic coordination number is 6. The coordination
geometry is octahedral (an octahedron has 6 corners).
There are two possibilities for closed packed structures: Cubic Close Packed (ccp) and
Hexagonal Close Packed (hcp)
Cubic Close Packed (ccp) also comes with a different name, Face Centered Cubic (fcc).
This cell has an additional atom in each face of the simple cubic lattice - hence the "face centered
cubic" name. The effective number of atoms is 3 per unit cell. In the picture below various
colors are used to help viewing how cells stack in the solid (the atoms are all the same).


The unit cell here is shown expanded for visibility. Actually, the corner atoms touch the one in
the center of the face. The name "close packed" refers to the packing efficiency of 74.05%. No
other packing can exceed this efficiency (although there are others with the same packing
efficiency).
If we stack the cells into a lattice we notice that the atoms form diagonal layers - the reason for
the colors is to make these stand out. Note that diagonal layers also form along our line of sight.
Since these cut across the other layers, each layer will contain all three colors.

These layers can be seen in the following way of constructing closed packed structures.
If we start with a hexagonal array of spheres (the blue "A" layer), that would be the most-packed
arrangement - there is no way to pack more spheres into a given area. The second close-packed
layer (the gold "B" layer), also hexagonal, will go atop the the first, so they nestle into the left-
pointing holes in the first. All spheres are actually the same atom, the colors are to help you keep
track of the layers.

Notice that there are two separate choices for the second layer; in the animation (all are taken
from the Structure of Crystals) above, we have arbitrarily chosen to cover the left-pointing
holes. We can put them over either all the "left-pointing" interstices or all the "right-pointing"
interstices. If we put them over the right-pointing interstices we generate a different layer,
labeled the green or "C" layer. Remember there are twice as many interstitial sites as
spheres. (One left-pointing and one right-pointing).
We can continue to stack these layers in any order, providing that no 2 identical layers are
adjacent. The cubic close (ccp = fcp) packed structure can be constructed from the A - B - C - A
- B - C . . . . . sequence. An alternate sequence might be B - A - C - B - A - C ... which
represents the same structure. The resulting structure is a 3-D analog of the hexagonal packing
in a plane - it is the most efficient way to pack spheres. Examples of fcc/ccp metals include
nickel, silver, gold, copper, and aluminum.
Hexagonal Close Packed (hcp). Another way of stacking these layers is to omit the "C" layers
altogether and alternate just "A" and "B". This is also a close-packed array and has 3 atoms per
unit cell, but the symmetry is different. It is called Hexagonal Close Packed (hcp). The
hexagonal close packed structure can be made by piling layers in the A - B - A - B - A - B . . . . .
sequence. An alternative sequence would be A - C - A - C - A ...

Examples of hcp metals include zinc, titanium, and cobalt. The unit cell is represented below:

Comparison of fcc/ccp and hcp. Both structures are composed of stacked hexagonal layers.
Their packing efficiencies is identical and equals:
P.E. = (volume of spheres within the unit cell) / (volume of cell)
For both ccp and hcp: P.E. = (4)(4/3 t r
3
) / (2
9/2
r
3
) = t/(3 x 2
1/2
) = 74.05 % - the highest
possible.
Since interstitial sites can be built only on one layer or between two layers, both hcp and ccp
have the same interstitial sites. There are three types of interstitial sites: trigonal, tetragonal and
octahedral. Three coordinate trigonal intersticial sites appear within a layer, the other two -
between layers. Let us consider a pair of layers - blue and gold.

Under each gold atom is a small space surrounded by 4 atoms in a tetrahedral arrangement.
This is a 4 - coordinate tetrahedral interstitial site

The cavities with repeating holes in two layers are surrounded by 6 atoms in octahedral
geometry. This is a 6 - coordinate octahedral interstitial site.

There are some subtle differences between these two close packed structures. The coordination
geometry about each atom is shown below. Note that while both structures have CN = 12 the
arrangements are slightly different. In hcp, the top and bottom three are directly above one
another. In ccp, they are staggered.

Another difference arises from the packing order. In the hcp, there are repeating holes in every
other layer. Thus, if we look directly down on the structure we can see tiny channels throught the
hcp structure. These are absent in ccp.
Body Centered Cubic (bcc) has an additional atom in the center of cubic cell.

The atoms in the picture above are spread out for better view. It is clear that effectively there 1 +
8*1/8 = 2 atoms per unit cell. The packing efficiency of bcc is considerably higher than that of
a simple cubic but lower then that of closed packed ones:
P.E. = (2)(4/3 t r
3
) / [(2

r)
3
/3
3/2
] = 3
1/2
t/8 = 68.02 %
The higher coordination number and packing efficency mean that this lattice uses space more
efficiently than simple cubic. BCC lattices are very common in metals, examples: iron,
chromium, tungsten, and sodium.

Ionic compounds generally have more complicated structures than metals. This is probably
because:
1. There are at least two kinds of particles in the lattice, generally of different sizes.
2. The cations attract the anions, but like ions repel one another. The structure must balance
both types of forces.
3. Many ions (e.g. nitrate, carbonate, azide) are very non-spherical in shape. They will thus
pack differently in different directions.
Cesium Chloride Cesium chloride crystallizes in a cubic lattice. The
unit cell may be depicted as shown. (Cs
+
is teal, Cl

is gold). The ions are

slightly moved apart allowing the interior to be viewed.
One way to describe the crystal is to consider the cations and anions
separately. We begin with the larger (gold colored) Cl
-
ions. Ignoring the
Cs
+
, we note that the Cl
-
themselves form a simple cubic anion
sublattice. Considering only the Cs
+
, they form a simple cubic cation sublattice.

We can describe the CsCl structure as two interpenetrating simple cubic cation and anion
sublattices. (The two sublattices are not necessarily the same, although in this example they are.)
In the simple cubic lattice there are large interstitial sites between each 8 atoms. Therefore CsCl
can be made by placing placing Cl
-
into the interstitial sites. The same crysrtal can be built in
the reverse order, by making sc stucture of Cl- and placing Cs
+
in the interstitial sites
The neighborhood in which each ion finds itself is obvious from the unit cell. Each Cs
+
is
surrounded by 8 Cl
-
(so the Cs
+
coordination number is 8) at the corners of each cube. Each Cl
-

is also surrounded by 8 Cs
+
at the corners of a cube, so the Cl
-
has CN = 8.
If we would have tried to build the Cl
-
sublattice as fcc, the interstitial sites for that lattice would
not be large enough to accomodate Cs
+
ions. Smaller Na
+
ions, on the other hand, can fit into
those cavities. As a result, Sodium chloride crystallizes in a cubic lattice where (red on the
picture) Cl
-
ions form fcc sublattice. The Na
+
(blue) also form an fcc sublattice.

There are 6 Cl surrounding each Na, and 6 Na around each Cl. We can look at the NaCl as made
up of fcc / ccp lattices interpenetrating. The Na's occupy the octahedral sites in the Cl sublattice,
and the Cl's occupy the octahedral sites in the Na sublattice.
These two crystals have MX stoichiometry. What about MX
n
, where n >1? Each unit cell has to
have n times more X than M.