1.

Define Bravais lattices and discuss different types of nonprimitive

Bravais lattices

The unit cell for these reasons is chosen as face-centered

cubic. It was showm by A. Bravais in 1848 that all possible three
dimensional space lattice are of fourteen distinct types. These
fourtenn lattice types ( also known as Bravais lattices ) are
derived from seven crystal systems.

2. What is the importance of studying close packed structures?.

Close Packed (cp)

These are two different names for the same lattice.

We can think of this cell as being made by inserting another atom into
each face of the simple cubic lattice - hence the "face centered cubic"
name.
The reason for the various colors is to help point out how the cells stack
in the solid. Remember that the atoms are all the same.
The unit cell is:

The unit cell is again 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.

A different and better way of looking at this structure

focuses on those layers.We start with a hexagonal array of spheres (the
blue "A" layer). Notice that this is a close-packed arrangement - there is
no way to pack more spheres into a given area.

We then place a second close-packed layer (the gold

"B" layer) 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 2 separate choices for
the second layer; in the animation below, 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 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 ...

The resulting structure is a 3-D analog of the

hexagonal packing in a plane - it is the most efficient way to pack
spheres.
horizontal vertical

However, the internal structures and relationships

can be examined by moving the spheres apart slightly.
horizontal vertical

There are two types of interstitial sites in an fcc

lattice. Let us consider a pair of layers - blue and gold. Remember, the
gold atoms cover all the left-pointing interstices in the blue layer, and
none of the right-pointing ones.

Under each gold atom is a small space

surrounded by 4 atoms in a tetrahedral arrangement. This is a 4 -
coordinate tetrahedral interstitial site.

If we look at the right-pointing holes in the blue

layer, we see that the gold layer does not nestle into them as it does the
left-pointing ones. These cavities are surrounded by 6 atoms in
octahedral geometry.
 2. How many tetrahedral and octahedral voids are there in a FCC unit
cell and where are these located?

A. Simple Cubic Cell

As you rotate the spacefill model around you will notice that all the
spheres (ions or atoms) are in contact with each other. Observe that in
the simple cubic cell the edge equals two atomic radii. The volume of
the unit cell then is the edge cubed (edge3). But the unit cell only
contains, on the lattice points, an eighth of the volume of the sphere (ion
or atoms). Because there are a total of eight one eighth volume spheres
in the cell the simple cubic unit contains one net particle. One important
question should be asked: what is the efficiency of packing same size
atoms in simple cubes?

B. Body-centered Cubic Cell

Rotate the body-centered cubic (bcc) unit cell. As the name suggests it
contains an ion or atom in the center of the cube. If all the spheres have
the same radius, like in metals, then the spheres centered on the lattice
points do not make contact with each other. Another way of looking at
the layout is using 2-dimensional layer diagrams. The bcc has 3 layers
(along the z-axis), which would look like this:
So in this case the edge is greater than two atomic radii of the lattice corners. To
determine the edge value we must rely on the diagonal of the two opposite corners of
the unit cell. This
cube diagonal is 4
atom radius. (See
calculation).

The number of
particles in a
bcc unit cell is
2, determined
as follows: 8
spheres on the
lattice corners
each with an
eighth of their volume within the cell (1 particle) and one sphere completely
embedded in the lattice.

We might expect to have a greater packaging efficiency because there are more
particles within the lattice compared to a simple cubic cell. But we should realize that
the lattice volume has increased accordingly. The ratio of the volumes where all
particles are equal gives us a 68.0%.

Potassium (alkali metal) and iron are examples of metals that arrange themselves in
bcc. The virus that causes foot and mouth disease in animals also exhibits bcc crystal
arrangements.
C. Face-centered Cubic Cell

Illustrated left is the face-centered cubic (fcc) unit cell. It has a particle
in the middle of each of the six faces of the cube. The two-dimensional
layer representation shows that there are six particles which have half of
their volumes within the lattice.

The total number of particles within

the lattice can be calculated as follows:
8 particles on the lattice corners (1
particle), 6 particles with half of their
volumes within the lattice (6 particles* 1/2 volume = 3 particles). This
gives us a total of 4
 Calculation of the edge value is quite straightforward. (See figure for
calculations)

Face-centered cubic cells

have a 74.0% packaging
efficiency for spheres or
ions of equal diameter.
Some examples of fcc
arrangements are:
aluminum, copper and
buckminsterfullerenes
C60 (bucky balls).

It is crucial that we consider that there are holes within these lattices (rotate the 3D fcc
model) which can be filled with smaller ions or particles - we will see this later - thus
increasing packaging efficiency. Compounds like salts fulfill this requirement. Ions of
opposite charge can occupy these spaces. The result is an organized three-dimensional
arrangement of ions and counter-ions.
D. Ionic Compounds

Ionic compounds are made up of anions and cations. Usually the larger anions make
up the framework of the crystal lattice and the smaller cations then occupy the spaces
or holes left between the framework of anions. Packing arrangements like simple
cubic (sc), cubic close-packed (ccp), hexagonal close-packed (hcp) are examples of
structures which minimize same charge interactions.

The Simple Cubic Hole

Let's start with anions packing in

simple cubic cells. As you can see in
Figure 6 the cation can sit in the hole
where 8 anions pack. An example of
this packing is CsCl (See the CsCl
file left; Cl- yellow, Cs+ green). This
lattice framework is arrange by the
chloride ions forming a cubic
structure. The smaller cesium cation
sits in the hole surrounded by 8 chloride ions. Alternatively, it can be
viewed as a chloride anion surrounded by 8 cesium cations. Both have
coordination number 8. Each unit cell has one cesium ion and one
chloride ion.

The cubic hole is quite large. Compare the sizes of Cs+ (1.69 Å) to Cl-
(1.81 Å). It is convenient at this point to clarify the misconception
concerning CsCl arrangement. Cesium chloride does not pack in a
body-centered cubic structure. In a body-centered cubic structure all the
atoms in the unit cell are identical (See section on Body- centered Cubic
Cell). As you may have noticed the cation occupying the center of the
cube is smaller than the anions on the corners of the cube.

The Octahedral Hole

The octahedron is a polyhedron made from 8 regular triangles. The

polyhedron can be constructed by one sphere surrounded by 6 equal
spheres (Figure 7A). If you connect the six centers of the surrounding
spheres you generate the
octahedron.

Face-centered cubic (fcc)

lattice structures provide a
framework for octahedral
holes. A typical example of
this setting is sodium
chloride (NaCl). The
chloride ions form
octahedral holes which the
smaller sodium ions occupy.
(See 3D NaCl file right;
Na+ fuchsia, Cl- green)
There are 4 octahedral holes
in a fcc with a relationship
 of one octahedral hole per anion.
It is important to notice that Na+ ions can be viewed as an
expanded fcc where the chloride ions occupy large octahedral
holes. This arrangement of ions give the Na+ ion as well as the Cl-
ion a coordination number of 6. Each unit cell thus contains 4
Na+ and 4 Cl-, with stoichiometry NaCl
(Figure 7B).

There are compounds where not all the

octahedral holes are filled. In the case of
cadmium chloride, CdCl2 (Figure 8), the large
chloride ions form a fcc framework. Only half
of the octahedral holes are filled by the smaller
cadmium ions, therefore, there will be 2
cadmium ions in a unit cell. At the same time the fcc unit cell
framework of the large anions contains 4 Cl-ions. Consequently, the
stoichiometry for cadmium chloride is CdCl2.

The Tetrahedral Hole

A classic example used to view

a tetrahedral structure is
methane, CH4. The carbon
atom has four equally distanced
hydrogen atoms, each
positioned on the corners of a
tetrahedron. The same idea can
be applied to close-pack spheres (Figure 9A). A sphere occupying a
tetrahedral hole has a coordination number of 4. Tetrahedral holes are
relatively small compared to cubic or octahedral holes.

A fcc arrangement has both tetrahedral and octahedral holes. (Move

your mouse over Figure 9B and see also the location of the octahedral
holes in a cubic close-pack structure.) There are 8 tetrahedral holes and 4
octahedral holes in a fcc unit cell.

The ionic compound sodium oxide

is a good example of a fcc cell
where the oxide ions form the
framework of the unit cell while
the quite small sodium ions
occupy all the tetrahedral holes.
As we take a closer look at the
lattice (see the sodium oxide 3D
file right; O2- red and Na+ pink,
and Figure 10A) you will notice
that there are 4 oxide ions (eight of
them at the corners of the cube
1
with /8 of their volume inside the cell and 6 centered on each face
sharing half of their volume with the unit cell; Figure 10B) and
eight sodium ions (occupying all the tetrahedral holes within the
unit cell). It follows that there are 2 tetrahedral and 1 octahedral
holes per anion in a fcc structure where the anions make the close-
pack framework. Thus the coordination number for Na+ is 4 and
for O2- is 8. Consequently the stoichiometry for sodium oxide is
Na2O.

As expected there can be partial filling of the tetrahedral holes. This is

appropriately illustrated by zinc sulfide (sphalerite). The 3D RasMol file
for zinc blende is shown left, S2- ions in yellow and Zn2+ in burgundy.
The large sulfide ions form the fcc framework. Only half of the
tetrahedral holes are filled by the small zinc ions. In order for each ion to
have an tetrahedral arrangement the zinc ions should occupy the
positions in the lattice such that the line that connects the ionic centers is
a diagonal of the cube in each layer and these lines are orthogonal to
each other (rotate the 3D zinc blende file to verify this characteristic).
Such an arrangement allows each atom to have a coordination number of
4 for which a tetrahedral geometry is viable. Other ionic compounds
which exhibit the same zinc blende arrangement are: AgI and CuCl.

It would be appropriate at this point to have a very brief overview of

more complex ionic structures. As we saw previously in a cubic close-
packed arrangement there are both tetrahedral and octahedral holes.
Certain ionic compounds have the structure of the mineral spinel,
MgAl2O4. It crystallizes in what is an approximate cubic close-packed
structure. The cations, Mg2+ and Al3+, in this structure occupy the
tetrahedral and octahedral holes (recall one octahedral hole and 2
tetrahedral holes per anion in an fcc). The unit cell contains 32 oxide
ions. That translates into 32 octahedral holes and 64 tetrahedral holes.
To have a stoichiometry of 1:2:4 (Mg:Al:O) means that Al3+ ions will
occupy half of the available octahedral holes while the Mg2+ ions should
fill only an eighth of the available tetrahedral holes. Use the 2D layer
diagram below to verify location of each type of hole as well as the

stoichiometry of spinel.

The RasMol 3D representation of spinel also helps visualize its unit cell.
The light pink atoms represent the anions, O2-, the rose colored atoms
represent the Al3+ in the octahedral holes and finally the white atoms
represent the Mg2+ ions in the tetrahedral holes.

Magnetite, Fe3O4, has the same approximate fcc arrangement with the
oxide anions occupying the lattice framework but the octahedral holes
are occupied by both divalent and trivalent iron cations. As a result
octahedral holes in the magnetite spinel arrangement are filled with
equal amounts of Fe3+ and Fe2+ ions. Charge balance and the general
arrangement of cations and anions is preserved.

There are also molecular networks which can be

seen as exhibiting an expanded fcc framework
with partial filling of the tetrahedral holes. As as
example we have diamond. We can think of it as
carbon atoms forming the expanded fcc
framework and also occupying half the
tetrahedral holes. This arrangement is also
common to semiconductors like SiC (silicon
carbide) and BN (boron nitride) and GaAs (gallium arsenide) among
others. We have to keep in mind that in molecular networks (such as
diamond) the coordination number is the number of bonds around each
atom. Observe on the left the 3D silicon carbide file (carbon atoms in
gray, silicon atoms in yellow) and Figure 11 on the right.

4. Define and differentiate between a symmetry operation and a

symmetry element with the help of a suitable example.
A symmetry operation is an action that leaves an object looking the same
after it has been carried out. For example, if we take a molecule of water
and rotate it by 180° about an axis passing through the central O atom
(between the two H atoms) it will look the same as before. It will also look
the same if we reflect it through either of two mirror planes, as shown in the
figure below.
Each symmetry operation has a corresponding symmetry
element, which is the axis, plane, line or point with respect to
which the symmetry operation is carried out. The symmetry
element consists of all the points that stay in the same place
when the symmetry operation is performed. In a rotation, the line
of points that stay in the same place constitute a symmetry axis;
in a reflection the points that remain unchanged make up a plane
of symmetry.
The symmetry elements that a molecule may possess are:
1. EE - the identity. The identity operation consists of doing
nothing, and the corresponding symmetry element is the
entire molecule. Every molecule has at least this element.
2. CnCn - an nn-fold axis of rotation. Rotation
by 360°/n360°/n leaves the molecule unchanged.
The H2OH2O molecule above has a C2C2 axis. Some
molecules have more than one CnCn axis, in which case the
one with the highest value of nn is called the principal axis.
Note that by convention rotations
are counterclockwise about the axis.
3. σσ - a plane of symmetry. Reflection in the plane leaves the
molecule looking the same. In a molecule that also has an
axis of symmetry, a mirror plane that includes the axis is
called a vertical mirror plane and is labeled σvσv, while one
perpendicular to the axis is called a horizontal mirror plane
and is labeled σhσh. A vertical mirror plane that bisects the
angle between two C2C2 axes is called a dihedral mirror
plane, σdσd.
4. ii - a center of symmetry. Inversion through the center of
symmetry leaves the molecule unchanged. Inversion
consists of passing each point through the center of
inversion and out to the same distance on the other side of
the molecule. An example of a molecule with a center of
inversion is shown below.
 5. SnSn - an n-fold improper rotation axis (also called a rotary-
reflection axis). The rotary reflection operation consists of
rotating through an angle 360°/n360°/n about the axis,
followed by reflecting in a plane perpendicular to the axis.
Note that S1S1 is the same as reflection and S2S2 is the
same as inversion. The molecule shown above has
two S2S2 axes.
The identity EE and rotations CnCn are symmetry operations that
could actually be carried out on a molecule. For this reason they
are called proper symmetry operations. Reflections, inversions
and improper rotations can only be imagined (it is not actually
possible to turn a molecule into its mirror image or to invert it
without some fairly drastic rearrangement of chemical bonds) and
as such, are termed improper symmetry operations.