To study various crystals structures.

Theory
Matter exist usually in solid or fluid (liquid, gas) state. According to modern concept matter
classification is specified as condensed state and gaseous state. Solids and liquids come under
condensed state. Any material whose position of constituent particles is fixed can be regarded as
solids.

Solids are characterized by incompressibility, rigidity and mechanical strength. This indicates that the
molecules, atoms or ions that make up as solid is closely packed. Thus in solids we will have a well
ordered molecular, atomic or ionic arrangement.
In general solids can be classified into:

 Crystalline-particles are orderly arranged (long range order).

 Amorphous-particles are randomly oriented.

If the atoms or molecules are uniquely arranged in crystalline solid or liquid we call it as a crystal
structure. A crystal posses long range order and symmetry. The main property of crystal structure is
its periodicity. This periodicity is due to the arrangement of atoms/molecules in the lattice points. The
crystal structure as a whole can be considered as the repetition of unit cell. For a given crystal
structure the shape of unit cell is same but varies from crystal to crystal.

X-ray diffraction studies reveal that the constituent particles (molecules, atoms or ions) are arranged
in a definite pattern in the crystal. To get the diffraction pattern the wavelength of light used must be
comparable with the atomic spacing.

Lattice
A crystal structure is formed only when the group of atoms is arranged identically at the lattice point.
The group of atoms or molecules is called a basis. Lattice point is actually an imaginary concept.

In other way, we can say that,

Lattice + Basis=crystal structure

Line joining any two points is a translation in lattice. Two non-collinear

translation leads to a plane lattice and three non coplanar translation leads to
a space lattice.

Unit cell
Unit cell can be considered as the building block of a crystal. It has the same
symmetry as the entire crystal. When we arrange the unit cell in 3D, we get
the bulk crystal. In other words it can be described as the smallest volume
which when repeated in all direction gives the crystal. The three edges a, b, c
along the axis and angle between them α, β and γ is termed as lattice
parameters. In 3D it is better to consider a parallelepiped as unit cell.

Unit cell can be of primitive as well as non primitive type. A primitive cell is a
minimum volume unit cell and has only one lattice point in it and the latter
contains more than one.
 In the given figure below, simple cube is a primitive cell. No.of atoms per unit cell is one for it. The
rest two is non primitive. No.of atoms per unit cell is 2 and 4 respectively.

Simple cubic (P) Body- centred cubic (I) Face centered cubic (F)

Bravais Lattice in Two dimension-Plane lattice

In general, number of lattices obtained is unlimited since
there is no restriction to the length a, b of the lattice
translations and on angle φ between them. Such a lattice
for arbitrary a, b and φ is known as oblique lattice. This
oblique lattice is invariant under rotation of 2π/n (with
n=1 and 2). It can also be made invariant under rotation
of 2π/n with n=3, 4 and 6.

For a=b and φ=900, we get square lattice

a≠b and φ=90 , rectangular a=b and φ=φ0, rhombus a=b and φ= 600, hexagonal
0

Bravais Lattice in Three dimension-Space lattice

Based on the lattice parameters a, b, c, α, β and γ and applying the restrictions as above, only 14
types of lattices are possible in three dimensions. One general (triclinic) and thirteen special. Only
seven different systems of axis are found to be sufficient to represent all Bravais lattice. This fourteen
space lattice is divided into seven crystal systems.

They are triclinic, monoclinic, orthorhombic, tetragonal, trigonal, hexagonal and cubic.

Serial
Lattice Systems Simple Base-centered Body-centered Face-centered Example
No:

1 triclinic(none) CuSO4.5H2O, K2Cr2O7

CaSO4.2H2O, FeSO4,
2 monoclinic(1diad) Na2SO4
 orthorhombic(3
3 KNO3, BaSO4
perpendicular diads)

4 rhombohedral(1 triad) As, Sb, Bi

5 tetragonal(1 tetrad) TiO2, SnO2, NiSO4

6 hexagonal(1 hexad) SiO2, Zn, Mg, Cd

7 cubic(4 triads) Au, Cu, NaCl

Atomic packing Fraction (APF)

Atomic packing fraction mainly gives us an idea about the arrangement of atoms/ions in solids. It will
give the efficiency with which the available space is being filled by atoms.

Packing fraction is defined as the ratio of volume of atoms occupying the unit cell to the volume of unit
cell.
Examples:

1. Simple Cubic

Consider a cube of side 'a' .Atoms of radius ‘r’ is placed at the corner. So that length
of cube a=2r.
1∗4𝜋𝑟 3
Volume of atoms in unit cell=
3
In a simple cubic structure, the atoms occupies at the eight corners. An atom at the
corner is equally shared by 8 unit cells. So the contribution of one atom to a unit cell
is 1/8. Therefore the no. of atoms per unit cell is (1/8)*8(corner atoms) =1.
Volume of unit cell=𝑎 3 = (2𝑟)3 = (8𝑟)3
4 3
𝜋𝑟 𝜋
𝐴𝑃𝐹 = 3 3 = = 52%
8𝑟 6

2. Body centered Cube

Consider a cube of side ‘a’, and atoms of radius ‘r’ are placed at corners and at
the body centre. Length of body diagonal, √3a=4r.
2∗4𝜋𝑟 3 8𝜋𝑟 3
Volume of atoms in unit cell= =
3 3
In a body centered cube, there will be one atom at the centre along with 8
corner atoms. This corner atom is shared by 8 unit cell and the atom at the
centre is not a shared one. Therefore no. of atoms per unit cell=
(1/8)*8(corner atoms)+1(body centre)=2.
4𝑟
Volume of unit cell= 𝑎 3 = ( )3
√3

3. Face centered Cube

Consider a cube of length ‘a’ and atoms of radius ’r’ are placed at the corners as
well as at the face centre. Length of face diagonal √2a=4r.

Volume of unit cell

In a face centered cube, each face possesses one atom along with 8 corner atoms.
The atoms at the faces are equally shared by two unit cell. Corner atoms by 8 unit
cells. So the no. of atoms per unit cell is=(1/8)*8(corner atoms)+(1/2)*6(atoms
at face)=4.
Volume of unit cell=