UNIT III: CRYSTAL STRUCTURE

Q. Explain different types of crystalline solids?

Crystalline solid: The solid having its constituent atoms, ions or molecules

arranged in a regular periodic three-dimensional pattern is called a

crystalline solid.

Ex: Quartz, rock salt, alum, calcite, diamond, etc.

Crystalline solids are further divided into two types:

a Single crystal

b Polycrystalline solid
Single crystal: The crystal having the same periodicity of pattern

throughout the certain sample is known as a single crystal.

Ex: Quartz, calcite, diamond, etc.

Polycrystalline solid: The crystal having periodicity of pattern restricted

to certain boundaries within the same sample is called polycrystalline

solid.

Ex: Rock salt, sand, etc.

Amorphous solid: The solid having its constituent atoms, ions or

molecules arranged in a random way is called an amorphous solid.

Ex: Glass, graphite, rubber and many plastics.

Q. Define space lattice and basis.

Q. Elaborate the statement: ‘lattice + basis = crystal lattice’

Space lattice: Space lattice is defined as a three dimensional array of lattice

points in which every point has identical surroundings.

Basis: The atom or group of atoms (or molecules) or ions associated with a

single lattice point is called basis. It is also called a motif.

Space lattice is an imaginary concept. It can be termed as the skeleton

upon which crystal structure is built. In a space lattice, it is noted that for a

particular direction, the distance between two consecutive lattice points is

the same. This property is called periodicity. Periodicity is different in

different directions.
Crystal lattice: When the imaginary sites of space lattice are filled with the

basis (atoms, molecules or group of atoms) then the product is called a

crystal lattice.

Thus we can say,

Space lattice + Basis = Crystal lattice

Unit Cell:

Q. What is the smallest building block of crystal structure known as?

The elementary pattern of minimum number of atoms or molecules which

fully represent all the characteristics of a crystal is called a unit cell.

There are two types of unit cell:

Primitive unit cell: Unit cell having all its lattice points only on its corners

is called a primitive unit cell.

Non-primitive unit cell: Unit cell having all its lattice points at its corners

as well as inside the body or on its surface is called a non-primitive unit

cell.
Primitive Unit Cell Non-primitive unit cell
Lattice constant/Lattice parameter:

Q. What are lattice constants or lattice parameters?

The three translational vectors a, b and c lie along the crystallographic

axes. The intercepts a, b and c are defined as the dimensions of the unit cell

and are known as primitives or basis vectors.

The sides a, b and c and the angles between them α, β and γ are known as

lattice parameters or lattice constants of unit cells.

Q. Explain Bravais Lattice.

Auguste Bravais has proved that there are only 14 ways of arranging

lattice points so that every lattice point will have identical surroundings.

According to Bravais, by taking different combinations of a, b, c, α, β

and γ values, we can have only 7 types of crystal systems. These 7 systems

are further divided into sub-system and make a total of 14 types.

System Lattice Type of unit cell Unit cell geometry

parameters

Cubic 𝑎=𝑏=𝑐 1 Simple

α = β = γ = 90 2 Body centered
3 Face centered
Tetragonal 𝑎=𝑏≠𝑐 1 Simple

α = β = γ = 90 2 Body centered

Orthorhom 𝑎 ≠ 𝑏 ≠ 𝑐 1 Simple

bic α = β = γ = 90 2 Body centered

3 Face centered

4 Base centered
Trigonal 𝑎=𝑏=𝑐 Simple

(Rhombohe α = β = γ ≠ 90°

dral)

Hexagonal a = b ≠ c Simple

α = β = 90°,

γ = 120°
Monoclinic a ≠ b ≠ c 1 Simple

α = γ = 90°, 2 Base centered

β ≠ 90°

Triclinic 𝑎≠𝑏≠𝑐 Simple

α≠ β≠ γ
Q. Explain Miller indices. How to calculate Miller indices?

Q. What are Miller indices?

Miller indices are the reciprocals of the intercepts, made by the plane on

the crystallographic axes, when reduced to smallest integers.

● Calculate (estimate) intercepts from a starting point (origin)

● take reciprocal of intercepts

● reduce the reciprocals to smallest integers

● we get Miller indices

Suppose a1, a2 and a3 are intercepts. Then
1 1 1
𝑎1
, 𝑎2
𝑎𝑛𝑑 𝑎3
are the reciprocals.

When we reduce these to the smallest integers we get Miller indices.

Q. Show schematically the principle planes (0 1 1), (1 0 1), (1 1 0), (1 1 1),

(1 0 0), (0 1 0), (0 0 1), (2 1 0), (1 2 0), (1 2 3).

(0 1 1)
1 1 1
0
, 1
, 1
∞, 1, 1
X, y, z

(1 0 1)
1 1 1
1
, 0
, 1
1, ∞, 1
X, y, z
(1 1 0)
1 1 1
1
, 1
, 0
1, 1, ∞
X, y, z

(2 1 0)
1 1 1
2
, 1
, 0
1
2
, 1, ∞
X, y, z
(1 2 3)
1 1 1
1
, 2
, 3
1 1
1, 2
, 3
X, y, z
Q. Obtain an expression for interplanar spacing between two adjacent

planes of Miller indices (h k l) in a cubic crystal.

The distance d between successive members of a series of parallel planes is

known as interplanar distance.

Consider two parallel crystallographic planes of a crystal structure having

Miller indices (h k l).

Let one of the planes is passing through origin and the other is making

intercepts OA, OB and OC along the three axes respectively.

𝑎 𝑏 𝑐
𝑂𝐴 = ℎ
, 𝑂𝐵 = 𝑘
, 𝑂𝐶 = 𝑙
Where a, b and c are the lattice constants of the crystal.
Now the perpendicular ON is drawn from origin to the second plane, such

that ON is interplanar distance.

𝑂𝑁 = 𝑑

Let, α, β and γ be the angles ON makes with the three crystallographic

axes respectively.

Therefore direction cosines of ON are given as,

𝑂𝑁 𝑑 𝑑ℎ
𝑐𝑜𝑠α = 𝑂𝐴
= 𝑎 = 𝑎
ℎ

𝑂𝑁 𝑑 𝑑𝑘
𝑐𝑜𝑠 β = 𝑂𝐵
= 𝑏 = 𝑏
𝑘

𝑂𝑁 𝑑 𝑑𝑙
𝑐𝑜𝑠 γ = 𝑂𝐶
= 𝑐 = 𝑐
𝑙
But from geometry,
2 2 2
𝑐𝑜𝑠 α + 𝑐𝑜𝑠 β + 𝑐𝑜𝑠 γ = 1
2 2 2 2 2 2
𝑑ℎ 𝑑𝑘 𝑑𝑙
2 + 2 + 2 =1
𝑎 𝑏 𝑐

for cubic system, 𝑎 = 𝑏 = 𝑐 therefore,

2
2 2 2
𝑑
𝑎
2 (ℎ +𝑘 +𝑙 )= 1
2
2 𝑎
𝑑 =
(ℎ2+𝑘2+𝑙2)
𝑎
𝑑ℎ𝑘𝑙 =
(ℎ2+𝑘2+𝑙2)
Q. Derive Bragg’s law for diffraction of x-rays from crystal planes.

Bragg gave a simple equation relating the wavelength of x-ray to the

angular position of the scattered beams and the separation of atomic

planes in the crystal.

2𝑑𝑠𝑖𝑛θ = 𝑛λ

Where,

d – interplanar distance

λ – wavelength of x-ray beam

n – order of reflection

θ – angle of incidence
Let us consider a set of parallel Braggs planes MN and PQ separated by

interplanar distance d. Let a beam of monochromatic x-ray of wavelength

λ represented by AB and DE is incident on these planes. The scattered

beam emerges along BC and EF.

The path difference Δ between the reflected rays BC and EF is given as,

∆ = 𝐺𝐸 + 𝐸𝐻 (i)
0
∠𝐴𝐵𝐺 = θ + α = 90 (ii)

BE is normal to the plane MN,

0
∠𝑀𝐵𝐸 = α + ∠𝐺𝐵𝐸 = 90 (iii)

From equation (ii) and (iii) we get,

α + ∠𝐺𝐵𝐸 = θ + α

so that,

∠𝐺𝐵𝐸 = θ

Similarly,
∠𝐸𝐵𝐻 = θ

In ΔBGE,

𝐵𝐸 = 𝑑
𝐺𝐸
sin θ = 𝑑

∴ 𝐺𝐸 = 𝑑 𝑠𝑖𝑛θ

Similarly, in ΔEBH,

𝐸𝐻 = 𝑑 𝑠𝑖𝑛θ

∴path difference,

∆ = 𝐺𝐸 + 𝐸𝐻

∆ = 𝑑 𝑠𝑖𝑛θ + 𝑑 𝑠𝑖𝑛θ
∆ = 2𝑑 𝑠𝑖𝑛θ (iv)

The rays BC and EF will constructively interface only when,

∆ = 𝑛λ

Where n = 1, 2, 3, . . . . is the order of reflection.

∴The condition for reinforcement of scattered wave is,

2𝑑 𝑠𝑖𝑛θ = 𝑛λ

This is Bragg’s law.

Q. State applications of Bragg’s law.

The x-ray diffraction technique is very much useful in determining the

crystal structure and identification of materials.

The diffraction pattern gives information about d-values and making use

of these d-values, the unit cell and the atomic position in the cell can be

obtained.
Q. What is void? Write a note on the tetrahedral and octahedral void.

The empty space within the unit cell which is left unutilized is called void.

There are two types of voids,

1. Tetrahedral void

2. Octahedral void

1. Tetrahedral void: Tetrahedral void is produced when an atom of layer B

is fitted on the valley formed by three adjacent atoms of layer A.

It is surrounded by four atoms. When the centre of these four atoms are

joined we get a tetrahedron shape that is why the void is called a

tetrahedral void.
2. Octahedral void: Octahedral void is produced when a valley formed by

three adjacent atoms of layer B is fitted on the valley formed by three

adjacent atoms of layer A.

It is surrounded by six atoms. When the centre of these six atoms are

joined we get an octahedron shape that is why the void is called an

octahedral void.
Q. Define the following terms (characteristics of Unit cell),

● Unit cell volume (V)

● Effective number of atoms per unit cell (Z)

● Atomic radius (r)

● Nearest neighbor distance (2r)

● Coordination number (CN)

● Atomic packing fraction (APF)

● Void space (%V)

● Density (ρ)
● Unit cell volume (V) : It is the volume of a unit cell.

● Effective number of atoms per unit cell (Z) : It is the total number of

atoms per unit cell considering the contribution of each atom towards

that cell.

● Atomic radius (r): The radius of an atom, expressed in terms of the

edge of the unit cell a.

● Nearest neighbor distance (2r): The nearest neighbor distance is the

distance between the centres of two atoms in contact. It is expressed in

terms of the edge of the unit cell a.

● Coordination number (CN): It is defined as the number of nearest

neighbor atoms which are simultaneously in contact with that atom.

● Atomic packing fraction (APF): It is defined as the ratio of volume of

effective number of atoms in the unit cell to the total volume of the

unit cell.

𝐴𝑃𝐹 =
( 𝑁𝑢𝑚𝑏𝑒𝑟 𝑂𝑓 𝐴𝑡𝑜𝑚𝑠
𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 ) (𝑉𝑜𝑙𝑢𝑚𝑒 𝑂𝑓 𝐸𝑎𝑐ℎ 𝐴𝑡𝑜𝑚)
𝑉𝑜𝑙𝑢𝑚𝑒 𝑂𝑓 𝑈𝑛𝑖𝑡 𝐶𝑒𝑙𝑙

● Void space (%V): The void space in the unit cell is the vacant space left

unutilized in the unit cell. It is equal to the (1 – APF). It is expressed in

percentage. Thus,

Void space = (1 – APF) x 100

It is also called interstitial space.

 ● Density(ρ): A unit cell possesses all the structural properties of the

bulk crystal, the density of a unit cell must be the same as that of the

bulk crystal. Thus,

𝑀𝑎𝑠𝑠 𝑍𝑊
ρ= 𝑉𝑜𝑙𝑢𝑚𝑒
= 𝑉

Where, W is the mass of each atom and Z is the effective number of atoms

in the unit cell.

𝑀
𝑊= 𝑁𝐴

M is the molecular weight of the material and NA is Avogadro’s number.

Hence, density can be written as,

𝑍𝑀
ρ= 𝑁𝐴𝑉
Q. Find following parameters for simple cubic crystal (SCC), body

centered cubic crystal (BCC) and face centered cubic crystal (FCC)

● Unit cell volume (V)

● Effective number of atoms per unit cell (Z)

● Atomic radius (r)

● Nearest neighbor distance (2r)

● Coordination number (CN)

● Atomic packing fraction (APF)

● Void space (%V)

● Density (ρ)

● Simple Cubic Crystal (SCC)

● Unit cell volume (V)

3
𝑉 =𝑎

● Effective number of atoms per unit cell (Z)

𝑍= ( ) (
𝑎𝑡𝑜𝑚
𝑐𝑜𝑟𝑛𝑒𝑟
×
𝑐𝑜𝑟𝑛𝑒𝑟
𝑐𝑒𝑙𝑙 )
𝑍 = ( )× ( )
1 8
8 1

𝑍=1
 ● Atomic radius (r)

In a SCC structure atoms are in contact along the edge of the unit cell.
 𝑎 = 2𝑟

𝑎
𝑟= 2

● Nearest neighbor distance (2r)

2𝑟 = 𝑎

● Coordination number (CN)

CN = 6

● Atomic packing fraction (APF)

In case of SCC unit cell, Z = 1

3
Volume of unit cell, 𝑉 = 𝑎

but 𝑎 = 2𝑟
 3 3
Hence, 𝑉 = 𝑎 = 8 𝑟

Volume of spherical atom,

4 3
𝑉= 3
π𝑟

𝐴𝑃𝐹 =
( 𝑁𝑢𝑚𝑏𝑒𝑟 𝑂𝑓 𝐴𝑡𝑜𝑚𝑠
𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 ) (𝑉𝑜𝑙𝑢𝑚𝑒 𝑂𝑓 𝐸𝑎𝑐ℎ 𝐴𝑡𝑜𝑚)
𝑉𝑜𝑙𝑢𝑚𝑒 𝑂𝑓 𝑈𝑛𝑖𝑡 𝐶𝑒𝑙𝑙
4 3
1× 3 π𝑟
𝐴𝑃𝐹 = 3 = 0. 52
8𝑟

● Void space (%V)

% void space = (1 – APF) x 100

% void space = (1 – 0.52) x 100

% void space = 48%

● Density (ρ)
𝑍𝑀
ρ= 𝑁𝐴𝑉

In case of SCC crystal, Z = 1

𝑀
Hence, ρ = 𝑁𝐴𝑉
● Body Centered Cubic Crystal (BCC)

● Unit cell volume (V)

3
𝑉 =𝑎

● Effective number of atoms per unit cell (Z)

𝑍= ( ) ( ) + 𝑏𝑜𝑑𝑦 𝑐𝑒𝑛𝑡𝑒𝑟𝑒𝑑 𝑎𝑡𝑜𝑚

𝑎𝑡𝑜𝑚
𝑐𝑜𝑟𝑛𝑒𝑟
×
𝑐𝑜𝑟𝑛𝑒𝑟
𝑐𝑒𝑙𝑙

𝑍 = ( )× ( )+ 1
1 8
8 1

𝑍=2

● Atomic radius (r)

 In a BCC structure atoms are in contact along the body diagonal.

2 2 2
(𝐴𝐷) = (𝐴𝐶) + (𝐶𝐷)
2 2 2 2
(𝐴𝐷) = (𝐴𝐵) + (𝐵𝐶) + (𝐶𝐷)
2 2 2 2
(𝐴𝐷) = (𝑎) + (𝑎) + (𝑎)
 2 2
(𝐴𝐷) = 3𝑎

∴ 𝐴𝐷 = 3 𝑎 (𝑖)
but also,
𝐴𝐷 = 𝑟 + 2𝑟 + 𝑟
𝐴𝐷 = 4𝑟 (𝑖𝑖)
from (i) and (ii)

4𝑟 = 3 𝑎
3𝑎
𝑟= 4

● Nearest neighbor distance (2r)

 3𝑎
2𝑟 = 2

● Coordination number (CN)

CN = 8

● Atomic packing fraction (APF)

In case of BCC cell, Z = 2
volume of unit cell, V = a3
but,
3𝑎
𝑟= 4

4𝑟
𝑎=
3
 3
∴𝑉 = ( )
4𝑟
3
3
64𝑟
𝑉=
3 3

4 3
volume of spherical atom, 𝑣 = 3
π𝑟

𝐴𝑃𝐹 =
( 𝑁𝑢𝑚𝑏𝑒𝑟 𝑂𝑓 𝐴𝑡𝑜𝑚𝑠
𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 ) (𝑉𝑜𝑙𝑢𝑚𝑒 𝑂𝑓 𝐸𝑎𝑐ℎ 𝐴𝑡𝑜𝑚)
𝑉𝑜𝑙𝑢𝑚𝑒 𝑂𝑓 𝑈𝑛𝑖𝑡 𝐶𝑒𝑙𝑙
4 3
2× 3 π𝑟 π 3
∴ 𝐴𝑃𝐹 = 64𝑟
3 = 8
3 3

𝐴𝑃𝐹 = 0. 68

● Void space (%V)

% void space = (1 – APF) x 100
 = (1 – 0.68) x 100
= 32%

● Density (ρ)
In case of BCC structure, Z = 2
2𝑀
∴ρ = 3
𝑁𝐴𝑎

● Face Centered Cubic Crystal (FCC)

● Unit cell volume (V)

3
𝑉 =𝑎

● Effective number of atoms per unit cell (Z)

𝑍 =⎡
⎣( 𝑎𝑡𝑜𝑚
𝑐𝑜𝑟𝑛𝑒𝑟) (×
𝑐𝑜𝑟𝑛𝑒𝑟
𝑐𝑒𝑙𝑙 ) (
⎤+ ⎡
⎦ ⎣
𝑎𝑡𝑜𝑚
𝑓𝑎𝑐𝑒 ) (
×
𝑓𝑎𝑐𝑒
𝑐𝑒𝑙𝑙 )⎤⎦
𝑍 =( × 8) + ( × 6)
1 1
8 2

𝑍=1+3
𝑍 = 4 𝑎𝑡𝑜𝑚𝑠

● Atomic radius (r)

In a FCC structure atoms are in contact along the face diagonal.
from figure,
2 2 2
(𝐴𝐹) = (𝐴𝐵) + (𝐹𝐵)
2 2 2
(𝐴𝐹) = (𝑎) + (𝑎)
2 2
(𝐴𝐹) = 2𝑎

∴𝐴𝐹 = 2𝑎 (𝑖)
Also,
𝐴𝐹 = 𝑟 + 2𝑟 + 𝑟
𝐴𝐹 = 4𝑟 (𝑖𝑖)
from (i) and (ii)

4𝑟 = 2𝑎
𝑎 2 𝑎
𝑟= 4
=
2 2
 ● Nearest neighbour distance (2 r)
𝑎
2𝑟 =
2

● Coordination number (CN)

CN = 12

● Atomic packing fraction (APF)

In case of FCC cell, Z = 4
Volume of unit cell, V = a3
𝑎
but 𝑟 =
2 2

𝑎 = 2 2𝑟
 3 3
∴𝑉 = (2 2𝑟) = 16 2𝑟
Volume of spherical atom,
4 3
𝑉= 3
π𝑟

𝐴𝑃𝐹 =
( 𝑁𝑢𝑚𝑏𝑒𝑟 𝑂𝑓 𝐴𝑡𝑜𝑚𝑠
𝑢𝑛𝑖𝑡 𝑐𝑒𝑙𝑙 )(𝑉𝑜𝑙𝑢𝑚𝑒 𝑂𝑓 𝐸𝑎𝑐ℎ 𝐴𝑡𝑜𝑚)
𝑉𝑜𝑙𝑢𝑚𝑒 𝑂𝑓 𝑈𝑛𝑖𝑡 𝐶𝑒𝑙𝑙
4 3
4× 3 π𝑟 π
∴𝐴𝑃𝐹 = 3 =
16 2𝑟 3 2

𝐴𝑃𝐹 = 0. 74

● Void space (%V)

% void space = (1 – APF) x 100
= (1 – 0.74) x 100
 = 26%

● Density (ρ)
In case of FCC structure, Z = 4
4𝑀
∴ρ = 3
𝑁𝐴𝑎
List of Formulae:
𝑎
1.𝑑 =
(ℎ2+𝑘2+𝑙2)
2.2𝑑𝑠𝑖𝑛θ = 𝑛λ
𝑍𝑀 𝑍𝑀
3.ρ = 𝑁𝐴𝑉
= 3
𝑁𝐴𝑎

𝑎
4.For SCC, 𝑟= 2

3𝑎
5.For BCC, 𝑟 = 4

𝑎
6.For FCC, 𝑟=
2 2
Numerical Problems:
3 𝑘𝑔
1.Molybdenum has a BCC structure. Its density is 10. 2 × 10 3 and its
𝑚

atomic weight is 95.94. Determine radius of Molybdenum atom. [4m]

2.Lattice constant for BCC iron at 20℃ is 2. 85Å. Density of Iron is 7870
𝑘𝑔
3 . Determine its atomic mass and radius. [4m]
𝑚

3.Silver has FCC structure and the atomic radius is 1.441 Å. Calculate the
density of silver. Atomic weight of silver is 108. [3m]
4.Aluminium has FCC structure. Its density is 2700 kg/m3. Calculate unit
cell dimension and atomic radius. Atomic weight of aluminium is
26.98. [3m]
5.The density of copper is 8980 kg/m3 and unit cell dimension is 3.61 Å.
Atomic weight of copper is 63.54. Determine the crystal structure. [3m]
6.The 𝑑110 interplanar spacing in a BCC metal vanadium is 2. 15Å. Find
its lattice constant a. [2m]
7.Find the spacing of (2 1 2) and (0 3 0) planes in a FCC crystal having
lattice constant of 5Å and also find radius. [3m]
8.The Bragg angle corresponding to the first order reflection from the
plane (1 1 1) in a crystal is 300 when X-rays of wavelength 1.75 Å are
used. Calculate interplanar spacing and lattice constant. [3m]
9.Gold with atomic radius 1.44 Å and FCC structure is being used to
determine the wavelength of X-ray. Calculate the wavelength of X-ray
if the (1 2 1) plane diffracts the beam by 350. Assume first order
diffraction. [3m]
10. An X-ray beam of wavelength 1.5 Å is diffracted by (1 1 0) planes of
Nickel crystal. The first order diffraction is obtained at an angle of
 0
27. 6 . Determine the lattice constant of the unit cell of Nickel having
FCC structure. [3m]
11. X-ray of unknown wavelength give first order Bragg reflection at
glancing angle 200 with (2 1 2) planes of copper having FCC structure.
Find the wavelength of X-rays. If the lattice constant for copper is 3.615
Å. [4m]
12. Bragg’s spectrometer is set for the first order reflection to be received
by the detector at glancing angle 100. Calculate the angle through
which the detector is rotated to receive the second order reflection
from the same face of crystal. [3m]
13. Gold with atomic radius 1.44 Å and face-centered cubic structure is
being used to determine the wavelength of X-rays. Calculate the
wavelength of X-rays if the (1 1 1) plane diffracts the beam by 32.10.
Assume first order diffraction. [3m]
14. X-rays of wavelength 1.5 Å are incident on NaCl crystal having a
grating spacing of 2.8 Å. What is the highest order that the crystal can
diffract? [2m]