Unit 1 Crystal Structure (18hrs)

Solids: Amorphous and Crystalline Materials. Lattice Translation Vectors. Lattice with a Basis – Unit Cell-
Elements of symmetry-Types of Lattices -two and three dimensional- Miller Indices-Reciprocal Lattice -
Brillouin Zones. Diffraction of X-rays by Crystals. Bragg’s Law. X- ray diffraction techniques-Inter atomic
forces. Types of bonding
Crystalline and Amorphous Solids
Solids are classified into two; crystalline and amorphous.
In a crystalline solid, atoms are arranged in a regular, periodic and repeated manner. Such a solid
possesses translational symmetry. ie, If the crystal is translated by any vector joining two atoms, the crystal
appears exactly the same as it did before the translation.
eg: Aluminium, Copper, Sodium, ………...
If the atoms are arranged in an irregular manner, it is called amorphous solid.
eg: Rubber, Plastic, Glass, ...........
Difference Between Crystalline and Amorphous Solids
Crystalline Solids Amorphous Solids
Long range orderly arrangement of constituents Short range, random arrangement of constituents
Definite shape Irregular shape
Generally crystalline solids are anisotropic in nature They are isotropic like liquids
They are true solids They are considered as pseudo solids or super
cooled liquids
Definite heat of fusion Heat of fusion is not definite
They have sharp melting points Gradually soften over a range of temperature and
so can be moulded
Note
A crystal with no defects or impurities made of completely identical repeating subunits is called a
perfect crystal.
But a perfect crystal is an ideal concept. The periodicity is interrupted in the surface of a crystal. It
is a kind of imperfection. Due to thermal vibrations of atoms at any temperature greater than 0 o K, the
crystal is distorted.
Crystal Lattice (Space Lattice)
Crystalline solids are those in which the atoms or molecules are arranged in a regular, periodic and
repeated manner in three dimensions. Each atom is fixed at a definite point at a finite distance from other
atoms. Each of them has a finite angular orientation to all other. This angular arrangement of the space
position of the atoms in a crystal is called space lattice. Hence a space lattice may be defined as an infinite
array of points in three dimensions in which every point has identical surroundings to that of every other
points in the array.
Types of Crystal Lattice
There are two types of lattices; the Bravais and non-Bravais. In a Bravais lattice all lattice points are
equivalent. Hence all atoms in the crystal are of the same kind.
If some of the lattice points are non-equivalent, it is called non-Bravais lattice. It is referred as a
lattice with a basis
Basis
The lattice points may or may not be atom sites. But each point is associated with one or more
atoms. Such a set of atoms situated near each site of Bravais lattice is called basis.
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Note
Lattice + Basis Crystal Structure
Lattice Translation Vectors
In order to represent lattice points in space a co-ordinate system is necessary. All the lattice points
in space can be generated by translating three non-coplanar vectors. The three non-coplanar directions
constitute a co-ordinate system.
In a space lattice if OX, OY and OZ are selected as crystal axis. Then the distance a, b and c between
two atoms along OX, OY and OZ respectively will be constant. These distances are called the primitives of
the crystal.
With respect to any lattice points chosen as origin, the location of any other lattice points can be
defined by the relation
T⃗ = n a⃗ + n b⃗ + n c⃗
where n1, n2 and n3 are integers.
Note
It is conventional to use the notation [n1, n2, n3] to specify a translational direction in a lattice.
Unit Cell
The unit cell is the smallest block from which the crystal is built up by repetition in three dimensions.
It is the smallest part of a crystal having all the structural properties of the given lattice.
Note
The smallest unit of volume of a crystal which contains the least number of atoms required to completely
specify the relative positions of all atoms present in a crystal is called a primitive cell. A unit cell may be
equal to a primitive cell or a multiple of it.
Lattice Parameters of a Unit Cell
The three sides of a unit cell are called crystallographic axis. They are chosen in such a way that they
pass regularly through the lattice points associated with each atom.
The angle between these three axes us called interfacial angles. The distances a, b and c between
two atoms along the crystallographic axis are called primitives. The interfacial angles and primitives
constitute the lattice parameters of the unit cell.

Bravais Lattices
There are various ways of positioning structureless points in space such that all points have identical
surroundings. These are called Bravais Lattices.
There are five Bravais lattices in two dimensions. They are oblique, square, hexagonal, rectangular
and centred rectangular lattices.
There are fourteen Bravais lattices in three dimensions. These fourteen lattices are classified into
seven systems. They are cubic, tetragonal, orthorhombic, trigonal, hexagonal, monoclinic and triclinic
Crystal Structure
All crystals are divided into seven crystal systems with respect to the shape of the elementary shell.
They are given below
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System Primitives Interfacial Angles Types .
Cubic a=b=c = β = γ = 90° Simple
Body centred
Face centred
Tetragonal a=b≠c = β = γ = 90° Simple
Body centred
Orthorhombic a≠b≠c = β = γ = 90° Simple
Base centred
Body centred
Face centred
Trigonal a=b=c  = β = γ ≠ 90° Simple
Hexagonal a=b≠c  = β = 90°, γ = 120° Simple
Monoclinic a≠b≠c  =  = 90  
o
Simple

Base centred
Triclinic a≠b≠c ≠β≠γ Simple
Elements of Symmetry
An operation that takes a crystal into itself is called a symmetry operation, ie, a crystal remains
invariant under a symmetry operation.
A crystal possesses following three types of symmetry,
i) Centre of symmetry
ii) Plane of symmetry
iii) Axis of symmetry
The total number of centre, plane and axes of symmetries possessed by a crystal is called as its
elements of symmetry
Centre of Symmetry (Inversion Centre)
It is an imaginary point in the crystal that any line drawn through it intersects the surface of the
crystal at equal distance on either side. ie, A cell has an inversion centre if there is a point at which the cell
remains invariant when the mathematical transformation 𝑟⃗   𝑟⃗ is performed on it.
All Bravais lattices are inversion symmetric. But a non-Bravais lattice may or may not have an
inversion centre depending on the symmetry of the basis.

Plane of symmetry (Reflection Plane)

It is an imaginary plane which passes through the centre of a crystal can divides it into two equal
portions which are exactly the mirror images of each other. When a mirror reflection in this plane is
performed the cell remains invariant.
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 A triclinic has no reflection plane, the monoclinic has one plane midway between and parallel to the
bases, the cubic cell has nine reflection planes.
Axis of symmetry (Axis of Rotation)
It is an imaginary line, passing through the crystal such that when the crystal is rotated about this
line, it presents the same appearance more than once in one complete revolution. (ie, in a rotation through
360°).
Suppose, the same appearance of crystal is repeated n times on one complete rotation, the angle of
rotation is given by 360°/n. Now the crystal is said to have an n fold symmetry.
The triclinic has no axis of rotation. The monoclinic has 2-fold axis normal to the base. The cubic
unit cell has three 4-fold axes of symmetry, four 3-fold axes and six 2-fold symmetry.
Symmetry Operation
A Symmetry operation is an operation that can be performed on a crystal that results in no change
in the appearance of an object. ie, A crystal remains invariant under a symmetry operation
Symmetry operation may be grouped into three classes. They are translation operations, point
operations and hybrid operations.
Translation Operation
A translation operation is defined as the displacement of a crystal parallel to itself by a crystal
translation vector. This is the simplest of the symmetry operation. Translation repeats the crystal a finite
number of times.
Point operation
It is an operation which would leave the structure of a crystal unchanged. The different point
operations are the rotation operation, reflection operation and inversion operation.
(a) Rotation operation
In this operation an object can be rotated about an axis through a certain angle so as to give the
unchanged picture of the object to a stationary observer. The axis is called the rotation axis.
The angle of rotation is given by
2π
 =
n
where n=1,2,3,4 and 6 cult multiplicity of rotation axis. The possible values of n are 1, 2, 3, 4 and 6. A rotation
corresponding to the value of n is called n-fold rotation.
If the operation of rotation results in a congruent set, it is called a proper rotation and axis is called
proper rotation axis.
(b) Reflection
A lattice is said to possess reflection symmetry if there exists a plane in the lattice which divides it
into two identical halves which are mirror images of each other.
Reflection across a line or plane changes the character of the lattice from left handed to right handed
and vice versa.
(c) Inversion
Inversion is a point operation which is applicable to 3D lattice only. The symmetry element implies
that each point located at 𝑟⃗ related to a lattice point has an identical point located at − 𝑟⃗ related to the
same lattice point. It also changes the character of the lattice from right handed to left handed.
Hybrid operations
The operations that form a hybrid operation are not symmetry operations independently. Some of
the hybrid operations are given below
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(a) The roto reflection
It is the combination of a n-fold rotation and a reflection at the plane, perpendicular to the rotation
axis.
(b) The roto inversion
This operation includes a n-fold rotation followed by an inversion.
(c) The screw translation
This is an operation combining a n-fold rotation with the translation parallel to the rotation axis.
(d) The glide reflection
This is the combination of a reflection with the translation parallel to the reflection plane.
Point groups
A point group in lattice is defined as the collection of symmetry operations which when applied about
a lattice point gives the lattice invariant .
The various combination of allowed rotation and reflection operations give rise to 32 allowed point
groups. The different point groups of a system give rise to crystals of different geometrical shape.
Space group
The set of symmetry operations emerging from the arrangement of point groups form a group of its
own known as space group .
In simple words, the group of all symmetry elements of a crystal structure is called space group. It
determines the symmetry of a crystal structure as a whole. There are 17 distinct space groups possible in 2D
and 230 in 3D.
Characteristics of a space group
a) The symmetry of a crystal structure is specified completely when the space group is known .
b) The space group is characterised by Bravis lattice and by the location of the point group and other
symmetry elements in a unit cell.
c) The space group through its symmetry elements determines the position of equivalent points within
the unit cell .
d) For a crystal structure specified by a particular space group, if only one point in a cell is occupied, it
is necessary that all equal and points will be occupied by identical atoms or molecules.
Miller Indices
A crystal contains planes of atoms. The orientation of these planes in a crystal may be described in
terms a group of three numbers called Miller indices.
Let a plane cuts the x-axis at a distance of 2a, y-axis at a distance of 2b and z-axis at a distance of c.
So the numerical parameters of the plane are 2, 2 and 1. Then take the reciprocals of these numbers. So we
get ½, ½ and 1. Convert these reciprocals into whole numbers by multiplying each with their LCM. So we
get 1, 1, 2. Hence the Miller indices of the plane is (1 1 2)
Hence Miller indices of a crystal plane is given by three smallest figures which are inversely
proportional to the numeric parameters of the plane.
Procedure for Finding Miller Indices
1. Write down the intercepts of the planes on the three crystallographic axes (Let they be 4a, 2b and c)
2. Take the numerical parameters of the plane (ie, 4, 2 and 1)
3. Take the reciprocals of these numbers (ie, ¼, ½ and 1)
4. Convert the reciprocals into whole numbers by multiplying each with their LCM (ie, 1, 2 and 4)
5. Then the Miller indices of the plane is (1 2 4)
Note
1. When a plane is parallel to one of the reference axis, its interception is infinity. Therefore, the Miller
index for that axis is zero
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 2. When the intercept of the plane is on the negative part of any axis, the Miller Index is distinguished
by placing a bar above the index

Space Between Miller Indices

Consider a simple unit cell with co-ordinate axes x, y and z respectively. Consider a set of planes
defined by Miller indices (h k l). One such plane ABC will have intercepts a/h, b/k and c/l on the x, y and z
axes respectively.
Draw ON perpendicular from O to the plane ABC. Let ON = d. Then d represents the distance
between adjacent planes. Let ON make angles ,  and  with the x, y and z-axis respectively.
According to the law of direction cosines,
cos2 + cos2  + cos2  = 1
But
d h
cos  = =d
a/h a
d k
cos  = =d
b/k b
d l
cos  = =d
c/𝑙 c
ℎ 𝑘 𝑙
𝑑 +𝑑 +𝑑 =1
𝑎 𝑏 𝑐
ℎ 𝑘 𝑙
𝑑 + + =1
𝑎 𝑏 𝑐
1
𝑑 =
ℎ 𝑘 𝑙
+ +
𝑎 𝑏 𝑐
1
𝑑=
ℎ 𝑘 𝑙
+ +
𝑎 𝑏 𝑐
For a cubical crystal a = b = c
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 𝑎
𝑑=
√ℎ + 𝑘 + 𝑙
Important Features of Miller Indices
1. A plane which is parallel to any one of the co-ordinate axes has an intercept of infinity (∞) and
therefore, the Miller index for that axis is zero.
2. All equally spaced parallel planes with a particular orientation have same index number (h k I).
3. Miller indices do not only define particular plane but a set of parallel planes.
4. It is the ratio of indices which is only of importance. The planes (211) and (422) are the same.
5. A plane passing through the origin is defined in terms of a parallel plane having nonzero intercepts.
6. All the parallel equidistant planes have the same Miller indices. Thus the Miller indices define a set of
parallel planes.
7. A plane parallel to one of the coordinate axes has an intercept of infinity.
8. If the Miller indices of two planes have the same ratio (i.e., 844 and 422 or 211), then the planes are
parallel to each other.
9. If (h k I) are the Miller indices of a plane, then the plane cuts the axes into a/h, b/k and c/l equal
segments respectively.
10. When the integers used in the Miller indices contain more than one digit, the indices must be
separated by commas for clarity, e.g., (3, 11, 12).
11. The crystal directions of a family are not necessarily parallel to one another. Similarly, not all members
of a family of planes are parallel to one another.
12. By changing the signs of all the indices of a crystal direction, we obtain the antiparallel or opposite
direction. By changing the signs of all the indices of a plane, we obtain a plane located at the same
distance on the other side of the origin.
13. The normal to the plane with indices (hkl) is the direction [hkl].
14. The distance d between adjacent planes of a set of parallel planes of the indices (h k I) is given by-

Reciprocal lattice
Every crystal has two lattices associated with it, the crystal lattice (or direct space lattice) and the
reciprocal lattice.
Each set of parallel planes in a direct lattice can be represented by a normal to these planes having
length equal to the reciprocal of the interplanar spacing. The normal are drawn with reference to any
arbitrary origin and points are marked at their ends. These points form a regular arrangement which is called
the reciprocal lattice.
Thus, each point in a reciprocal lattice is a representative point of a particular parallel set of planes.
Construction of reciprocal lattice
A reciprocal lattice of direct lattice is constructed by the following method.
(1) Some arbitrary point is taken as the origin.
(2) From the origin draw normals to every set of parallel planes of the direct lattice.
(3) Take length of each normal equal to 2π times the reciprocal of interplanar spacing for the corresponding
set of planes.
(4) The terminal points of these normals form the reciprocal lattice.
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Primitive Translation Vectors of Reciprocal Lattice
Let a⃗, b⃗, c⃗ be the primitive translation vectors of a direct space lattice for a crystal forming a primitive
unit cell. The volume of this unit cell is given by
V = a⃗ . b⃗ × c⃗ = b⃗ . (c⃗ × a⃗) = c⃗ . a⃗ × b⃗
Then the reciprocal lattice vectors are given by
b⃗ × c⃗
A⃗ = 2
a⃗ . b⃗ × c⃗
c⃗ × a⃗
B⃗ = 2
⃗
b . (c⃗ × a⃗)
a⃗ × b⃗
C⃗ = 2
c⃗ . a⃗ × b⃗
Show that reciprocal lattice vectors are orthogonal to two axis vectors.
Let a⃗, b⃗, c⃗ be the primitive translation vectors of a direct space lattice and A⃗, B⃗ and C⃗ be the reciprocal
lattice vectors.
We have
b⃗ × c⃗
A⃗ = 2
a⃗ . b⃗ × c⃗
Hence
b⃗ × c⃗
A⃗ . a⃗ = 2 = 2
b⃗ × c⃗

A⃗ . b⃗ = 0 𝑎𝑛𝑑 A⃗ . c⃗ = 0
(Since A⃗ is normal to b⃗ and c⃗ )
Similarly
B⃗. b⃗ = 2 and B⃗. a⃗ = 0 𝑎𝑛𝑑 B⃗ . c⃗ = 0
And
C⃗ . c⃗ = 2 and C⃗. a⃗ = 0 𝑎𝑛𝑑 C⃗ . b⃗ = 0
Thus each of the reciprocal lattice vectors is orthogonal to two of the axis vectors of the direct space lattice
of the crystal.
Reciprocal Lattice to sc Lattice
Let a⃗, b⃗, c⃗ be the primitive translation vectors of a simple cubic cell
a⃗ = 𝑎 𝑥 , b⃗ = 𝑎 𝑦 𝑎𝑛𝑑 c⃗ = 𝑎 𝑧̂
where 𝑥, 𝑦 and 𝑧̂ being unit vectors along the directions of co-ordinate axes.
The volume of the cubic cell is
V = a⃗ . b⃗ × c⃗ = b⃗ . (c⃗ × a⃗) = c⃗ . a⃗ × b⃗ = 𝑎
The primitive translation vectors of the reciprocal sc lattice are given by
b⃗ × c⃗ 𝑎 𝑦 × 𝑎 𝑧̂ 2
A⃗ = 2 = 2 = 𝑥
a⃗ . b⃗ × c⃗ 𝑎 𝑎

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 c⃗ × a⃗ 𝑎 𝑧̂ × 𝑎 𝑥 2
B⃗ = 2 = 2 = 𝑦
b⃗ . (c⃗ × a⃗) 𝑎 𝑎

a⃗ × b⃗ 𝑎𝑥 × 𝑎𝑦 2
C⃗ = 2 = 2 = 𝑧̂
c⃗ . a⃗ × b⃗ 𝑎 𝑎

Reciprocal Lattice to bcc Lattice

Let a⃗, b⃗, c⃗ be the primitive translation vectors of a body centred cubic lattice
𝑎
a⃗ = (𝑥 + 𝑦 − 𝑧̂ )
2
𝑎
b⃗ = (−𝑥 + 𝑦 + 𝑧̂ )
2
𝑎
c⃗ = (𝑥 − 𝑦 + 𝑧̂ )
2
where 𝑥, 𝑦 and 𝑧̂ being unit vectors along the directions of co-ordinate axes.
The volume of the primitive cell is
V = a⃗ . b⃗ × c⃗ = b⃗ . (c⃗ × a⃗) = c⃗ . a⃗ × b⃗
Now
𝑎 𝑎
b⃗ × c⃗ = (−𝑥 + 𝑦 + 𝑧̂ )  (𝑥 − 𝑦 + 𝑧̂ )
2 2
𝑎
= (−𝑥 + 𝑦 + 𝑧̂ )  (𝑥 − 𝑦 + 𝑧̂ )
4
𝑎
= (𝑥 + 𝑦)
2
𝑎 𝑎
V= (𝑥 + 𝑦 − 𝑧̂ ) . (𝑥 + 𝑦)
2 2
𝑎
= (𝑥 + 𝑦 − 𝑧̂ ) . (𝑥 + 𝑦)
4
𝑎
= (1 + 1)
4
𝑎
=
2
The primitive translation vectors of the reciprocal bcc lattice are given by
b⃗ × c⃗
A⃗ = 2
a⃗ . b⃗ × c⃗
𝑎
(𝑥 + 𝑦)
= 2 2
𝑎
2
2
= (𝑥 + 𝑦)
𝑎
c⃗ × a⃗
B⃗ = 2
⃗
b . (c⃗ × a⃗)
𝑎
(𝑦 + 𝑧̂ )
= 2 2
𝑎
2
9
 2
= (𝑦 + 𝑧̂ )
𝑎
a⃗ × b⃗
C⃗ = 2
c⃗ . a⃗ × b⃗
𝑎
(𝑧̂ + 𝑥 )
= 2 2
𝑎
2
2
= (𝑧̂ + 𝑥 )
𝑎
Note
𝑥 𝑦 𝑧̂
−1 1 1 = 𝑥 (1 + 1) − 𝑦 (−1 − 1) + 𝑧̂ (1 − 1)
1 −1 1
= 2 𝑥 + 2𝑦
Reciprocal Lattice to fcc Lattice
Let a⃗, b⃗, c⃗ be the primitive translation vectors of a body centred cubic lattice
𝑎
a⃗ = (𝑥 + 𝑦)
2
𝑎
b⃗ = (𝑦 + 𝑧̂ )
2
𝑎
c⃗ = (𝑧̂ + 𝑥 )
2
The volume of the primitive cell is
V = a⃗ . b⃗ × c⃗ = b⃗ . (c⃗ × a⃗) = c⃗ . a⃗ × b⃗
Now
𝑎 𝑎
b⃗ × c⃗ = (𝑦 + 𝑧̂ )  (𝑧̂ + 𝑥 )
2 2
𝑎
= (𝑦 + 𝑧̂ )  (𝑧̂ + 𝑥 )
4
𝑎
= (𝑥 + 𝑦 − 𝑧̂ )
4
𝑎 𝑎
V= (𝑥 + 𝑦) . (𝑥 + 𝑦 − 𝑧̂ )
2 4
𝑎
= (𝑥 + 𝑦) . (𝑥 + 𝑦 − 𝑧̂ )
8
𝑎
= (1 + 1)
8
𝑎
=
4
The primitive translation vectors of the reciprocal fcc lattice are given by
b⃗ × c⃗
A⃗ = 2
a⃗ . b⃗ × c⃗

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 𝑎
(𝑥 + 𝑦 − 𝑧̂ )
= 2 4
𝑎
4
2
= (𝑥 + 𝑦 − 𝑧̂ )
𝑎
c⃗ × a⃗
B⃗ = 2
⃗
b . (c⃗ × a⃗)
𝑎
(𝑦 + 𝑧̂ − 𝑥 )
= 2 4
𝑎
4
2
= (𝑦 + 𝑧̂ − 𝑥 )
𝑎
a⃗ × b⃗
C⃗ = 2
c⃗ . a⃗ × b⃗
𝑎
(𝑧̂ + 𝑥 − 𝑦)
= 2 4
𝑎
4
2
= (𝑧̂ + 𝑥 − 𝑦)
𝑎
Note
𝑥 𝑦 𝑧̂
0 1 1 = 𝑥 (1 − 0) − 𝑦 (0 − 1) + 𝑧̂ (0 − 1)
1 0 1
= 𝑥 + 𝑦 − 𝑧̂
The primitive translation vectors of a hexagonal space lattice are
𝒂 𝒂 𝒂 𝒂
𝐚⃗ = 𝒙+ 𝒚 , ⃗𝐛 = − 𝒙 + 𝒚 and 𝐜⃗ = 𝒄𝒛
𝟐 𝟏𝟔 𝟐 𝟏𝟔
Find the volume of the primitive cell and primitive translations of the reciprocal lattice.
V = a⃗ . b⃗ × c⃗
Now
𝑎 𝑎
b⃗ × c⃗ = − 𝑥+ 𝑦 × 𝑐𝑧̂
2 16
𝑎𝑐 𝑎𝑐
= 𝑦+ 𝑥
2 16
𝑎 𝑎 𝑎𝑐 𝑎𝑐
a⃗ . b⃗ × c⃗ = 𝑥+ 𝑦 . 𝑦+ 𝑥
2 16 2 16
𝑎 𝑐 𝑎 𝑐
= +
32 32
𝑎 𝑐
=
16
𝑎 𝑐
V=
16

11
 b⃗ × c⃗
A⃗ = 2
a⃗ . b⃗ × c⃗
𝑎𝑐 𝑎𝑐
2 𝑦 + 16 𝑥
= 2
𝑎 𝑐
16
16 𝑎𝑐 𝑎𝑐
= 2 𝑦+ 𝑥
𝑎 𝑐 2 16
2
= ( 8𝑦 + 𝑥 )
𝑎
c⃗ × a⃗
B⃗ = 2
b⃗ . (c⃗ × a⃗)
𝑎 𝑎
c⃗ × a⃗ = 𝑐𝑧̂  𝑥+ 𝑦
2 16
𝑎𝑐 𝑎𝑐
= 𝑦− 𝑥
2 16
𝑎𝑐 𝑎𝑐
2 𝑦 − 16 𝑥
⃗
B = 2
𝑎 𝑐
16
16 𝑎𝑐 𝑎𝑐
= 2 𝑦− 𝑥
𝑎 𝑐 2 16
2
= ( 8𝑦 − 𝑥 )
𝑎
a⃗ × b⃗
C⃗ = 2
c⃗ . a⃗ × b⃗
𝑎 𝑎 𝑎 𝑎
a⃗ × b⃗ = 𝑥+ 𝑦  − 𝑥+ 𝑦
2 16 2 16
𝑎 𝑎 𝑎
= 𝑧̂ + = 𝑧̂
32 32 16
𝑎
16 𝑧̂
⃗
C = 2
𝑎 𝑐
16
2
= 𝑧̂
𝑐
Note
𝑥 𝑦 𝑧̂
𝑎 𝑎
0 = 𝑧̂ 𝑎 + 𝑎 = 𝑎 𝑧̂
2 16 32 32 16
−𝑎 𝑎
0
2 16
Properties of reciprocal lattice
(1) The direct lattice is the reciprocal lattice of its own reciprocal lattice (simple cubic lattice is self-
reciprocal while BCC and FCC lattices are reciprocal of each other).
(2) Each point in a reciprocal lattice corresponds to a particular set of parallel planes of the direct lattice .
(3) The distance of a reciprocal lattice point from an arbitrary fixed origin is inversely proportional to the
interplanar spacing of the corresponding parallel planes of the direct lattice.

12
(4) The volume of unit cell of the reciprocal lattice is inversely proportional to the volume of the
corresponding unit cell of the direct lattice.
Brillouin Zones
A Brillouin zone is defined as a Wigner-Seitz primitive cell in the reciprocal lattice. The first Brillouin
zone is the smallest volume enclosed by planes that are the perpendicular bisectors of the reciprocal lattice
vectors drawn from the origin. The first Brillouin zone can also be defined as the set of points that can be
reached from the origin without crossing any Bragg planes.

There are also second, third, etc., Brillouin zones. The second Brillouin zone is the set of points that
can be reached from the first Brillouin zone by crossing only one plane. The areas of the first and second
Brillouin Zones are the same. Similarly, the nth Brillouin zone can be defined as the set of points that can be
reached by crossing (n – 1) Bragg planes. But these Brillouin zones are rarely used. As a result, the first
Brillouin zone is often called simply the Brillouin zone.

Brillouin Zone Construction in Two Dimensions

1. Using the real space lattice vectors find the reciprocal lattice vectors and construct the reciprocal lattice.
2. One of the points in the reciprocal lattice is then designated as the origin.
3. Draw a line connecting this origin point to one of its nearest neighbours. This line is a reciprocal lattice
vector as it connects two points in the reciprocal lattice.
4. Then draw on a perpendicular bisector to the first line. This perpendicular bisector is a Bragg Plane.
5. Draw the Bragg Planes corresponding to the other nearest neighbours.
6. The locus of points in reciprocal space that have no Bragg Planes between them and the origin defines
the first Brillouin Zone. It is equivalent to the Wigner-Seitz unit cell of the reciprocal lattice.
7. Then draw on the Bragg Planes corresponding to the next nearest neighbours.
8. The second Brillouin Zone is the region of reciprocal space in which a point has one Bragg Plane between
it and the origin.
Diffraction of x-rays
The most essential condition for the diffraction to occur is that the opening or slit width has to be
comparable or less than the wavelength of light used. Since x-rays have very short wavelength, ordinary
ruled grating used with ordinary light cannot produce diffraction with x-rays. Hence Laue suggested the use
of a natural crystal as a closely spaced 3D grating. Since a crystal consist of a 3D array of regularly spaced
atoms, Laue reasoned that the equally spaced layers of atoms would act like a diffraction grating.
x-ray Diffraction Methods
The various experimental x-ray diffraction methods are the following
(a) Laue's method
In this method a single crystal is held stationary in a beam of x-ray having continuous wavelength.
The crystal selects and produces diffraction corresponding to discrete values of λ for which planes of spacing
d exist and angle of incidence satisfies Bragg's relation.
(b) Rotating crystal method
In this method a single crystal is rotated about a fixed axis in a beam of monochromatic x-rays. The
variation of θ brings different atomic planes into a position for Bragg's reflection.
(c) Powder method
In this method a powdered sample of crystalline material is placed in a fixed position in a
monochromatic beam. Among the distribution of various crystalline orientation there will be some for which
the angle of incident satisfy incidence satisfies Bragg's law.
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Bragg's law

Consider two parallel lattice planes of a crystal having separation d between them. Let a narrow
monochromatic beam of x-ray be incident on these planes at a glancing angle θ. The beam is partially
reflected at the successive parallel layers. The intensity of the reflected beam at certain angles will be
maximum when the two reflected wave front have a path difference equal to an integral multiple of the
wavelength of the x-ray.
Consider the two parallel beam I and II reflected by two atoms A and B in two adjacent layers. The
atom B being vertically below A. The ray reflected from B travel a longer distance than that reflected from
A. To find the path difference, draw AC and AD perpendicular to the direction of the incident and the
reflected rays. Each of these lines makes an angle θ with AB.
From figure,
BC = BD = AB sinθ
= d sinθ
Therefore path difference between the two wave trains
= BC+BD
= 2d sinθ
Therefore the condition for constructive interference between the two rays is
2d sinθ = nλ
where n is an integer.
This is known as Bragg's equation. Using this theory Laue pattern of diffraction spots can be explained.
Laue's Method
X-rays from the X-ray tube is collimated into a fine beam by two slits S1 and S2. The beam is now
allowed to pass through a zinc sulphide (ZnS) crystal. The emergent rays are made to fall on a photographic
plate P. The diffraction patten so obtained consists of a central spot at O and a series of spots arranged in a
definite pattern about O. The central spot is due to the direct beam, whereas the regularly arranged spots
are due to the diffraction from the atoms of the various crystal planes. These spots are known as Laue spots.
The diffraction pattern can be explained by the Braggs law
2d sin = n
From this the interplanar distance of the crystalline substance can be calculated
The Laue experiment has established the following facts :
(i) X-rays are electromagnetic waves of extremely short wave length.
(ii) The atoms in a crystal are arranged in a regular three-dimensional lattice.

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Rotating Crystal Method
In this method a narrow beam of monochromatic radiation is allowed to fall on a fragment of crystal.
The beam gets diffracted. The crystal is turned around an axis perpendicular to the beam while the exposure
is taking place. When the crystal is rotated, the variation in the angle θ brings different atomic planes into
the position for reflection. The diffracted beam is recorded photographically upon a film bent into a cylinder
around the axis of rotation.
The diffracted ray gives small distinct spots on the film. Beams from all planes parallel to the rotation
axis will lie in a horizontal plane. Planes with other orientation will reflect in layers above and below the
horizontal plane. Thus the reflected spots form parallel lines. If the wavelength of the incident beams is
known, the spacing d between the crystal plane can be calculated by using Bragg's equation ,
2d sinθ = nλ.
The plane which always contain the incident beam during the whole reflection cannot reflect.
Similarly a plane with spacing so small that λ/2d>1 also cannot deflect. The reflection form planes in different
orientation may overlap and make the identification of spots difficult. Hence the crystal is oscillated through
a limited angular range instead of being rotated through full 360°. The limited range reduces the possibility
of overlapping.
The powder crystal method
The powder method of analysis is a considerably more powerful method of crystal analysis. In this
method the specimen of a crystal powder is held in a fixed position in the path of a monochromatic beam of
x-rays. In the powder the tiny crystals will have random orientation. Hence all possible diffraction planes will
be available to the monochromatic radiation for Bragg's reflection to take place. Such reflection will take
place from many sets of parallel planes lying at different angles to the incident x-ray beam. Moreover each
set will give not only first order reflection but also those of higher orders as well. Since whole orientation are
equally likely, the reflected race will form a cone whose axis lies along the direction of the incident beam.
The semi vertical angle of the cone is twice the glancing angle for that particular set of planes. For each set
of planes and for each order there will be such a cone of diffracted rays. If a photographic plate is set with
its plane normal to the incident beam, concentric circular rings will be obtained. By finding the radius of such
circle, the consequent glancing angles can be calculated. From this the interplanar distance of the crystalline
substance can be calculated using the Bragg's equation 2dsinθ=nλ .
Experimental arrangement

X-rays from tube are monochromatised by passing them through a filter F which absorbs all but one
wavelength of the incident x-ray. After being collimated by two fine slits S1 and S2, the beam falls on the

15
powder specimen C enclosed on a fine capillary tube of non diffracting material or simply coated with gum on
a thin wire suspended on an axis of a cylindrical camera (Debye- Scherrer camera). The photographic film is
mounted around the inner surface of the camera so as to cover nearly the whole of the circumference. Since
the film is of narrow width, only parts of the circular rings register on the film as shown in figure. The
curvature of these arcs reverses after the angle of diffraction exceeds 90°. If R is the radius of one circle and
X is the radius of the cylinder then
tan2θ = R/X
or 2θ = R/X ( Since θ is small)
Therefore θ = R/2X
Using this value of θ in Bragg's formula interplanar spacing d can be calculated.
Amorphous Solids and Liquids
In amorphous solids the atoms are arranged in a random fashion.
An amorphous solid is a liquid that does not flow. Its atomic structure is disordered like that of a
liquid but it is rigid and holds its shape like a solid.
The atoms in amorphous solids are fixed in space. They do not drift as they do in liquids. So
amorphous solids are referred as supercooled liquids.
A liquid has a structure. But the order in a liquid is restricted only to the few shells of neighbours
surrounding the central atom. As one goes farther and farther atoms, their distribution relative to the central
atom becomes entirely random. This is why a liquid has a short range order. But in a crystal the positions of
all atoms are exactly known once the position of the central atom is given. Thus a crystal has both short
range and long range orders.
The interatomic force is responsible for the crystallinity of a solid. When a solid melts, the change in
volume is considerably small. So the distance between atoms and hence the interatomic force remains same.
When a solid melts, the thermal kinetic energy of the atoms increases. But the interatomic forces are strong
enough to impart a certain partial order to the liquid.
Consider an atom as the central atom. Draw a spherical shell of radius R and thickness R around
this atom. Let n be the number of atoms per unit volume (concentration). Then the number of atoms in the
given shell is
N = n 4 R2 R
The structural properties of the liquid depends on the value of ‘n’. The concentration ‘n’ verses R in
liquid mercury as revealed by x-ray diffraction is shown in figure.
For small values of R the value of n = 0. This is because, as other atoms approach the central atom
very closely strong repulsive forces arise. The curve has a primary peak at R  3 Ao. This is due to
the attractive interatomic force. Beyond which it oscillates a few times before reaching a certain
constant value. The oscillations in the curve arise from an interplay between the forces of the central
atom and the forces of the near neighbours. At large values of R, the value of n approaches a
constant value
Pair Distribution Function
The correlation between the atoms is expressed in terms of a quantity called pair distribution
function. It is defined as the ratio of the concentration of atoms nR to the concentration of atoms no at large
distance
n
g =
n
Interatomic Forces
The force between atoms of an element is called interatomic force. An atom consists of positively
charged protons and negatively charged electrons. They are equal in number. So atom is electrically neutral.
16
 When two atoms are brought close to a distance comparable to the size of the atom, there is
interaction between theses charges. This gives rise to interatomic force.
There is force of attraction between the electrons of an toms and the neutrons of the other atom.
At the same time there is force of repulsion between the electrons of the two atoms and also between the
two nuclei.
Consider two atoms placed along a straight line. The variation of force between them with distance
is shown in figure.
When the atoms are quite far away, there is no force of interaction between them. As they are
brought closer, at first there is attractive force between them. There will be no force of repulsive force at
distance greater than about three times the diameter of the atoms. With decrease in distance the attractive
force increases. After a certain distance repulsive force also comes into effect. When the electron shells of
the atoms overlap the repulsive force increases rapidly.
When the separation between the two atoms is equal to the sum of the radii of the two atoms, the
resultant force becomes zero. This distance ro is called the equilibrium separation. Thus when the distance
between the atoms is greater than ro, the attractive force is greater. When the distance of separation is less
than ro, the repulsive force is greater.
Note
The variation of interatomic potential energy with the distance r between the two atoms is shown
in figure. At large distance the PE is slightly negative. As the distance is decreased, PE becomes more
negative and at ro the negative value is maximum. When r is less than ro, the PE is less negative and finally it
becomes positive.
At equilibrium separation the PE is minimum. This energy is called dissociation energy.
Types of Bonding
Bonding
The ability to hold the atoms or ions together is called bonding. The basic requirements of types of
bonding is that all bound system should have minimum energy in their stable form.
The forces acting in the atoms are electrostatic on nature. The individual atoms of a crystalline solid
are held together as one system with different types of bonds existing between them. These bonds are
classified into five idealised types.
1. Ionic bonding
2. Covalent bonding
3. Van der Waal bonding
4. Hydrogen bonding
5. Metallic bonding

Ionic bond
Ionic bond arises from the transfer of one or more electrons from an electropositive atom to an
electronegative atom. Thus, a positive and negative ion are produced. The two atoms involved in ionic
bonding are different from each other. The electropositive atom has a low ionic energy. The electronegative
elements are of high electron affinity. They are ready to take up an additional electron to complete their
outermost valence orbit and thus acquire stable configuration.
The two oppositely charged ions thus formed attract each other with an electrostatic force. This gives
rise to an attractive potential given by
−1 Z Z e
V=
4πε r
e
= −
4πε 𝑟
17
where Z1e is the charge of one ion and Z2e is that of the other ion separated by a distance r and  is a constant
called Madelung constant. This has the same value for all crystals of the same structure. This energy keeps
the atom bound inside the solid.
An ionic bond can exist between two atoms when one of them have as many valence electrons as
are required by the other to complete its outermost valence orbit.
Properties of ionic bond
1. The ionic bonds are the strongest of all the bonds
2. The ionic bonded crystals are strong, hard and brittle.
3. The ionic bonded molecules in their aqueous solutions or in the molten state are good conductors of
electricity.
4. Such crystals are transparent to visible light.
5. The dielectric constant changes with the frequency of AC applied.
6. Crystals are quite soluble in ionising solvents like water.
7. They are usually crystalline.
Covalent bond
Atoms can attain a stable electronic configuration by sharing unpaired electrons amongst them.
The type bonding resulting from the sharing of one or more electrons by the atoms is known as
covalent bonding. Each atom participating in a covalent bond contribute an electron to the bond and these
electrons are shared by both the atom. The sharing takes place in such a way that an electron with spin up
pairs with another electron with spin down, in accordance with Pauli's exclusion principle. An attractive
potential Va arises due to the pairing of electrons with anti parallel spins and the repulsive potential Vr arises
due to the electrons with parallel spins.
Properties of covalent bonding
The main properties of covalent crystals are
1. These substances are made up of individual covalent molecules with weak intermolecular forces.
2. The substances are generally insoluble in ordinary liquids but soluble in ether benzene etc.
3. Covalent crystals are very hard.
4. Their dielectric constant is independent of applied field.
5. They generally exhibit structural and space isomerism.
6. The conductivity of covalent crystal varies over a wide range.
Van der Waal Bond
The atoms of inert gases like helium and argon spherically symmetrical and have no valence electron,
as their outermost electron orbits are completely filled. They are therefore incapable of forming any bond.
However these molecules condense to liquid and solid state with the decrease of energy. To explain this, Van
der Waal suggested some type of attractive force between this molecules and atoms of inert gases. These
are weak attractive forces which become relatively stronger in the liquid or solid state. The Van der Waal
attraction between two molecules a distance r apart is proportional to 𝑟 , so that it is significant only for
molecules which are very close together. Thus Van der Waal force is a short range force falling rapidly as the
atoms separate.
Polar molecules have a permanent electric dipole moment. Such molecules tend to align themselves
with ends having opposite kind of charge adjacent to each other. In this orientation, the molecules strongly
attract each other. If there are polar and nonpolar molecules, the electric field of the polar molecules causes
a separation of charge in the other (non-polar) molecules. So that positive charge lies nearer to the negative
end, thus resulting in an attractive force .
Even two non-polar molecules can attract each other by the above process. It may be imagined that
the electron cloud may be concentrated at one end of the atom or molecule at a certain moment and a
fraction of a second later, it may be located that the other end of that atom or molecule. Thus instantaneous
concentration of the electron cloud sets up a temporary dipole called the instantaneous dipole. The energy
of the system is decreased by an attractive interaction between two such instantaneous dipoles. Thus Van
der Waal's force are caused by dipole-dipole and dipole-induced dipole interaction. These forces depend
upon the following factors.
18
 (1) Number of electrons present in the molecule.
The forces increase with the increase in number of electrons in a molecule.
(2) Molecular size
The larger the molecular size, greater will be surface area and stronger is the Van der
Waal's interaction.
(3) Effect of pressure
If the pressure is increased, the molecules are pressed together resulting in a stronger.
attraction.
(4) Condition of temperature
Lower the temperature, lesser is the movement of the molecules and stronger the
molecular interactions and hence greater the Van der Waal force.
Properties
1. As Van de Waal force is weak, the inert gas crystal have low melting and low boiling points.
2. They inert gas crystals change their state easily.
3. Van der Waal forces in inert gas crystals give rise to properties like friction, surface tension, viscosity,
cohesion, adhesion etc.
4. Due to Van der Waal forces, there is always a difference between the pressure exerted by a real gas
and that of an ideal gas.
5. The inert gas usually adopt cubic close packed FCC structure except He^3 and He^4.
6. The inert gas crystals are brittle and lack strength.
7. The inert gas crystals have very high ionization energy.
Hydrogen bonding
A specially strong type of Van der Waal bond occurs between certain molecules containing hydrogen
atoms. The hydrogen atom, having a single electron, loses the same to the other constituent atom (or atoms)
leaving behind a poorly shielded proton, which holds together two electronegative atoms with a binding
energy of the order of 0.1 eV. The H+ ion(proton) can have only two near neighbour negative ions because
its radius is 10 -15m which is thousands of times smaller than the radius of other ions. The Van der Waal's
forces are very strong and vary in accordance with inverse square law.
Metallic bonding
For metals, the ionization energy is low. They have vacant valency orbitals and have a few valency
as compared to the number of valency orbitals. Thus in the atoms of metals, the electrons on the outermost
orbits are loosely bound. These are called free electrons or conduction electrons. One or two such electrons
can be detached from the parent atom due to the attraction of adjacent atomic cores.
The remainder portion of atom, which is a positively charged sphere is called a kernel. The free electrons
are mobile in nature and move from one kernel to another throughout the metal lattice. Thus the metal
crystal may be pictured as an arrangement of positive ions immersed in a sea of mobile electrons. The
motion of these electrons is such that they are simultaneously near to two or more kernel's and bind them
together. The bond thus formed between the metal atoms is known as metallic bond.
Hence a metallic bond is due to the result of simultaneous attraction of an electron by two or more
than two positive ions of the metal. Thus a metallic bond is also partially electrostatic in nature. Each free
electron is on an average, close to one nucleus or another, than it would have been if belonged to the isolated
atom. This results in the decrease of potential energy of the electron forming the crystal. This decrease in
energy is responsible for the metallic bond.
Note
The metallic bond is weaker than the covalent bond due to the fewer electrons bonding the nuclei.
Properties
1. They are good conductors.
2. Heat is produced in the metals when an electric current is passed.
3. The electrical resistance increases with the heating of metals.

19
4. Metal crystals are of unlimited size due to the unsaturated nature of the bonds.
5. They are malleable and ductile.
6. Metals have high tensile strength.
7. They have high thermal and electrical conductivity.

20