UNIT - I

Different types of Chemical Bonds

1. Ionic or Electrovalent Bond
The bond formed between two different atoms, one of which has low ionization energy and the
other has high electron affinity, by transfer of valence electrons from one atom to the other is
called Ionic bond.
Example: NaCl

Suppose a chlorine atom and a sodium atom approach one another. Sodium atom can release one
electron to get stable configuration and at the same time chlorine atom can accept one electron so
as to form a complete electronic configuration in its M shell. This process of adding an extra
electron to the chlorine atom is accompanied by the appreciable decrease in the potential energy.
The energy lost will appear in the form of heat and light during the reaction or formation of
NaCl. When sodium atom loses one electron it becomes a positive ion ie) anion, and as chlorine
atom gains one electron, it becomes a negative ion ie) cation.

The ions attract each other with coulombic forces which lead to the formation of an electrovalent
or ionic bond between two neighboring Na and Cl atoms. at the same time, the two ions achieve
noble gas structure(completely filled shell).
Properties of Ionic solids:

 In ionic crystals, oppositely charged ions are joined together by strong electrostatic forces
 They are hard and brittle substances
 They have high melting and boiling point.
 They conduct electricity in molten state and in the form of solution but pure and dry ionic
solids are good insulators because all the electrons are tightly bound with the ions involved in
the bond formation.
 They are not ductile
 Ionic bonds are non-directional. So that in an ionic crystal, a cation tends to surround itself
by as many anions as possible and vice versa.
2. Covalent bond or Homopolar Bond
A covalent bond is formed when two or more similar or dissimilar atoms achieve stability by
sharing valence electrons between themselves.
Example: Ge, Si, Diamond
Properties:
 Covalent bond is formed between two atoms when they share one or more pair of
electrons between them.
 These bonds are directional. The bond is formed in a direction where the shared two
electron clouds are overlapping with each other and it has directional character. That is
why, it is also called homopolar bond.
 Covalent compounds are soluble in nonpolar solvents
 Covalent compounds are existing in solids, liquids and gases
 Only the covalent solids are existing in crystalline structure.
 Electrical conductivity is increased by suitable doping impurities
 Covalent compounds have comparatively low melting and boiling point.
 Covalent solids are hard
3. Metallic bonds
In metals, each atom loses all its valence electrons and becomes a positively charged ion.
These free and mobile electrons form a kind of electron cloud or gas which permeates all
atoms. These valence electrons are not bounded directly to an individual atom but they move
freely in the sphere of influence of other atoms and are bound to different atoms at different
times and that too part of the time.
Thus, a metallic bond results from the sharing of variable number of electrons by a variable
number of atoms. The cohesion of a metallic crystal is due to the attraction of the positive
nuclei and the valence electrons passing between them. The delocalization of the valence
electrons leads to decrease in both kinetic and potential energy and is responsible for metallic
bonding.
 Metallic bonds are responsible for holding the atoms together in metals and their alloys
 This type of bonding is weaker than ionic and covalent bonds which are called saturated
bonds but stronger than Van der waals type
 Metallic solids have crystalline structure. Unlike other type of crystals, metallic crystals
can be deformed without fracture since the electron gas behaves as a lubricant which
permits the atoms to slide fast one another
 Metallic crystals possess a high degree of crystal symmetry due to symmetrical
arrangements of positive ions.
 Metallic bond is non-directional since this bond can exist only when there is large
aggregate of metallic atoms
 Since the metallic bonds are weak, the melting point and boiling point are lower than the
ionic and covalent compounds
 Since there are enormous number of free electrons, this type of materials has high
thermal and electrical conductivity
 Metals are opaque to light since the light energy is absorbed by the free electrons
4. Hydrogen Bond
It is a particular type of dipole bond in which one of the atom is a hydrogen atom. The other
atom has a high affinity to attract electron from the hydrogen atom. Thus, it is a special type
of dipole bond made between similar molecules, each molecule having one end as a
hydrogen atom converted into a positive ion by a strongly electronegative adjacent atom in
the same molecule. Hydrogen bond is formed by a hydrogen ion located between two anions.
Since hydrogen has only one electron it can lose it to either of the two adjoining ions with the
result that there is and equal probability of finding the electron on either ion. The positive
hydrogen ion tends to draw the two anions more closely together than their normal separation
in crystals so that such a shortening of their interatomic separation serves to indicate the
presence of a hydrogen bond.
Properties
 The bond between water molecule is strong enough to persist in the liquid state.
 The hydrogen bonds are directional
 Hydrogen bonded solids have low melting points. because in such solids no valence
electrons are available, they are good insulators.
  They are transparent to light since there are no free electrons
 They are soluble in both polar and non-polar solvents
 Solids which have hydrogen bond may be crystalline or non-crystalline. Moreover, as
these solids are formed of elements of low atomic numbers, they have low densities
 These bonds are stronger than dispersion bonds but are weaker than primary bonds. Thus,
these bonds have enough strength to exist in liquid and gaseous states.

Crystal
type Units that Physical property
Bonding
occupy
force
lattice sites Hardness Brittleness Melting Electrical
Examples
point conductivity
Very low
Quite hard Relatively
Ionic Ionic Ions Very high (high in NaCl, CaO
and brittle high
molten state)
Electrostatic
attraction Positive
Metallic between +ve ions in Variable Very low Variable Very high Cu, Fe, Ag
ions and sea electron gas
of electrons
Sharing of
Diamond,
Covalent electron Atoms Very hard Medium Very high Very low
SiC, SiO2
pairs
Molecular
Ice, I2,
Molecular interation Molecules Very soft Low Very low Very low
Fullerene
forces

Lattice energy of ionic crystals

NaCl crystal consist of Na+ and Cl- ions. It is assumed that the ionic charges have spherical
symmetry and the force between them depends upon the distance between them and is non
directional. There are two types of forces acting between them. These are long range
electrostatic coulomb force and short range repulsive force. When the electron clouds are
overlapping with each other, the repulsive force is created and that repulsive force depends
upon the compressibility of the crystal. Let the distance between two successive ions in NaCl
crystal lattice be r. Let us take a sodium ion, named A, which is surrounded by six chlorine
ions at a distance r. Assuming that e is the ionic charge of each ion,
2
−6 e
the coulomb energy due to these six chlorine ions is equal to =
4 π ε0 r
further it is surrounded by 12 sodium ions at a distance √ 2 r and the coulomb energy from
12 e2
these ions =
4 π ε0 √ 2 r
similarly, the coulomb energy due to eight chlorine ions which is at a distance √ 3 r from the
2
−8 e
sodium ion A is equal to =
4 π ε0 √ 3 r
further A is surrounded by six sodium ions which are at a distance 2r and by 24 chlorine ions
at a distance √ 5 r . Thus the total amount of coulomb energy of A is given by

[ ]
2
−e 6 12 8 24
U coulomb = − + + ….
4 π ε 0 r √ 1 √2 √3 √5
Here, the negative sign indicates the attractive force and the positive sign indicates the
repulsive force. Since the coulomb energy decreases with increase of distance, it will be
enough to take the effect of nearest ions only to calculate the coulomb energy of A.
2
−e
The coefficient of is a natural number whose value depends upon the structure of the
4 π ε0 r
crystal and is called madelung constant, A' .
For sodium crystal, madelung constant A' =¿
2
−1.748 e
Therefore, U coulomb =
4 π ε0 r
Thus, the coulomb energy is an attractive energy. If there is only coulomb energy, then the
crystal lattice will be deformed. To avoid this, there is a repulsive force between ions. When
the ions are very close to each other, their valence electron orbits begin to overlap. Due to
this, a repulsive force is created and repels the ions. The value of the repulsive energy is
B'
about n . The values of B' and n depend upon the properties of ions in the crystal. Thus, the
r
total potential energy of an ion under equilibrium conditions is given by
2
−1.748 e B'
U ( r)= + n
4 π ε0 r r
The value of n varies from 9 to 15. The crystal lattice energy is the energy required to form
the crystal lattice by placing the constituents of that crystal.
 Difference between crystalline solids and amorphous
Crystalline Solids Amorphous Solid
1) i) They have a regular three-dimensional i) They do not have regular arrangement of
arrangement of atoms, ions or molecules due particles, therefore do not have well defined
to which they have well defined geometrical particles.
shape.
2) ii) They have long range order(which means ii) They have short range order
the arrangement of atoms is repeated over a
great distance.)
3) iii) They have sharp melting point i.e., they iii) They do not have sharp melting point i.e.,
melt at a particular temperature. they melt over a range of temperature.
4) iv) They have high and fixed heat of fusion, iv) They do not have fixed heat of fusion.
i.e., high energy is required to melt 1 mole of
crystalline solid.
5) v) They are anisotropic, i.e., they have v) They are isotropic, i.e., they have same
different optical and electrical properties in properties in all directions.
different directions.
6) vi) They are true solids, i.e., they show all vi) They are pseudo – solids, i.e., they do not
the characteristic properties of solids. show all the characteristic properties of
solids.
vii) They undergo a clean cleavage
vii) They cut irregularly

Lattice points

crystals are composed of a periodic array of atoms. The structure of all crystals can be described
in terms of a lattice, with a group of atoms attached to each lattice point called basis.
Basis + Lattice = crystal structure
 Lattice points denote the position of atoms or molecules in the crystals or it is a point in a crystal
with specific arrangement of atoms, reproduced many times in the crystal. The translational part
of the repetitions in the crystal is given by the lattice vectors.

Choose a point within the repeated unit cell. It can be any point. Translate that point and all the
surrounding atoms in the crystal basis by the repeat distance and direction, i.e., the lattice vector.
Then the point is repeated, as are all the spatial relationships among the surrounding atoms. Let
a1 and a2 are the lattice vectors. Every lattice point can be located as rmn = ma1+ na2(m, n are
integers) or in three dimensional case: rlmn = la1+ m a2+ na3 (l, m, n are integers)
Two points, r and r’ related by translational vector r’ = r + la1+ m a2+ na3 (l, m, n are integers) are
equivalent environmentally. Note that a1, a2 and a3 are lattice vectors and properties of the
materials.

Here are some things to know about lattice vectors:

1. Lattice vectors connect two lattice points.
[Link] lattice point may be reached from any other by the vector addition of an integral number
of lattice vectors.
3. Non-integral combinations of the lattice vectors give the atomic positions of the crystal basis.
4. Rational lattice directions connect one lattice point to another and are specified by integral
components of the lattice vectors.

Space Lattice

An infinite three-dimensional array of points showing how atoms or molecules are arranged in a
crystal is known as space lattice.
Unit cell

The unit cell is the smallest block or geometric figure from which the entire crystal is built up by
repetition in three dimensions.

Lattice parameters of a unit cell

i) crystallographic axes(x, y, z)
The lines drawn parallel to the lines of intersection of any three faces of the unit cell which
do not lie in the same plane are called crystallographic axes(x, y, z).
ii) interfacial or interaxial angle(α, β, γ)
The angles between the three crystallographic axes are known as interfacial or interaxial
angle.
iii) Primitives or characteristic intercepts
The intercepts a, b and c define the dimensions of a unit cell and are known as its Primitives
or characteristic intercepts. These three quantities a, b and c are also called the fundamental
translational vectors.
The primitives a, b and c and interfacial angles α, β, γ are the basic lattice parameters
because they determine the form and actual size of the unit cell and hence the space lattice.

Primitive cell

The primitive cell is a parallelepiped specified by the primitive translation vectors. The unit cell
formed by the primitives a, b and c is called primitive cell. In this cell, there is only one lattice
point. If there are two or more lattice points, then it is not a primitive cell. In case of simple cubic
lattice, the primitive cell and unit cell are equal since it has only one lattice point in its unit cell.

Seven crystal system and 14 types of Bravais lattice

Based on the unit cell dimensions and the interfacial angles, the 7 crystal systems are divided
into 14 types of Bravais lattices.

N° Crystal Unit cell Bravais lattices Examples

System Dimensions
 and angles
1 Cubic a=b=c ; Primitive(simpl PO
α=β=γ=90° e)
Na
Face centered
Ag, Au, Pb
Body centered

TiO2
Primitive
a=b≠c; KH2PO
2 Tetragonal
α=β=γ=90°
Body centered

Primitive

a≠b≠c; Face centered BaSO4

Orthorhombi
3
c
α=β=γ=90° Body centered K2SO4

Base centered α-S

CaSO4.2H2O
Primitive
a≠b≠c;
(gypsum)
4 Monoclinic α=γ=90° β≠90
°
K2MgSO4.6H2
Base Centered
O
K2Cr2O7
a≠b≠c;
5 Triclinic Primitive
α≠β≠γ≠90°

Calcite
Rhombohedr a=b=c;
6 Primitive
al α=β=γ≠90°

Quartz
a=b≠c;
7 Hexagonal α=β=90° γ=12 Primitive
0°
1. Simple cubic lattice

NUMBER OF ATOMS PER UNIT CELL (n)

 The total number of atoms present in a unit cell is
known as number of atoms per unit cell.
COORDINATION NUMBER (CN)
 It is the number of nearest neighboring atoms to a
particular atom.
ATOMIC RADIUS (r)
 It is the radius of an atom. It is also defined as half the
distance between two nearest neighboring atoms in a
crystal.
In simple cubic structure, atoms are present only at the corners of the cube. Consequently,
these atoms touch along the cube edges. This structure is loosely packed because each corner
atom has only six nearest neighbors. So, the coordination number is six. That is, each atom
has four neighbors in the same plane, one vertically above and one immediately below,
giving a total of six nearest neighboring atoms. If r is the atomic radius and a is the side of
a
the cube then, r = .
2

since each corner atom is shared by eight surrounding cubes, the contribution of each corner
atom to this particular unit cell is 1/8.
1
Therefore, total number atoms present in the unit cell = 8 × =1 atom . In this case, the unit
8
cell is equal to the primitive cell.
ATOMIC PACKING FACTOR (APF)
 It is the ratio of volume occupied by the atoms or molecules
in an unit cell (v) to the total volume of the unit cell (V).

APF = No. of atoms present in the unit cell x Volume of the atom
----------------------------------------------------------------
Volume of the unit cell
v
APF= ; v = 1  4/3 r3; V = a3
V
4 3
1× π r
 APF = 3
3
a
 a
substituting r = , we get,
2
APF = 4 π ¿ ¿
Therefore packing density = /6 = 0.5236 ≈ 0.52
Thus 52 percent of the volume of the simple cubic unit cell is occupied by atoms and the
remaining 48 percent volume of the unit cell is vacant or void space.

2. Body centered cubic structure

 A body centered cubic structure has eight comer atoms and one body centered atom.
 The atom at the center touches all the eight corner atoms.
 The BCC structure is shown in the figure.
 In BCC unit cell, each and every corner atom is shared by eight adjacent unit cells.
1
So, the total number of atoms contributed by the corner atoms is = 8 × =1
8
A BCC unit cell has one full atom at the center of the unit cell.
The total number of atoms present in a BCC unit cell = 1+1 = 2.
CO-ORDINATION NUMBER (CN)
 Let us consider a body centered atom. The nearest neighbor for a body centered atom is a
corner atom. A body centered atom is surrounded by eight corner atoms. Therefore, the
co-ordination number of a BCC unit cell = 8.
ATOMIC RADIUS (R)
For a BCC unit cell, the atomic radius can be calculated
From figure AB = BC = AD = ‘a’ and CD = 4r.

Atomic Packing Fraction:

From the triangle, ACD,
CD2 = AC2 + AD2
CD2 = 2a2 + a2
(4r)2 = 3a2
16r2 = 3a2
3 a √3
2
i.e. r2 = = a
16 4
v
APF=
V
 v = 2  4/3 r3; V = a3
4 3
2× π r
 APF = 3
3
a
substituting r =
√3 a ,
4
we get,
3
4 √3 a
APF =
2× π (
3 4
)
=
√3 π = 0.68
3 4
a
Therefore, packing density = 68% so it is not a closely packed structure. Thus, 68 percent of
the volume of the BCC unit cell is occupied by atoms and the remaining 32 percent volume
of the unit cell is vacant or void space.
3. Face centered cubic structure
This structure contains eight corner atoms and one atom present at the center of each face.
The atoms are in contact with the diagonal atoms. Thus, there are eight corner atoms and six
face centered atoms.

In three-dimensional packing of spheres, the third layer is placed in octahedral voids and created
a layer which is different from first (A) and second (B) layer, therefore marked as 'C' layer. This
pattern is known as face centered cubic (FCC) or cubic close packing (CCP). Metals like iron,
gold, silver, platinum, copper, nickel show such type of close packing. In FCC, face centered
atom is in contact with six other atoms in its own layer and also touch three atoms of above layer
and three atoms of below layer. Hence the coordination number is 12.
Each of the 6 face centered atoms is shared by the two adjoining cubes. Hence a total of 6/2 = 3
such atoms belong to the unit cell. The contribution of each corner atom to this unit cell is 8.
1 6
Hence total number of atoms per unit cell = 8 × + =4. Let ‘r’ be the radius of sphere and ‘a’ be
8 2
the edge length of the cube

As there are 4 sphere in fcc unit cell, ∴ Volume of four spheres = 4 (4/3 πr3). In Fcc, the corner
spheres are in touch with the face centred sphere. Therefore, face diagonal AC is equal to four
times the radius of sphere, AC= 4r

But from the right angled triangle ACD

AC = AD2 + DC2 = √a2 + a2= √2a

4r = √2a

4r
or a = =2 √ 2 r
√2
packing Factor = volume occupied by atoms in the unit cell / Volume of the unit cell

4 3
4× πr
PF = 3
3
=0.74=74 %
(2 √ 2r )

4. Hexagonal Close Packed Structure

 There are three layers of atoms present in the HCP structure. At the bottom layer, the central
atom has 6 nearest neighboring atoms in the same plane. Further, the second layer which is at
a distance c/2 from the bottom layer has three atoms. Third layer(top) is similar to the bottom
layer in the arrangement of atoms and it is at a distance c from the bottom layer. Thus, it has
the stacking sequence of ABAB…..

i) Coordination number of HCP structure

If we take the bottom layer, the central atom has 6 nearest neighboring atoms in the same
plane. Further, at a distance c/2 from the bottom layer, there are two layers. One is above and
another is below the bottom layer containing three atoms in each layer. So totally, there are
12 nearest neighboring atoms. Therefore, the coordination number = 12

ii) Atomic radius

The nearest neighboring distance 2r = a

iii) c/a ratio

Let c be the height of the unit cell and a be the distance between two neighboring atoms.
Consider the triangle ABO in the bottom layer of the HCP structure. Here, A, B and O are
the lattice points and exactly above these at a perpendicular distance c/2 the next layer atom
lies at C.

AA
'
' a √3
Cos30° = ; A A = AB cos 30 °=
AB 2

' 2 a √3 a
But AX = 2/3 A A = . =
3 2 √3
In the triangle AXC, (AC)2 = (AX)2+(CX)2

(CX)2 = (AC)2 - (AX)2

¿
c
=√ 8/3=1.633
a

iv) Packing Fraction

Area of the base = 6. (area of the triangle ABO)

a √3 a 3 √ 3
2
1
= 6 × × AB ×O O' =3 ×a × =
2 2 2

a 3 √3
2
Hence volume of the HCP structure = Area of the base . height c = .c
2

If we consider the top layer, which has totally seven atoms. Each corner atom contributes 1/6
atom to the unit cell and the centre atom contributes ½ atom to the unit cell. Hence, the total
1 1 3
contribution by the top layer to the unit cell = × 6+ = . Similarly, the contribution of
6 2 2
3
bottom layer also . The central layer contributes 3 atoms fully because all the central layer
2
atoms are well inside the unit cell.

3 3
Therefore total number of atoms per unit cell = + +3=6
2 2

4 3
6×
πr
v 3
Packing fraction = = 2 substituting 2 r=a∧c =√ 8/3
V a 3 √3
.c
2

π
Therefore, packing fraction = =0.74 ≈74 %
3 √2

Thus the density of packing is 74% and hence it is a close packed structure.

Number of Nearest distance

Lattice Maximum packing
lattice points/atoms between lattice Example
type density
per unit cell points

Simple
cubic
1 a=2r π /6 = 52 % Phosphor

a=4r/√ 3
Body
centered 2
√3 π = 68 % Tungsten
a
cubic 2r = √ 3 8
2
 π
Face a = 2√ 2 r
centered 4 3 √2 Aluminum
cubic 2r = a/√ 2
= 74 %

π
Hexagonal 6 a = 2r 3 √2 Quartz
= 74 %

Diamond structure:

 It is formed by carbon atoms.

 Every carbon atom is surrounded by four other carbon atoms situated at the corners of
regular tetrahedral by the covalent linkages.

 The diamond cubic structure is a combination of two interpenetrating FCC sub lattices
displaced along the body diagonal of the cubic cell by 1/4th length of that diagonal.

 Thus, the origins of two FCC sub lattices lie at (0, 0, 0) and (1/4, 1/4,1/4)

 The points at 0 and 1/2 are on the FCC lattice, those at 1/4 and 3/4 are on a similar FCC
lattice displaced along the body diagonal by one-fourth of its length.
 In the diamond cubic unit cell, there are eight corner atoms, six face centered atoms and four
more atoms.

 No. of atoms contributed by the corner atoms to a unit cell is 1/8×8 =1.

 No. of atoms contributed by the face centered atoms to the unit cell is 1/2 × 6 = 3

 There are four more atoms inside the structure.

 No. of atoms present in a diamond cubic unit cell is 1 + 3 + 4 = 8.

 Since each carbon atom is surrounded by four more carbon atoms, the co-ordination number
is 4.

ATOMIC RADIUS(R)

From the figure, in the triangle WXY,

( )( )
2 2
a a
XY2 = XW2 + WY2 = +
16 16

2
2a
XY =
8

Also, in the triangle XYZ,

2 2 2
2 a a 3a
2 2
XZ = XY + YZ = + =
8 16 16

But XZ = 2r
2
3a
(2r)2 =
16

Atomic radius r =
√3 a
8

Atomic packing factor (APF)

APF = No. of atoms present in the unit cell x Volume of the atom
----------------------------------------------------------------
Volume of the unit cell
 Miller Indices

 The crystal lattice may be regarded as made up of an infinite set of parallel equidistant

planes passing through the lattice points which are known as lattice planes.

 In simple terms, the planes passing through lattice points are called ‘lattice planes’.

 For a given lattice, the lattice planes can be chosen in a different number of ways.
 The orientation of planes or faces in a crystal can be described in terms of their intercepts on
the three axes.

 Miller introduced a system to designate a plane in a crystal.

 He introduced a set of three numbers to specify a plane in a crystal.

 This set of three numbers is known as ‘Miller Indices’ of the concerned plane.

Miller indices is defined as the reciprocals of the intercepts made by the plane on the three

axes.

Steps to determine Miller indices

i) Find the intercepts on the axes in terms of the lattice constants a1, a2, a3. The axes
may be those of a primitive or nonprimitive cell.
ii) Take the reciprocals of these numbers.
iii) Reduce the numbers to three smallest integers by multiplying the numbers with the
same integral multipliers.
iv) The results, enclosed in parenthesis (hkl), are called the Miller indices.

Example

 Plane ABC has intercepts of 2 units along X-axis, 3

units along Y-axis and 2 units along Z-axis
Step 1: The intercepts are 2,3 and 2 on the three axes.
Step 2: The reciprocals are 1/2, 1/3 and 1/2.
Step 3: The least common denominator is ‘6’. Multiplying each reciprocal by LCD,
we get, 3,2 and 3.
Step 4: Hence Miller indices for the plane ABC is (3 2 3)
IMPORTANT FEATURES OF MILLER INDICES

For the cubic crystal especially, the important features of Miller indices are,
i) A plane which is parallel to any one of the co-ordinate axes has an intercept of
infinity (). Therefore, the Miller index for that axis is zero; i.e. for an intercept at
infinity, the corresponding index is zero.
ii) A plane passing through the origin is defined in terms of a parallel plane having non-
zero intercepts.
iii) All equally spaced parallel planes have same ‘Miller indices’ i.e. The Miller indices
do not only define a particular plane but also a set of parallel planes. Thus, the planes
whose intercepts are (1 1 1), (2 2 2), (-3 -3 -3) etc., are all represented by the same
set of Miller indices.
iv) It is only the ratio of the indices which is important in this notation. The (6 2 2)
planes are the same as (3 1 1) planes.

v) If a plane cuts an axis on the negative side of the origin, corresponding index is
negative. It is represented by a bar, like (1 0 0). i.e. Miller indices (1 0 0) indicates
that the plane has an intercept in the –ve X –axis.
Perpendicular distance between two parallel planes in a cubic crystal lattice
  Let α ' , β ' ∧γ ' (different from the interfacial angles,  and ) be the angles between co-
ordinate axes X, Y, Z and ON respectively.

 The intercepts of the plane on the three axes are,

a a a
OA= , OB= , OC = −−−−−−−(1)
h k l

d1 d1 d1
From the figure, we have, cos α ' = '
, cos β =
'
, cos γ = −−−(2)
OA OB OC

From the property of direction of cosines, cos 2 α ' + cos2 β ' + cos2 γ '=1−−(3)

Using equation 1 in 2, we get,

' d1 h ' d1 k ' d1l

cos α = , cos β = , cos γ = −−−−−(4 )
a a a
 2 2 2 2 2 2
d1 h d1 k d1 l
Substituting equation (4) in (3), we get, 2
+ 2
+ 2
=1
a a a

(h ¿ ¿ 2+k +l )
2 2
d 12 =1 ¿
a2

d 1 =a /(h ¿ ¿2+ k +l )¿
2 2 2 2

Let d 1=ON

i.e. the perpendicular distance between the origin and the 1st plane ABC is,

a
d 1=ON =
√( h ¿ ¿ 2+k 2 +l2)¿
Now, let us consider the next parallel plane. Let OM=d2 be the perpendicular distance of this

plane from the origin. The intercepts of this plane along the three axes are

' 2a ' 2a ' 2a

OA = , OB = , OC =
h k l

2a
OM =d 2=
√(h ¿ ¿ 2+ k 2 +l2)¿
• Therefore, the interplanar spacing between two adjacent parallel planes of Miller indices
(h k l ) is given by, NM = OM – ON i.e. Interplanar spacing

a
d=d 2−d 1=
√(h ¿ ¿2+ k 2 +l2)¿
Reciprocal Lattice

Reciprocal lattice is also called Fourier lattice, k- lattice, or momentum lattice in

contrast to real lattice or direct lattice.

 The concept of ‘reciprocal lattice’ provides a device for tabulating both the slopes and
the interplanar spacings of the planes of a crystal lattice.

i) In a crystal, there exist many sets of planes with different orientations and spacing.
These planes can cause diffraction.
ii) If we draw normals to all sets of planes, from a common origin, then the end
points of normals form a lattice which is called as ‘reciprocal lattice’.
 iii) Each point in the reciprocal lattice preserves the characteristics of the set of
planes which it represents.
iv) Its direction with respect to the origin represents the orientation of the planes.
v) Its distance from the origin represents the interplanar spacing of the planes.

Consider all the planes belonging to a single zone. Since all the planes to be considered
are parallel to a common line, known as zone line, the normals to these planes lie in the
same plane (normal to the zone axis). In this way, these planes can be represented by a
two dimensional reciprocal lattice.

 A lattice point is taken as common origin. From the common origin, draw a normal to
each plane. Place a point on the normal to each plane (h k l) at a distance from the
1
origin equal to the reciprocal of the interplanar spacing . Such points form a periodic
d hkl
array called reciprocal lattice.

1
Length of each normal = σ hkl=k .
d hkl

K is the scale factor chosen for the construction of the reciprocal lattice.
 2π
With a lattice constant of .
a
Facts and relations of Reciprocal Lattice:

Bragg's Equation

A crystal is considered to be composed of series of parallel and equidistance plane. X-rays are
used to study the internal structure of crystal because

1)The interplanar distance of most of the crystal and wavelength of x-ray are of comparable
range.

2)X-ray have greater penetration power as compared to any other rays.

Let us consider BB', CC' and DD' are some of the planes of a crystal. Let us consider a beam of
monochromatic x-ray PQ is incident on a first plane BB' with an angle θ and reflected along QR.
Similarly, the another beam XY is incident on a plane CC' with an angle and reflected along YZ.

Then from figure, the path difference between the reflected rays=MY+NY — i)

For ΔQMY,

Sinθ = MY/QY

sin θ=MY/d

MY=dsinθ

Similarly, in ΔQNY,

sin θ=NY/QY

NY=dsinθ

Hence, path difference=dsinθ+dsinθ = 2dsinθ — ii)

According to Bragg's law, the path difference between the reflected rays must be a integral
multiple of wavelength of x-ray used.

i.e nλ=2dsinθ — iii)

where, n=1,2,3.......... represent the order of reflection.

Equation iii) is the required Bragg's equation.

Basic Crystal Concepts
Unit Cell

A crystal is an array of atoms packed together in a regular pattern. A unit cell of a

pattern is a piece of the pattern which, when repeated through space without rotation
and without gaps or overlaps, reconstructs the pattern to infinity. For filling space
without holes, a unit cell must be either a parallelogram (in 2D) or a parallelepiped (in
3D).

The symmetries of a pattern determine the shape of the unit cell. For example, mirror
symmetry requires a rectangular (in 2D) or tetragonal (in 3D) unit cell. There is an
infinite number of possible unit cells for any pattern (e. g., a given unit cell can
generate a family of unit cells by repeated doublings in size). By custom, the unit cell
is chosen to be the smallest one that reveals the special geometry characteristic of the
symmetry. Thus, although an oblique parallelogram can be used for a pattern with 4-
fold symmetry in 2D, a square is preferred.

When a unit cell is repeatedly translated to fill all of 2D or 3D space, the vertices of
all the unit cells in the filled space constitute a lattice. A lattice is an infinite array of
regularly-spaced points. All points in the lattice have identical "environments" --- the
view from every point in the lattice is identical to that from any other point in the
lattice. The absolute positions of the points of a lattice, and hence the unit cell, are
arbitrary with respect to a pattern.

Not all lattice points need coincide with unit cell vertices. Primitive unit cells use
every lattice point as a unit cell vertex. Non-primitive unit cells, however, contain
extra lattice points not at the corners.

A primitive unit cell contains exactly one lattice point. For example in 2D, each
primitive unit cell joins four lattice points, each of which counts for 1/4 because every
lattice point is shared among four unit cells. In 2D, a non-primitive unit cell has one
additional lattice point exactly centered within it and is called a body-centered non-
primitive unit cell. In 3D, non-primitive cells are of three kinds:

 end-centered : an extra lattice point is centered in each of two opposing faces

of the cell
 face-centered : an extra lattice point is centered in every face of the cell
 body-centered : an extra lattice point is centered in the exact middle of the cell

Although primitive unit cells are simpler than non-primitive unit cells, the non-
primitive unit cell is preferred when its geometry is more favorable (simpler). For
instance, a rectangular non-primitive cell would be chosen over a rhomboid primitive
cell. In general, the unit cell used is the smallest one with the most regular geometry.

Lattice and Unit Cell Parameters

A lattice may be specified by two non-coincident vectors in 2D, and by three non-
coplanar vectors in 3D. The vectors lie along the edges of the unit cell, and are labeled
a, b, and (in 3D) c. The magnitude of the vectors is given by the dimensions of the
unit cell in the real crystal under study.

The faces of the unit cell are labeled as follows:

 A : edges defined by lattice vectors b and c

 B : edges defined by lattice vectors a and c
 C : edges defined by lattice vectors a and b
Similarly, the inter-facial angles of the unit cell are defined to be:

 alpha : angle between edges b and c

 beta : angle between edges a and c
 gamma : angle between edges a and b

Lattice Systems: the 14 Bravais Lattices

Lattices can be classified into "systems", each system being characterized by the
shape of its associated unit cell. In three dimensions, the lattices are categorized into
seven crystal lattice "systems". Within several of these, lattices supporting non-
primitive unit cells can be defined. The classification scheme yields a total of 14
possible lattices (called Bravais lattices).

The lattice symbols used for classification are as follows:

 P : primitive
 B : end-centered on B-face (convention for Monoclinic systems)
 C : end-centered on C-face (convention for Orthorhombic systems)
 I : body-centered
 F : face-centered
 R : rhombohedral primitive

System # of lattices in system Lattice symbols

Triclinic (Anorthic) 1 P

Monoclinic 2 P, B

Orthorhombic 4 P, C, I, F

Tetragonal 2 P, I

Isometric (Cubic) 3 P, I, F

Trigonal/Rhombohedral 1 P or R

Hexagonal 1 P
In two dimensions, there are only four possible unit cell shapes and two possible
lattice symbols:

Cell shape Lattice symbol

General parallelogram (rhomboid) p

Rectangle p, c

Square p

Rhombus with 60 degree angle p

CRYSTAL: Translationally periodic arrangement of ATOMS in space.

LATTICE: Translationally periodic arrangement of POINTS in space.

BASIS (or MOTIF): An atom or a group of atoms associated with each lattice point in crystal.

CRYSTAL=LATTICE+BASIS

LATTICE of a crystal tells how to repeat (the periodicity of the crystal).

BASIS tells what to repeat according to the lattice to get the crystal

LATTICE TRANSLATION: A vector from one lattice point to another.

UNIT CELL: A finite region of space which when translated by all lattice translations, or a
subset of lattice translations, can fill the entire space without gaps or overlaps (i.e., it tiles the
space).

Thus all the information about a crystal can be deduced if its unit cell is given.

A given crystal or the associated lattice can have infinitely many differently shaped and sized
unit cells.

The most common unit cell shape is parallelopiped. It is also common, though not necessary, to
take the corners of the unit cell at the lattice points. If these are the only lattice points, the unit
cell is PRIMITIVE. If there are lattice points other than those at the corners, it is
NONPRIMITIVE. Primitive unit cell will have effectively one lattice point per cell. A non
primitive one will have more than one lattice point per cell.