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CRYSTAL PHYSICS

Introduction
A solid is that form of matter that possesses rigidity and hence possesses a definite shape and a
definite volume. There are two types of solids:

Crystalline solids
Solids with a definite geometric pattern.
Examples: Iron, copper, silver, sulphur etc. are some elements which form crystalline solids.
Potassium chloride, sodium nitrate etc are some of the compounds, which are crystalline.

Amorphous solids
Solids with particles not arranged in a regular fashion. They have only short range order or even
the particles are disordered in some cases.
Substances whose particles do not possess a regular orderly arrangement but have short range
order. When amorphous solids are heated they become crystalline at some temperature.
Properties of amorphous solids are:

They do not have sharp melting point.

Under go liquefaction over a broad range of temperature.

Do not possess characteristics heats of fusion.

When heated and cooled slowly they become crystalline.

Example: Glass and plastics.


















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Difference between amorphous and crystalline solids



Classification of Crystalline solids






Some substances adopt different structural arrangements under different conditions. Such
arrangements are called Polymorphs.

Example: Diamond and graphite are two different polymorphic forms of carbon.



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Lattice Points:

The atomic arrangement in a crystal is called crystal structure. In a perfect crystal there is
a regular arrangement of atoms. It is very convenient to imagine points in space about which
these atoms are located. Such points in space are called Lattice Points and totality of such
points forms a crystal lattice or space lattice.

Space Lattice:
A three-dimensional space lattice may
be defined as an infinite array of points in three
dimensions in which every point has an
environment identical to that of any other point in the array.

The Basis and Crystal Structure:
Associating with every lattice point a unit assembly of atoms or molecules identical in
composition, arrangement and orientation forms the crystal structure. This unit assembly is
called the basis. When the basis is repeated with correct periodicity in all directions, it gives the
actual crystal structure. The crystal structure is real, while the lattice is imaginary. Thus
Lattice + Basis = Crystal structure





Above figures show crystal structure from Space lattice and Basis. It is observed from the figure
that the basis consists of one atom. The number of atoms in the basis may vary from a single
atom to many atoms. For example in sodium and copper, the basis is single atom and in NaCl
and CsCl, the basis is diatomic.









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Unit Cell:


The atomic order in crystalline solids indicates that the small groups of atoms form a
repetitive pattern. Thus in describing crystal structures, it is often convenient to subdivide the
structure into small repeat entities called unit cells. A unit cell is chosen to represent the
symmetry of the crystal structure, where in all the atomic positions in the crystal may be
generated by translation of the unit cell integral distances along each of its edges. Thus the unit
cell is the basic building block of the crystal structure. Therefore unit cell is defined, as a unit
cell is the smallest geometric figure, the repetition of which in three dimensions will give the
actual crystal structure. Unit cell for most crystals are parallelepiped or cubes having three sets
of parallel faces. The choice of a unit cell is not unique but can be constructed in a number of
ways as shown in the figure. The unit cell should be chosen in such a way that it gives the
symmetry of crystal lattice.
The figure above shows a unit cell of a three-dimensional crystal lattice.

Lattice Parameters of a unit cell:

In order to define lattice parameters, we should first define axes. The crystallographic
axes are those lines drawn parallel to the lines of intersection of any three faces of the unit cell
which do not lie in the same plane. The angles between the three crystallographic axes are
known as interfacial angles and are denoted by o,| and . The intercepts a, b and c on
crystallographic axes
(x, y and z ) define the dimensions of unit cell and are known as primitives or characteristic
intercepts on the axes. These primitives and interfacial angles constitute the lattice parameters of
the unit cell. It is thus obvious that if the values of these intercepts and interfacial angles are
known, we can easily determine the form and actual size of the unit cell.

Primitive Cell: Primitive cell is defined as the unit cell that contains one lattice point only.









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Crystal Systems:

The lattice is made-up of a repetition of unit cells and a unit cell can be completely
described by the three vectors a

, b

and c

where the length of vectors and the angles between


them (o,|, ) are completely specified. The vectors a

, b

may or may not be equal. Also,


the angles , o,| and may or may not be right angles. Based on these conditions, there are seven
different crystal systems. If atoms exist only at the corners of the unit cells, the seven crystal
systems will yield seven types of lattices. These seven basic crystal systems are distinguished
from one another by the angles between the three axes and the intercepts of the faces along them.
The basic crystal structures are:

(1) Cubic system:

a = b = c and o = | = = 90
o

The crystal axes are perpendicular
to one another and repetitive interval
is the same along the three axes.
Examples: Au, Cu and NaCl




(2) Tetragonal system:

a = b = c and o = | = = 90
o

The crystal axes are perpendicular
to one another. The repetitive intervals
along the third axis is different.
Examples: TiO
2
, SnO
2
and NiSO
4




(3) Orthorhombic system:

a = b = c and o = | = = 90
o

The crystal axes are perpendicular
to one another, but the repetitive intervals
are different along all the three axes.
Examples: KNO
3
, BaSO
4
and PbCO
3








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(4) Monoclinic system:

a = b = c and o = = 90
o
= |
The crystal axes are perpendicular
to one another, but the third is
obliquely inclined. The repetitive
intervals are different along all
the three axes.
Examples: CaSO
4
.2H
2
O, FeSO
4
and Na
2
SO
4






(5) Triclinic system:

a = b = c and o = | = = 90
o

None of the crystal axes is perpendicular to any of
the other and repetitive intervals are different along
all the three axes.
Examples: K
2
Cr
2
O
7
and CuSO
4
.5H
2
O



(6) Trigonal (or Rhombohedral) system:

a = b = c and o = | = = 90
o

The three axes are equal in length
and are equally inclined to each other
at an angle other than 90
o
.
Examples: As, Sb, Bi and Calcite






(7) Hexagonal system:

a = b = c and o = | = 90
o
= 120
o

Two axes of the unit cell are equal
in length in one plane at 120
o

with each other and third axes
is perpendicular to this plane.
Examples: SiO
2
, Zn, Mg and Cd


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Bravais Lattices:

Space lattices can be classified according to their symmetry. In 1848, Bravais showed that
fourteen classes of lattices were sufficient in three dimensions. According to Bravais there are
fourteen types of space lattices in the seven systems of crystals, which are called Bravais
Lattices. The seven crystal systems and the fourteen lattices are tabulated in the table.


S.No. Crystal System Number of
lattices in the
system
Bravais lattice Unit Cell length
and interfacial
angles
1 Cubic 3 1. Simple
2. Body centered
3. Face centered
a = b = c
o = | = = 90
o


2 Tetragonal 2 1. Simple
2. Body centered
a = b = c
o = | = = 90
o

3 Orthorhombic 4 1. Simple
2. Base centered
3. Body centered
4. Face centered

a = b = c
o = | = = 90
o

4 Monoclinic 2 1. Simple
2. Base centered
a = b = c
o = | = 90
o

= 90
o

5 Triclinic 1 1. Simple a = b = c
o = | = = 90
o

6 Trigonal 1 1. Simple a = b = c
o = | = = 90
o

7 Hexagonal 1 1. Simple a = b = c
o = | = 90
o

= 120
o





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The 14 Bravais Lattices




Coordination number:

Coordination number is defined as the number of equi-distant nearest neighbors that an
atom has in the given structure.

Nearest neighbor distance:

The distance between the centers of two nearest neighboring atoms is called nearest
neighbor distance. It will be 2r if r is the radius of the atom

Atomic Packing Factors:

The fraction of the space occupied by atoms in a unit cell is known as atomic packing
factor. It is the ratio of the volume of the atoms occupying the unit cell to the volume of the unit
cell relating to that structure.



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Simple Cubic Structure (SC):

















Simple cubic structure is shown in the figure. In a simple cubic lattice there is one lattice point at
each of the eight corners of the unit cell. Each atom in this lattice is surrounded by six
equidistant nearest neighbors hence the coordination number is six. In this structure, eight unit
cells share each corner atom. Hence share of each corner atom to a unit cell is 1/8 of an atom.
Therefore the total number of atoms (or effective number of atoms) in one unit cell will be
8
1
x 8 = 1.


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Thus SC is a primitive cell. The atoms in this structure touch each other along the cube edge.
Hence nearest neighbor distance (2r) = a , where a is the side of the cube and r is radius of
atoms.

Volume of the atoms in unit cell v = t
3
4
r
3


Volume of unit cell V = a
3
= (2r)
3

Atomic packing factor for simple cubic (SC)
structure is =
3
3
4
r
v
3
(2 ) 6 V r
t
t
= = = 0.52 or 52%

Hence SC is a loosely packed structure. The element polonium at a certain temperature region
exhibits this structure.

Body centered Cubic Structure (BCC):



In this structure, a unit cell contains 8 atoms
at the eight corners and another atom at the body
center. Eight unit cells share each corner atom.
Therefore the number of atoms per unit cell in a
BCC structure is
(
8
1
x 8) + 1 = 2

The corner atoms dont touch each other, but each corner atom touches the body center atom
along body diagonal. Hence coordination number = 8.
The side of the cube is a and radius of atom is r. From the figure,
the nearest neighbor distance 2r = a
2
3


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Volume of all the atoms in a unit cell v = 2 x t
3
4
r
3

Volume of unit cell = a
3
= (
3
4r
)
3

Atomic packing factor =
3
3
4
2 r
v
3
4
3
V
r
t
=
| |
|
\ .
= 0.68 or 68%
Packing factor is 68%. Li, Na, K and Cr exhibit this structure.

Face centered Cubic Structure (FCC):


When atoms sit on lattice points, sometimes it is easier to see coordination geometries by
looking at lattice points rather than atoms.

In the case of FCC lattice, there are eight atoms at the eight corners of the unit cell and
six atoms at the centers of six faces shown in figure. The unit cell face is common to two unit
cells and there are twelve points surrounding it situated at a distance equal to half the face
diagonal of the unit cell. Thus coordination number of FCC is 12. Each of the six face centered
atoms is shared by two adjoining cubes. 8 surrounding unit cells share each of the corner atoms.
Total number of atoms per unit cell = ( 8
8
1
) + ( 6
2
1
)
From the figure (4r) = \2a
Nearest neighbor distance 2r = a
2
2


where r is radius of atom and a is side of the cube.
Volume of all the atoms in unit cell (v) = 4 x t
3
4
r
3

Volume of unit cell (V) = a
3

Atomic packing factor =

12


v
V
=
3
3
4
4
3
4
2
r
r
t
| |
|
\ .
= 0.74 or 74%

Therefore FCC is a close packed Structure. Copper, aluminum, lead and silver have this
structure.

Relationship between lattice constant and density of a crystal: (cubic only)

Let be the density of the material.
The volume of a unit cell for a cubic lattice is a
3
.
Hence mass of the unit cell = a
3
.

Let n be the number of atoms or molecules in a unit cell.
Mass of an atom or molecule =
A
N
M
; where M is the atomic or molecular weight and N
A
is
the Avogadro number.

A
N
nM
a =
3
or 3
A
N
nM
a

=
























13

CRYSTAL PLANES & DIRECTIONS

Crystal directions:



Miller indices:
The crystal lattice may be regarded as made-up of a large number of parallel equi-distant
planes, passing through the lattice points. These planes are known as lattice planes. Miller
evolved a method to designate a set of parallel planes in a crystal by three numbers (h, k, l),
known as Miller indices.

Determination of Miller indices:
The steps in the determination of Miller indices of a set of parallel planes are given
below:

Determine the coordinates of the intercepts made by the plane along the three crystallographic
axes
(x, y & z).
For example, a plane has intercepts 2a, 3b, c.
Express the intercepts as multiples of the unit cell dimensions or lattice parameters along the
axes.

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c
c
b
b
a
a
,
3
,
2

2, 3, 1
Determine the reciprocal of these numbers
1
1
,
3
1
,
2
1

Reduce these reciprocals to the smallest set of integral numbers by multiplying them with their
LCM and enclose them in bracket. (3, 2, 6).

In general Miller indices are denoted by ( h, k, l )

Thus, Miller indices may be defined as the reciprocals of the intercepts made by a plane on the
crystallographic axes when reduced to small numbers.
Miller indices have a ratio between them, which is the same as the ratio between the reciprocals
of the intercepts.

Important Features of Miller indices of Crystal Planes:

All the parallel equi-distant planes have the same Miller indices. Thus Miller indices define a set
of parallel planes.
A plane parallel to one of the coordinate axes has an intercept of infinity and a Miller index of
zero for that axis.
If the Miller indices of two planes have the same ratio ((8,4,4) and (4,2,2)), then the planes are
parallel to each other.
If a plane passes through the origin, it is defined in terms of a parallel plane having non-zero
intercept.



















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Important Crystal planes:





Inter-planar spacing between successive planes having
Miller indices (h,k,l): (cubic crystal only)




















Let (h, k, l) be the Miller indices of the plane ABC shown in the figure. The cube edge is
a. This plane belongs to a family of planes whose Miller indices are (h, k, l). Let OM = d
1
be
the perpendicular distance of the plane ABC from the origin. Let o

, |

and

be the angles
between the Coordinate axes x, y, z respectively and OM.
O
A
B
C
Q
R
P
M
N

16


The intercepts of the plane on the three axes are

l
a
OC
k
a
OB
h
a
OA = = = , ,
OM is normal to the plane ABC. From the figure we can write

1 1 1
' , ' , '
d d d
Cos Cos Cos
OA OB OC
o | = = =
From the direction Cosines relation we have

2 2 2
' ' ' 1 Cos Cos Cos o | + + =

1
2
2
1
2
2
1
2
2
1
= + +
OC
d
OB
d
OA
d

1
2
2 2
1
2
2 2
1
2
2 2
1
= + +
a
l d
a
k d
a
h d

| | 1
2 2 2
2
2
1
= + + l k h
a
d

2 2 2
2
2
1
l k h
a
d
+ +
=

2 2 2
1
l k h
a
d
+ +
=

Let ON = d
2
be the perpendicular distance of the next plane PQR parallel to the first plane ABC.
The intercepts of this plane on the three crystallographic axes are
2 2 2
, ,
a a a
OP OQ OR
h k l
= = =
and
2
2 2
" , " and "
d d d
Cos Cos Cos
OP OQ OR
o | = = =
From directional Cosines relation we have

2 " 2 2
" " 1 Cos Cos Cos o | + + =

2
2 2
2 2 2
1
d d d
OP OQ OR
| |
| | | |
+ + =
| | |
\ . \ .
\ .

1
2 2 2
2
2
2
2
2
2
= |
.
|

\
|
+ |
.
|

\
|
+ |
.
|

\
|
a
l d
a
k d
a
h d

( ) 1
2
2 2 2
2
2
= + + |
.
|

\
|
l k h
a
d


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2 2 2
2
l k h
a 2
d
+ +
=

Thus the inter planar Spacing (d) between two adjacent parallel planes of Miller indices (h k l) in
a cubic lattice is
d
hkl
= d
2
d
1

2 2 2
2a
h k l
=
+ +
2 2 2
a
h k l

+ +

2 2 2
hkl
a
d
h k l
=
+ +

This gives inter-planar spacing of planes whose Miller indices are (h k l).

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