Solid State Chemistry

A crystalline solid possesses rigid and long-range order. In a crystalline

solid, atoms, molecules or ions occupy specific (predictable) positions.

An amorphous solid does not possess a well-defined arrangement and

long-range molecular order.

A unit cell is the basic repeating structural unit of a crystalline solid.

lattice At lattice points:

point Atoms
Molecules
Ions

Unit Cell Unit cells in 3 dimensions

Lattice
BRAVAIS LATTICES
Shared by 8 unit Shared by 2 unit
cells cells
1 atom/unit cell 2 atoms/unit cell 4 atoms/unit cell
(8 x 1/8 = 1) (8 x 1/8 + 1 = 2) (8 x 1/8 + 6 x 1/2 = 4)
Types of Holes From Close-Packing of Spheres
Hexagonal Closest Packed (HCP) Cubic Closest Packed (CCP)
At room temperature crystal structures for
several elemental metals
Atomic Radius
Metal Crystal Structure
(nm)
Aluminum FCC 0.1431
Cadmium HCP 0.1490
Chromium BCC 0.1249
Cobalt HCP 0.1253
Copper FCC 0.1278
Gold FCC 0.1442
Iron (Alpha) BCC 0.1241
Lead FCC 0.1750
Magnesium HCP 0.1599
Molybdenum BCC 0.1363
Nickel FCC 0.1246
Platinum FCC 0.1387
Silver FCC 0.1445
Tantalum BCC 0.1430
Titanium (Alpha) HCP 0.1445
Tungsten BCC 0.1371
Zinc HCP 0.1332
 Crystallographic Planes
Miller Indices: Reciprocals of the (three)
axial intercepts for a plane, cleared of
fractions & common multiples. All
parallel planes have same Miller indices.

Algorithm
1. Read off intercepts of plane with axes in
terms of a, b, c
2. Take reciprocals of intercepts
3.Reduce to smallest integer values
4.Enclose in parentheses, no
commas i.e., (hkl)

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 Crystallographic Planes
z

example a b c c
1. Intercepts 1 1
2. Reciprocals 1/1 1/1 1/
1 1 0
y
3. Reduction 1 1 0
a b
4. Miller Indices (110) x
z
example a b c
1. Intercepts 1/2 c
2. Reciprocals 1/ 1/ 1/
2 0 0
3. Reduction 2 0 0 y
4. Miller Indices (100) a b

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 Crystallographic Planes
z

example a b c
c
1. Intercepts 1/2 1 3/4
2. Reciprocals 1/ 1/1 1/
2 1 4/3 y
b
3. Reduction 6 3 4 a

x
4. Miller Indices (634)

Family of Planes {hkl}

Ex: {100} = (100), (010), (001), (100), (010), (001)

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Crystallographic Planes

29
 X-Ray
z
Diffraction
z
Pattern
z
c c c

y (110) y y
a b a b a b
Intensity (relative)

x x x
(211)

(200)

Diffraction angle 2
Diffraction pattern for polycrystalline -iron (BCC)
Adapted from Fig. 3.22, Callister 8e.

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 X-Rays to Determine Crystal Structure
Incoming X-rays diffract from crystal planes.
de
te
ct
or

1
in ray
co s
ys
X- reflections must

m
ra be in phase for
X-
in

2
g
a detectable signal

1
ng

extra
o i
2
g Adapted from Fig. 3.20,
distance
ut

o Callister & Rethwisch 8e.
travelled
by wave 2 spacing
d between
planes

Measurement of X-ray
n
critical angle, c, intensity d
(from 2 sin c
allows computation of
detector)
planar spacing, d.

c
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 Why Is Symmetry
Important?
Identification of Materials
Prediction of Atomic Structure
Relation to Physical Properties
Optical
Mechanical
Electrical and Magnetic
 CRYSTAL SYMMETRY

Crystals have inherent symmetry.

The definite ordered arrangement of the faces
and edges of a crystal is known as `crystal
symmetry.
It is a powerful tool for the study of the internal
structure of crystals.
Crystals possess different symmetries or
symmetry elements.
 CRYSTAL SYMMETRY

The seven crystal systems are characterised by

three symmetry elements. They are

Centre of symmetry

Planes of symmetry

Axes of symmetry.
 PLANE OF SYMMETRY

A crystal is said to have a plane of symmetry, when

it is divided by an imaginary plane into two halves,
such that one is the mirror image of the other.

In the case of a cube, there are three planes of

symmetry parallel to the faces of the cube and six
diagonal planes of symmetry
 AXIS OF SYMMETRY

This is an axis passing through the crystal such that if

the crystal is rotated around it through some angle,
the crystal remains invariant.
The axis is called `n-fold, axis if the angle of rotation
is .

If equivalent configuration occurs after rotation of

180, 120 and 90, the axes of rotation are known as
two-fold, three-fold and four-fold axes of symmetry
respectively.
 If equivalent configuration occurs after rotation of 180,
120 and 90, the axes of rotation are known as two-
fold, three-fold and four-fold axes of symmetry .
If a cube is rotated through 90, about an axis normal to
one of its faces at its mid point, it brings the cube into
self coincident position.
Hence during one complete rotation about this axis, i.e.,
through 360, at four positions the cube is coincident
with its original position.Such an axis is called four-fold
axes of symmetry or tetrad axis.
 If n=1, the crystal has to be rotated through an angle =
360, about an axis to achieve self coincidence. Such an
axis is called an `identity axis. Each crystal possesses an
infinite number of such axes.

If n=2, the crystal has to be rotated through an angle =

180 about an axis to achieve self coincidence. Such an
axis is called a `diad axis.Since there are 12 such edges in
a cube, the number of diad axes is six.
 If n=3, the crystal has to be rotated through an
angle = 120 about an axis to achieve self
coincidence. Such an axis is called is `triad
axis. In a cube, the axis passing through a
solid diagonal acts as a triad axis. Since there
are 4 solid diagonals in a cube, the number of
triad axis is four.
If n=4, for every 90 rotation, coincidence is
achieved and the axis is termed `tetrad axis.
It is discussed already that a cube has `three
tetrad axes.
 If n=6, the corresponding angle of rotation is
60 and the axis of rotation is called a hexad
axis. A cubic crystal does not possess any
hexad axis.

Crystalline solids do not show 5-fold axis of

symmetry or any other symmetry axis higher
than `six, Identical repetition of an unit can take
place only when we consider 1,2,3,4 and 6 fold
axes.
 CENTRE OF SYMMETRY
It is a point such that any line drawn through it will
meet the surface of the crystal at equal distances
on either side.
Since centre lies at equal distances from various
symmetrical positions it is also known as `centre
of inversions.
It is equivalent to reflection through a point.
A Crystal may possess a number of planes or
axes of symmetry but it can have only one centre
of symmetry.
For an unit cell of cubic lattice, the point at the
body centre represents the `centre of
symmetry and it is shown in the figure.
 SYMMETRICAL ELEMENTS OF CUBE

(a) Centre of symmetry 1

(b) Planes of symmetry 9
(Straight planes -3,Diagonal planes -6)
(c) Diad axes 6
(d) Triad axes 4
(e) Tetrad axes 3
----
Total number of symmetry elements = 23
----
Thus the total number of symmetry elements of a cubic structure is
23.
 ABSENCE OF 5 FOLD SYMMETRY

We have seen earlier that the crystalline solids show only

1,2,3,4 and 6-fold axes of symmetry and not 5-fold axis of
symmetry or symmetry axis higher than 6.
The reason is that, a crystal is a one in which the atoms or
molecules are internally arranged in a very regular and
periodic fashion in a three dimensional pattern, and
identical repetition of an unit cell can take place only
when we consider 1,2,3,4 and 6-fold axes.
 COMBINATION OF SYMMETRY
ELEMENTS

Apart from the different symmetry elements different

combinations of the basic symmetry elements are also
possible.
They give rise to different symmetry points in the
crystal.

The combination of symmetry elements at a point is

called a `point group.