Chapter-2:

Solid state chemistry

Arrangements of atoms in 3D,

 close packing vs simple packing of spheres,

Packing of identical atoms in 2D

B B B B
C C C

Close (hexagonal) packing

Primitive (square) packing
Large holes, low space filling Small holes, high space filling

2
Primitive, Body center (BCC) Face center (FCC) unitcells
Packing efficiency:

Packing efficiency is the percentage of space occupied by

molecules  packed inside the lattice. It is the total of all the
molecular contribution.

Packing efficiency is in the order:

Cubic < BCC < FCC
 Sphere Packings: Closest Packings

Unit cell CN Atoms/unit cell % space filled

Simple cubic 6 1 52.36

Body centered cubic 8 2 68.02

Face centered cubic 12 4 74.04

(or ccp)

Hexagonal close 12 6 74.04

packed

6
Introduction of Miller indices (planes and directions) in cubic
system:
A lattice row defines a crystallographic direction.
A direction is represented in square brackets
In cubic system, [hkl] direction is always perpendicular to the (hkl) plane.

Direction in the unitcell is the vector connected by two coordinates the origin and
The final coordinate. It is used to denoted by [ ].
In the below example the direction [110] is shown with red arrow in FCC unitcell.
c

o
a
b
direction [110] is shown
with black arrow in BCC direction [111] is shown
unitcell with black arrow in BCC
unitcell
 Crystallographic planes

Crystallographic planes are defined purely from the shape and dimensions of
the unit cell.

The crystallographic plane may be represented by

hx + ky + lz = 1

The intercepts of the plane on X, Y, Z will be 1/h, 1/k, 1/l respectively.

h, k, l, are integers and are known as Miller indices.

A family of lattice planes is defined by a sequence of three integers,

and these are included within braces (curved brackets): (h k l).

The symbol is used to indicate set of planes that are equivalent.

Ex: (010), (100), (001) in cubic crystal are equivalent and represented as 100
 Miller planes:
Planes parallel to YZ-plane of the unit cell is (h00)
Planes parallel to XZ-plane of the unit cell is (0k0)
Planes parallel to XY-plane of the unit cell is (00l)
Miller plane connected by 2 or more coordinates in the unitcell.
It is used to denoted by ( ).
In the below example the plane (110) is shown with ACFD atoms in FCC.
c[001]

[100]
o a
[010]
b
(110) plane
(110) plane
Crystallographic planes parallel to X, Y and Z axis are defined by indices (0kl),
(h0l) and (hk0).
(100), (110), (111), (300), (-100), (012), (10-1), (10-2), (202) planes in a cube.

O
z
Position of various Miller planes:
y
x
𝒉 , 𝒌,𝒍 𝒉 ,𝒌,𝒍
𝒉 ,𝒌,𝒍 𝒉 ,𝒌,𝒍

𝒉.𝒌 ,𝒍 𝒉 ,𝒌,𝒍
𝒉 ,𝒌,𝒍 𝒉 ,𝒌,𝒍
 Hexagonal system

(000Ῑ) (10Ῑ0)
 Unit cell

A unit cell is the smallest repeating unit which shows the full
symmetry of the crystal.

The unit cell is a box

with:
• 3 sides - a, b, c
• 3 angles - , , 
 Unit cell
This is NOT a unit cell even though they are all the same -
empty space is not allowed!