Objectives

By the end of this section you should:

know how atom positions are denoted by
fractional coordinates
be able to calculate bond lengths for octahedral
and tetrahedral sites in a cube
be able to calculate the size of interstitial sites
in a cube
know what the packing fraction represents
be able to define and derive packing fractions
for 2 different packing regimes

Fractional coordinates
Used to locate atoms within unit cell
1.

0, 0, 0

2.

, , 0

3.

, 0,

4.

0, ,

Note 1: atoms are in contact along

face diagonals (close packed)
Note 2: all other positions
described by positions above (next
unit cell along)

Octahedral Sites

Coordinate , ,
Distance = a/2

Coordinate 0, , 0 [=1, , 0]
Distance = a/2

In a face centred cubic anion array, cation octahedral sites at:

,
0 0,
0 0, 0 0

Tetrahedral sites

Relation of a
tetrahedron to a cube:
i.e. a cube with alternate
corners missing and the
tetrahedral site at the
body centre

Can divide the f.c.c. unit cell into 8 minicubes by

bisecting each edge; in the centre of each minicube
is a tetrahedral site

So 8 tetrahedral sites in a fcc

Bond lengths
important dimensions in a cube

Face diagonal, fd
(fd) = (a2 + a2) = a 2

Body diagonal, bd
(bd) = (2a2 + a2) = a 3

Bond lengths:
Octahedral:
half cell edge, a/2
Tetrahedral:
quarter of body diagonal,
1/4 of a3
Anion-anion:
half face diagonal,
1/2 of a2

Sizes of interstitials
fcc / ccp
Spheres are in contact along
face diagonals
octahedral site, bond distance
= a/2
radius of octahedral site
= (a/2) - r
tetrahedral site, bond distance
= a3/4
radius of tetrahedral site
= (a3/4) - r

Summary
f.c.c./c.c.p anions
4 anions per unit cell at: 000

4 octahedral sites at:

00

00

00

4 tetrahedral T+ sites at:

4 tetrahedral T- sites at:

A variety of different structures form by occupying T+ Tand O sites to differing amounts: they can be empty, part
full or full.
We will look at some of these later.
Can also vary the anion stacking sequence - ccp or hcp

Packing Fraction
We (briefly) mentioned energy considerations in
relation to close packing (low energy configuration)
Rough estimate - C, N, O occupy 203
Can use this value to estimate unit cell contents
Useful to examine the efficiency of packing - take
c.c.p. (f.c.c.) as example

So the face of the unit

cell looks like:

Calculate unit cell side in

terms of r:
2a2 = (4r)2
a = 2r 2
Volume = (162) r3
Face centred cubic - so number of atoms per unit cell
=corners + face centres = (8 1/8) + (6 1/2) = 4

Packing fraction
The fraction of space which is occupied by atoms is
called the packing fraction, , for the structure
space occupied by atoms
=
available space

For cubic close packing:

4 3
r

3
4

074
.
3
16 2 r
3 2
The spheres have been packed together as closely as
possible, resulting in a packing fraction of 0.74

Group exercise:
Calculate the packing fraction for a primitive unit cell

Primitive

Close packing
Cubic close packing = f.c.c. has =0.74
Calculation (not done here) shows h.c.p. also has
=0.74 - equally efficient close packing
Primitive is much lower: Lots of space left over!
A calculation (try for next time) shows that body
centred cubic is in between the two values.
THINK ABOUT THIS! Look at the pictures - the
above values should make some physical sense!

Summary
By understanding the basic geometry of a
cube and use of Pythagoras theorem, we
can calculate the bond lengths in a fcc
structure
As a consequence, we can calculate the
radius of the interstitial sites
we can calculate the packing efficiency for
different packed structures
h.c.p and c.c.p are equally efficient packing
schemes