Week 2-3 Lectures:

Crystalline Solids
• E.g. diamond, graphite
• Regular shape i.e. fixed geometric patterns
• Incompressible
• Definite /specific boiling points
• Diffract X-rays

1
Atomic arrangements in materials

2
3
Crystals are everywhere!
Unit Cells
• While there are several types of unit cells, we are going to be
primarily interested in 3 specific types.
• Cubic
• Body-centered cubic
• Face-centered cubic
Definitions
1. The unit cell

“The smallest repeat unit of a crystal structure, in 3D,

which shows the full symmetry of the structure”

The unit cell is a

box with:
• 3 sides - a, b, c
• 3 angles - , , 
 Seven unit cell shapes

• Cubic a=b=c ===90°

• Tetragonal a=bc ===90°
• Orthorhombic abc ===90°
• Monoclinic abc ==90°,   90°
• Triclinic abc     90°
• Hexagonal a=bc ==90°, =120°
• Rhombohedral a=b=c ==90°

Think about the shapes that these define - look at the

models provided.
Shared by 8 Shared by 2
unit cells unit 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)
 lattice points

2D example - rocksalt
(sodium chloride, NaCl)

We define lattice points ; these are points

with identical environments
Choice of origin is arbitrary - lattice points need not be atoms - but
unit cell size should always be the same
This is also a unit cell -
it doesn’t matter if you start from Na or Cl
- or if you don’t start from an atom
This is NOT a unit cell even though they are all the same - empty
space is not allowed!
In 2D, this IS a unit cell
In 3D, it is NOT
Summary

 Unit cells must link up - cannot have

gaps between adjacent cells
 All unit cells must be identical
 Unit cells must show the full symmetry
of the structure
The “Hard Sphere Model” and Ionic Radii

Form X-ray crystallography we obtain inter-nuclear

distances.

Convenient to consider these distances as the sum

of two contributions

i.e. the ionic radii of the two ions, r+ and r-.

r+ r-

Internuclear
separation

21
Assume that ions in ionic solids are hard incompressible
spheres of precise and well-defined radius.

Is this a reasonable assumption?

When there are significant covalent interactions the

assumption is less valid.

In general the assumption works well enough to be useful.

22
How do we split up a given inter-nuclear distance
into r+ and r- contributions?

Several different procedures

e.g. the Pauling scale and the Goldschmidt scale.

They differ slightly but generally are in fair

agreement.

23
Given the assumptions and approximations with the
hard sphere model, why use it ???

The hard sphere model provides a very useful way of

classifying and describing a large number of
structures.

Note that ionic radii “change” depending upon the

coordination number.

24
Ion sizes Li+ Be2+
in pm O2- F-
60 31
140 136
Na+ Mg2+ Al3+
S2- Cl-
95 65 50
184 181
K+ Ca2+ Ga3+
Se2- Br-
133 99 62 198 195
Rb+ Sr2+ In3+ Sn4+ Sb5+
Te2- I-
148 113 81 71 62
221 216

From Zumdahl, Chemistry 6th ed.

25
Radius Ratios, r+/r-

Generally (not always) anions are bigger than cations.

Therefore ionic structures are often described in terms of
the packing arrangement of anions.
The smaller cations fill interstitial sites (holes).

With “large” cations (r+/r- approx. 1) the cations tend to

adopt coordination number (C.N.) 8.

With “small” cations and larger anions (r+/r- < about 0.4)
the cations tend to adopt C.N. 4.

Cations of “intermediate” size tend to adopt C.N. 6.

26
 Geometrical calculation using the strict hard sphere
model leads to the prediction of the coordination
number of simple salts based on the radius of cations
and anions as follow:-
r+/r- > 0.73 gives C.N. 8
r+/r- < 0.41 gives C.N. 4
0.73 > r+/r- > 0.41 gives C.N. 6

In view of he hard sphere model (r+/r-) calculate the coordination number of the
following solids
(i) 60LiI216 Ratio = 0.27 CN = 4
(ii) 148RbF136 Ratio = 1.088 CN = 8
(iii)113SrCl2181 Ratio = 0.624 CN = 6

27
Lecture
Close packing of spheres
- hexagonal close packing
- cubic close packing (FCC)
- interstitial sites
Non-close packing of spheres
- simple cubic
- body-centred cubic
Carbon allotropes
- Diamond
- Graphite
- Fullerenes

28
Close Packing of Spheres

Everyday examples:
Fruit stand - apples, oranges etc.
Bag of marbles
Triangle of reds on snooker table

A layer of close-packed
spheres.

Note there are 2

“depressions” for each
sphere on each side of
the layer.
29
 When considering close packed spheres it is easier to visualise the
packing if the spheres are not touching.

A single layer of spheres. 2 layers of spheres.

Note in the representation of the double layer that only one half of the
depressions formed by the red spheres are occupied by black spheres.

30
 Red spheres: A layer
Black spheres: B layer

3rd layer stacking directly above

1st layer ABA stacking.

The 3rd layer can stack directly

above the first layer (ABA
stacking) or offset from both the
red and black layers (ABC
stacking).

31
Hexagonal Close Packing

If the 3rd layer stacks above the 1st and the 4th above
the 2nd and this process is continued then we have
ABABABAB… stacking.

This is known as hexagonal close packing (HCP).

32
Alternative representations of HCP

A A

B B

A A

Hexagonal Close Packing

33
Cubic Close Packing

If the 3rd layer is offset from both the red layer and the
black layer and this stacking sequence is continued then we
have ABCABCABC… stacking.

This is known as cubic close packing (CCP).

Red spheres - A layer

Black spheres - B layer
Yellow spheres -C layer

Cubic close packing is also known as face-centred cubic (FCC).

34
Alternative representations of CCP (FCC)

3-fold axis 3-fold axis

A

Note that the close packed hexagonal layers are stacked normal to
the cube solid diagonal.

Cubic close packing (face-centred cubic)

35
In both arrangements (CCP and HCP) the spheres occupy 74 % of the
volume of the structure.

Arrangements of the 12 nearest neighbours about one packing atom for

CCP and HCP:

CCP HCP

36
Two types of interstitial sites (holes) are formed between the 2 layers:

Octahedral sites - Sites surrounded by six spheres arranged at the

corners of an octahedron.

Tetrahedral sites - Sites surrounded by four spheres arranged at the

corners of a tetrahedron.

37
In both HCP and CCP there are 6 octahedral sites around each sphere and
6 spheres around each octahedral site.

The ratio of octahedral sites to spheres is therefore 1:1.

In both HCP and CCP there are 8 tetrahedral sites around each sphere
and 4 spheres around each tetrahedral site.

The ratio of tetrahedral sites to spheres is therefore 2:1.

Each sphere has 6 octahedral sites and 8 tetrahedral sites around it.

38
An octahedral site is considerably larger than a tetrahedral site and
both are much smaller than the spheres.

For tetrahedral sites: r/R = 0.225

where
R = radius of close packed sphere
r = radius of largest sphere which can fit into the tetrahedral site.

For octahedral sites: r/R = 0.414

where
R = radius of close packed sphere
r = radius of largest sphere which can fit into the octahedral site.

39
 Consider the
octahedral sites in A
HCP

B
Octahedral sites:
green spheres
A
Spheres:oct sites 1:1

Note that the octahedral sites appear in vertical columns,

perpendicular to the sheets.

Each octahedral site “shares” a triangular face with the

neighbouring octahedral site above and with the site below.

NOTE: Trigonal prismatic arrangement of octahedral sites

around spheres.
40
 Consider the tetrahedral sites in HCP

A A

B B

A A

Spheres:tetrahedral sites 1:2

There are downward-pointing tetrahedral sites shown in the left

diagram and upward-pointing tetrahedral sites shown in the right.

41
 Consider the octahedral sites in CCP:

Easier to consider from

“FCC” perspective.

Remember ABCABC…
stacking sequence
occurs along a body
diagonal.

The yellow spheres represent octahedral sites.

4 spheres and 4 octahedral sites per unit cell i.e. 1:1 ratio.

Note: Octahedral sites form a FCC lattice.

- Different to HCP.

42
 Consider the tetrahedral sites in CCP:

Note: 4 spheres and 8

tetrahedral sites per unit cell
i.e. 1:2 ratio.

Yellow spheres - tetrahedral sites.

Yellow spheres form a simple cubic lattice.

43
Summary of close packing

Spheres occupy 74% of volume.

Oct sites : spheres Tet sites : spheres

1:1 2:1

HCP CCP
ABABAB… stacking ABCABC… stacking

Oct sites form trigonal Oct sites form octahedral

prismatic geometry geometry about each
about each sphere sphere

44
Lecture 4: Simple Cubic
Spheres arranged at the vertices of a cube.
Each sphere makes contact with six other spheres.

The interstitial sites are cubic with

8 spheres around each site and 8
sites around each sphere.

r/R = 0.732.

The spheres (when touching)

occupy 52.4 % of the volume of
the structure.

45
Body-Centred Cubic

Spheres are arranged at the vertices AND at the centre of a cube.

This is denser than simple cubic packing but not as

dense as HCP and CCP – the spheres occupy 68
% of the volume of the structure.

Can be derived from 2 interpenetrating simple

cubic lattices.

The energies of the CCP, HCP and BCC alternatives often differ by very little.

CCP and HCP pack with equal efficiency. BCC is 92% as dense as the others.

In HCP and CCP each atom has 12 nearest neighbours.

In BCC there are only 8 nearest neighbours but the next 6 are only 15 % further away.
46
Carbon Allotropes

Carbon has many allotropic forms - many discovered recently.

Infinite 2D and 3D structures, in addition to finite structures.

The bonding in each allotropic form is dominated by covalent

interactions.

Although covalent interactions are directional, sphere packing models

can be a useful aid in describing the structure.
Diamond*
Diamond has a cubic structure which may be simply related to the CCP
arrangement.

(Note difference between CCP and CCP arrangement.)

Carbon atoms at the corners and midpoint of faces of a cube.

Fill every second tetrahedral site of the cube with a carbon atom.

Every other octant of the cube is vacant.

47
Diamond*
Diamond has a cubic structure which may be simply related to the CCP
arrangement.

(Note difference between CCP and CCP arrangement.)

Carbon atoms at the corners and midpoint of faces of a cube.

Fill every second tetrahedral site of the cube with a carbon atom.

Every other octant of the cube is vacant.

48
Face-centred cubic
arrangement of carbon
atoms with every 2nd
tetrahedral site occupied by
an equivalent C atom.

C atoms in “tetrahedral sites”

are highlighted in blue.

49
 In diamond all C atoms are
The extended diamond network equivalent and all bonds are
equivalent.

If tetrahedral centres are

connected by staggered bonds
then the diamond structure will
result.

50
This highly symmetrical and dense structure makes diamond one of the
hardest materials known.

It has a high density and a high refractive index.

Apparent in the structure of diamond is an adamantane-type unit.

Adamantane is a
hydrocarbon and has the
formula C10H16.

51
Diamonds are often described as being brilliant.
• The refractive index of a diamond
is 2.42.
• This compares to a value of 1.52
for glass (1.0 for air).

• Diamonds are extremely hard.

• The hardness of diamond makes them
extremely valuable in industry for:
- cutting
- drilling
- grinding
- polishing
52
Lecture :
Graphite*
2-dimensional hexagonal grid structure.

Each carbon forms a -bond with its 3 neighbours.

The remaining electron on each carbon becomes part of a

delocalised  system

All C-C distances are equal.

A “stick” representation
of part of the 2D
structure of graphite.

53
The C-C bonds (1.415 Å) are a little longer than they are
in benzene which is consistent with the assumed bond
order of 1.333.
No carbon atom is directly
above another in adjacent
layers.

Most common type of

stacking is ABABAB
although ABCABC stacking
is also known.

The separation between

sheets is 3.35 Å.
54
It is possible to place molecules or ions between the
layers; this is known as intercalation.

Intercalation is possible because of the weak attraction

between layers.

The weak attraction between layers also means that the

2D sheets can slide past each other.

This is the reason that graphite has a “greasy” feel to it.

Graphite is used as a dry lubricant.

55
Intercalation of alkali metals into graphite

Addition of K to graphite produces a paramagnetic copper-

coloured compound, K+[C8]-

Structural changes
K+ lies in between sheets.
The staggered sheets become eclipsed.
Interlayer separation increased from 3.35 to 5.40 Å.

Electrical conductivity is significantly enhanced with

additional electrons added to the delocalised system.

56
Alkali metal intercalates are highly reactive
- ignite in air
- explode on contact with water

It is possible to substitute K+ with d-block metal ions such as Mn(II), Fe(III) and
Cu(II) by reacting with metal chlorides to form species such as MnC16, FeC24,
CuC16.

Heating KC8 leads to as series of decomposition products in which the metal is lost
in sequential steps.

KC8 KC24 KC36 KC48 KC60

   

57
Intercalation of anions can also occur.

Compounds of the type [C24]+[HSO4]-.24H2O can be formed when

graphite is treated with conc. H2SO4 and a little HNO3 and CrO3.

The oxidation of the graphite sheet results in enhanced electrical

conductivity.

Other intercalation compounds can be formed with Cl2, Br2 and ICl.

Some of the intercalation compounds are useful catalysts e.g. KC8 is a

hydrogenation catalyst.

58
Other allotropes of carbon are also known.

For example: C60 - buckminsterfullerene.

A soccer ball form of carbon.

Note that all C atoms are identical and

trigonal.

The structure resembles the geodesic

domes designed by the American
architect Buckminster Fuller.

59
 The soot from pure graphite electrodes in a helium atmosphere contains
significant quantities of fullerenes.

It may be separated from graphite because it is soluble in organic solvents

like toluene.

In the solid state C60 molecules pack in a CCP

arrangement !

There are a number of derivatives of C60.

C60F60 is also known.

K3C60 is superconducting below 18 K.

http://sbchem.sunysb.edu/msl/fullerene.html

60
There are a number of analogues of C60 with different
number of C atoms such as C70, C84, C90, C94 and C540.

They represent the general class of molecules known

as the fullerenes.
C70 C540

http://sbchem.sunysb.edu/msl/fullerene.html
http://en.wikipedia.org/wiki/Fullerene

61
Related to these molecules are the carbon nanotubes

Cylindrical carbon
molecules of the
fullerene family,
with at least one
end typically capped.

http://www.personal.rdg.ac.uk/~scsharip/tubes.htm

62
Two distinct groups of carbon nanotubes

Single-walled nanotubes (SWNT)

Diameter~ 1nm
Excellent conductors (in theory 1000 times > Cu)
Tensile strength (directional) measured at 63 GPa
(c.f. steel 1.2GPa)
Directional thermal conductors
Expensive

Multi-walled nanotubes (MWNT)

Insulators

63
http://nanoengineeringmedical.asmedigitalcollection.asme.org/article.aspx?articleid=1452169
The allotropes of carbon exhibit remarkable
structural diversity.

Tetrahedral carbon atoms (sp3) lead to infinite 3D structures.

Trigonal carbon atoms (sp2) lead to 2D graphite or fullerene related structures.

64
 Lecture

MILLER INDICES
PROCEDURE FOR FINDING MILLER INDICES
DETERMINATION OF MILLER INDICES
IMPORTANT FEATURES OF MILLER INDICES
CRYSTAL DIRECTIONS
SEPARATION BETWEEN LATTICE PLANES

65
 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.

66
 MILLER INDICES

DIFFERENT LATTICE PLANES

PH 0101 UNIT 4 LECTURE 2 67

 MILLER INDICES
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.

68
 MILLER INDICES

Procedure for finding Miller Indices

Step 1: Determine the intercepts of the plane along the axes

X,Y and Z in terms of the lattice constants a, b and c.

Step 2: Determine the reciprocals of these numbers.

Step 3: Find the least common denominator (lcd)

and multiply each by this lcd.
Step 4:The result is written in parenthesis.
This is called the `Miller Indices’ of the plane in the
form (h k l)
69
 ILLUSTRATION

PLANES IN A CRYSTAL

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

units along Y-axis and 2 units along Z-axis.

70
 ILLUSTRATION

DETERMINATION OF ‘MILLER INDICES’

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)

71
 MILLER INDICES

IMPORTANT FEATURES OF MILLER INDICES

For the cubic crystal especially, the important features of Miller

indices are,

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.

72
Examples

Plane parallel to Y and Z axes

( 1 0 0 ) plane

In the above plane, the intercept along X axis is 1 unit.

The plane is parallel to Y and Z axes. So, the intercepts

along Y and Z axes are ‘’.
Now the intercepts are 1,  and .
The reciprocals of the intercepts are = 1/1, 1/ and 1/.
Therefore the Miller indices for the above plane is (1 0 0).

73
 MILLER INDICES

IMPORTANT FEATURES OF MILLER INDICES

A plane passing through the origin is defined in terms of a

parallel plane having non zero intercepts.

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.

74
 MILLER INDICES

IMPORTANT FEATURES OF MILLER INDICES

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.

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.

75
MILLER INDICES OF SOME IMPORTANT PLANES

76
 PROBLEMS

Worked Example:
A certain crystal has lattice parameters of 4.24, 10 and 3.66 Å on X, Y, Z
axes respectively. Determine the Miller indices of a plane having
intercepts of 2.12, 10 and 1.83 Å on the X, Y and Z axes.
Lattice parameters are = 4.24, 10 and 3.66 Å
The intercepts of the given plane = 2.12, 10 and 1.83 Å
i.e. The intercepts are, 0.5, 1 and 0.5.
Step 1: The Intercepts are 1/2, 1 and 1/2.
Step 2: The reciprocals are 2, 1 and 2.
Step 3: The least common denominator is 2.
Step 4: Multiplying the lcd by each reciprocal we get, 4, 2 and 4.
Step 5: By writing them in parenthesis we get (4 2 4)

Therefore the Miller indices of the given plane is (4 2 4) or (2 1 2).

77
 PROBLEMS

Worked Example:
Calculate the miller indices for the plane with intercepts 2a,
- 3b and 4c the along the crystallographic axes.

The intercepts are 2, - 3 and 4

Step 1: The intercepts are 2, -3 and 4 along the 3 axes

1 1 1
Step 2: The reciprocals are , and
2 3 4

Step 3: The least common denominator is 12.

Multiplying each reciprocal by lcd, we get 6 -4 and 3

Step 4: Hence the Miller indices for the plane is  6 4 3

78
 Lecture 11_Crystallographic Planes
example a b c z
1. Intercepts 1 1 
1/1 1/1 1/
c
2. Reciprocals
1 1 0
3. Reduction 1 1 0 y
4. Miller Indices (110)
a b
x
z
example a b c
1. Intercepts 1/2   c
2. Reciprocals 1/½ 1/ 1/
2 0 0
3. Reduction 2 0 0
y
4. Miller Indices (200) a b
x
Crystallographic Planes
example a b c
1. Intercepts 1/2 1 3/4
2. Reciprocals 1/½ 1/1 1/¾
2 1 4/3 z
3. Reduction 6 3 4
c

4. Miller Indices (634)

 y
a b
x

80
 CRYSTAL DIRECTIONS

In crystal analysis, it is essential to indicate certain

directions inside the crystal.
A direction, in general may be represented in terms of
three axes with reference to the origin.In crystal system,
the line joining the origin and a lattice point represents
the direction of the lattice point.

81
 CRYSTAL DIRECTIONS

To find the Miller indices of a direction,

Choose a perpendicular plane to that direction.

Find the Miller indices of that perpendicular plane.

The perpendicular plane and the direction have

the same Miller indices value.

Therefore, the Miller indices of the perpendicular

plane is written within a square bracket to
represent the Miller indices of the direction like [ ].
82
IMPORTANT DIRECTIONS IN CRYSTAL

83
 Atom Positions in Cubic Unit Cells

• Cartesian coordinate system is use to locate atoms.

• In a cubic unit cell
 y axis is the direction to the right.
 x axis is the direction coming out of the paper.
 z axis is the direction towards top.
 Negative directions are to the opposite of positive directions.

• Atom positions are

located using unit
distances along the
axes.
 Directions in Cubic Unit Cells
• In cubic crystals, Direction Indices are vector components of directions resolved
along each axes, resolved to smallest integers.
• Direction indices are position coordinates of unit cell where the direction
vector emerges from cell surface, converted to integers.

Figure 3.11

3-16
 Direction Indices - Example

• Determine direction indices of the given vector.

Origin coordinates are (3/4 , 0 , 1/4).
Emergence coordinates are (1/4, 1/2, 1/2).

Subtracting origin coordinates

from emergence coordinates,
(1/4, 1/2, 1/2)-(3/4 , 0 , 1/4)
= (-1/2, 1/2, 1/4)
Multiply by 4 to convert all
fractions to integers
4 x (-1/2, 1/2, 1/4) = (-2, 2, 1)
Therefore, the direction indices are [ 2 2 1 ]
 DESIRABLE FEATURES OF MILLER INDICES

The angle ‘’ between any two crystallographic directions

[u1 v1 w1] and [u2 v2 w2] can be calculated easily. The
angle ‘’ is given by,
u1 u 2  v1 v 2  w1 w 2
cos 
(u12  v12  w12 )1/ 2 (u 22  v 22  w 22 )1/ 2

The direction [h k l] is perpendicular to the plane (h k l)

87
 DESIRABLE FEATURES OF MILLER INDICES

The relation between the interplanar distance and the

interatomic distance is given by,

for cubic
a crystal.
d 
h 2  k 2  l2

If (h k l) is the Miller indices of a crystal plane then the

intercepts made by the plane with the crystallographic
axes are given as a b c
, and
h k l
where a, b and c are the primitives.
88
 PROBLEMS

Worked Example
Find the angle between the directions [2 1 1] and [1 1 2] in a cubic
crystal.

The two directions are [2 1 1] and [1 1 2]

We know that the angle between the two directions,

u1 u 2  v1 v 2  w1 w 2
cos  
(u12  v12  w12 )½  (u 22  v 22  w 22 )½

89
 PROBLEMS

In this case, u1 = 2, v1 = 1, w1 = 1, u2 = 1, v2 = 1, w2 = 2

(2  1)  (1  1)  (1  2) 5
 cos   
22  12  l2  12  12  22 6

(or) cos  = 0.833

 = 35° 3530.

90
 SEPARATION BETWEEN LATTICE PLANES

Consider a cubic crystal of side ‘a’, and a

plane ABC.
This plane belongs to a family of planes
whose Miller indices are (h k l) because
Miller indices represent a set of planes.
Let ON =d, be the perpendicular distance of
the plane A B C from the origin.

91
SEPARATION BETWEEN LATTICE PLANES

PH 0101 UNIT 4 LECTURE 2 92

 SEPARATION BETWEEN LATTICE PLANES

• 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

(6) a
d   d 2  d1  
h 2  k 2  l2

93
 PROBLEMS

Worked Example

The lattice constant for a unit cell of aluminum is 4.031Å

Calculate the interplanar space of (2 1 1) plane.

a = 4.031 Å
(h k l) = (2 1 1)
a 4.031  1010
Interplanar spacing d 
h 2  k 2  l2 2 2  12  12
 d = 1.6456 Å or 1.65 x 10-10 (m)

94
 PROBLEMS
Worked Example:
Find the perpendicular distance between the two planes indicated by
the Miller indices (1 2 1) and (2 1 2) in a unit cell of a cubic lattice with a
lattice constant parameter ‘a’.
We know the perpendicular distance between the origin and the plane is (1 2 1)
a a a
d1   
h12  k12  l12 12  22  12 6
and the perpendicular distance between the origin and the plane (2 1 2),
a a a a
d2    
h 2
2 k 2
2  l 2
2 2 2
 1 2
 2 2
9 3

The perpendicular distance between the planes (1 2 1) and (2 1 2) are,

a a 3a  6a a(3  6)
d = d1 – d2 =    d = 0.0749 a
6 3 3 6 3 6

95
X-ray Production
 X-radiation
X-rays are part of the electromagnetic spectrum. X-radiation
(composed of X-rays) is a form of electromagnetic radiation. X-
rays have a wavelength in the range of 10 to 0.01 nanometers,
corresponding to frequencies in the range 3 × 10 16 Hz to 3 × 1019
Hz and energies in the range 120 eV to 120 keV. They are
shorter in wavelength than UV rays and longer than gamma
rays. In many languages, X-radiation is called Röntgen
radiation, after Wilhelm Conrad Röntgen, who is generally
credited as their discoverer.
X-rays from about 0.12 to 12 keV (10 to 0.10 nm wavelength)
are classified as "soft" X-rays, and from about 12 to 120 keV
(0.10 to 0.010 nm wavelength) as "hard" X-rays, due to their
penetrating abilities.
X-rays are a form of ionizing radiation, and exposure to them
can be a health hazard.
Electromagnetic spectrum
Electromagnetic spectrum
 Anode Cathode

kVp KINETIC ENERGY OF ELECTRONS

CATHODE --------

MADE OF TUNGSTEN + 1%-3% THORIUM

TUNGSTEN

Z # 74

MELTING POINT- 3,410 DEG. CELSIUS

X-RAY PRODUCTION
• BREMSSTRAHLUNG RADIATION

• CHARACTERISTIC RADIATION
Bremsstrahlung and characteristic X-rays
• There are two different atomic processes that can produce X-ray photons.
• One is called Bremsstrahlung and is a German term meaning "braking
radiation“.

• The other is called characteristic X-rays (K-shell emission).

• They can both occur in the heavy atoms of tungsten.
• Tungsten is often the material chosen for the target or anode of the x-ray
tube.
 BREMSSTRAHLUNG
RADIATION
If an incoming free electron gets close to the nucleus of a target
atom, the strong electric field of the nucleus will attract the electron,
thus changing direction and speed of the electron.

The Electron looses energy which will be emitted as an X-ray

photon. The energy of this photon will depend on the degree of
interaction between nucleus and electron, i.e. the passing distance.

X-rays originating from this process are called bremsstrahlung.

Bemsstrahlung is a German word directly describing the process:
"Strahlung" means "radiation", and "Bremse" means "brake
Bremsstrahlung Radiation
BREMS
DIFFERENT DEGREES OF
DECCELERATION
X-RAYS

HEAT
Characteristic X-rays
• The high energy electron can also cause an electron close to
the nucleus in a metal atom to be knocked out from its place.
• This vacancy is filled by an electron further out from the
nucleus. The well defined difference in binding energy,
characteristic of the material, is emitted as a monoenergetic
photon.
• When detected this X-ray photon gives rise to a characteristic
X-ray line in the energy spectrum.
Characteristic Radiation

KE OF PROJECTILE ELECTRON > BINDING ENERGYORBITAL ELECTRON

CHARACTERISTIC CASCADE
TUNGSTEN-74
BINDING ENERGIES
OF DIFFERENT SHELL ELECTRONS

K-70 KEV
L-12 KEV
M-2.8 KEV
CHARACTERISTIC X-RAYS

L K
70-12 = 58 keV

M K 70-3 = 67 keV

M
L 12-3 = 9 keV
TRANSFER OF ELECTRONS
BETWEEN OUTER SHELLS
RESULTS IN:

HEAT PRODUCTION !
X-RAYS PRODUCTION AN INEFFICIENT
PROCESS
80 KVP

99.4% HEAT 0.6% X-RAYS

% EFFICIENCY= K * Z * kVp

K = 1 * 10-4
X-ray Continuum and Characteristic radiation spectra
Characteristic vs. Bremsstrahlung X-rays

• Characteristic X-ray require 70 kVp or higher.

Based upon the energy of the k-shell electron.
• Bremsstrahlung X-rays can be produced at any
projectile electron energy. In diagnostic
radiography most of the x-rays are
bremsstrahlung x-rays.
X-ray Emission Spectrum
• If a relative number of x-ray photons were plotted as a function of
their energies we can analyze the x-ray emission spectrum.
• Understanding the x-ray emission spectra is key to understanding how
changes in kVp, mA, time and filtration affects the optical density and
contrast of the radiograph.
Discrete X-ray Spectrum
• Characteristic x-rays have a precisely fixed or discrete energies.
• These energies are characteristic of the differences between electron
binding energies of a particular element.
• For tungsten you can have one of 15 energies .
Discrete X-ray Spectrum
• There are 15 energies
• There are 5 vertical line
representing K x-rays.
• 4 representing L x-rays.
• Remaining represent
lower energy outer shell
electrons.
Discrete X-ray Spectrum
• K x-rays are the only
characteristic x-rays of
tungsten that have
sufficient energy to be of
value in radiography.
Continuous X-ray Spectrum
• The Bremsstrahlung x-
ray energies range from
zero to a peak and back
to zero.
• This is referred to as the
Continuous X-ray
Spectrum.
Continuous X-ray Spectrum
• The majority of the
useful x-rays are in the
continuous spectrum.
• The maximum energy
will be equal to the kVp
of operation.
• This is why it is called
kVp (peak).
Four Factors Influencing the X-ray
Emission Spectrum
• 1. The electrons accelerated from the cathode do not all have the
peak kinetic energy. Depending upon the type of rectification and
high voltage circuits, many electrons will have very low energy that
produces low energy x-rays.
Four Factors Influencing the X-ray
Emission Spectrum
• 2. The target is relatively thick. Many of the bremsstrahlung x-ray
emitted result from multiple interactions of the projectile electrons.
• Each successive interaction results in less energy.
Four Factors Influencing the X-ray
Emission Spectrum
• 3. Low energy x-rays are more likely absorbed by the target.
• 4. External filtration is always added to the tube assembly. This
added filtration serves to selectively remove the lower energy
photon.
Minimum Wavelength
• As a photon wavelength increases, the photon energy decreases.
Therefore the maximum x-ray energy is associated with the minimum
x-ray wavelength.
• Since the minimum wavelength of x-ray emissions corresponds to the
maximum photon energy, the maximum photon energy is equal to the
kVp.
 Lecture
X-Ray Powder Diffraction

129
What is a powder?
• In the context of powder diffraction, a powder is a sample that
consists of many small crystallites with a wide range of different
orientations in space.
• Ideally, a random and uniform distribution of orientations
• Only some small fraction of the crystallites in the sample are in
the correct orientation to contribute to the diffracted intensity
in a given peak

Only crystallites that are in

the symmetrical reflection
2q condition and fulfill Bragg’s
law contribute to diffraction
 What is X-ray Powder Diffraction (XRD)

• X-ray powder diffraction (XRD) is a rapid analytical technique primarily used

for phase identification of a crystalline material and can provide information
on unit cell dimensions. 
• In other methods a single crystal is required whose size is much larger than
microscopic dimensions. However, in the powder method as little as 1 mg of
the material is sufficient for the study.
• The analyzed material is finely ground, homogenized, and average bulk
composition is determined

131
 History
• Max von Laue, in 1912, discovered that crystalline substances act
as three-dimensional diffraction gratings for X-ray wavelengths
similar to the spacing of planes in a crystal lattice.
• The powder method was devised independently by Debye and
Scherrer in Germany and by Hull in America at about the same
time.

132
Fundamental Principles of X-ray
Powder Diffraction (XRD)
•  X-ray diffraction is based on constructive interference of monochromatic
X-rays and a crystalline sample.

• These X-rays are generated by a cathode ray tube, filtered to produce

monochromatic radiation, collimated to concentrate, and directed toward
the sample.

• For every set of crystal planes , one or more crystals will be in the correct
orientation to give the correct Bragg angle to satisfy Bragg's equation.

• Each diffraction line is made up of a large number of small spots, each

from a separate crystal.

• Each spot is so small as to give the appearance of a continuous line. Every

crystal plane is thus capable of diffraction.

133
• The powdered sample generates the concentric cones of diffracted
X-rays because of the random orientation of crystallites in the
sample.
• Hence, instead of the sample generating only single diffraction spots,
it generates cones of diffracted X-rays, with the point of all of the
cones at the sample.
• The powder diffracts the x-rays in accordance with Bragg’s law to
produce cones of diffracted beams.
• These cones intersect a strip of photographic film located in the
cylindrical camera to produce a characteristic set of arcs on the film.
• When the film is removed from the camera, flattened and processed,
it shows the diffraction lines and the holes for the incident and
transmitted beams.
• The x-ray pattern of a pure crystalline substance can be considered
as a “fingerprint” with each crystalline material having, within limits,
a unique diffraction pattern

134
 Electronic 1D detectors
• 1D position sensitive detectors based on many
different types of technology are available.
• Fast data collection, but not as efficient as a 2D detector
• But access to high 2q by curving the detector

INEL curved detector at Cal Tech Braun linear PSD at ORNL/HTML

 THE POWDER METHOD

  2dSin 
Cubic crystal

2
4 a
(h 2  k 2  l 2 )  2 sin 2 


 2
(h 2  k 2  l 2 )  sin 2 
a2  2
( h 2
 k 2
 l 2
)
4 sin 
The experimental arrangement of powder crystal method is
shown in fig.1. its main feature are outlined as below: A is
a source of X-rays which can be made monochromatic by a
filter Allow the X-ray beam to fall on the powdered
specimen P through the slits S1 and S2.

The function of these slits is to get a narrow pencil of X-

rays. Fine powder, P, struck on a hair by means of gum is
suspended vertically in the axis of a cylindrical camera.

This enables sharp lines to be obtained on the photographic

film which is surrounding the powder crystal in the form of
a circular arc. 

137
Applications Identification
• The most common use of powder (polycrystalline) diffraction is chemical
analysis. This can include phase identification (search/match) X-ray
powder diffraction is most widely used for the identification of unknown
crystalline materials (e.g. minerals, inorganic compounds).
• Other applications include: identification of fine-grained minerals such
as clays and mixed layer clays that are difficult to determine optically

138
• Determination of unit cell dimensions.
measurement of sample purity .
• Most useful for cubic crystal. Used for determining
the complex structure of metals and alloys.
• Useful to make distinction between the allotropic
modifications of the same substance.

139
 •  Strengths and Limitations of X-ray Powder
Diffraction (XRD)?

• Strengths :- Powerful and rapid (< 20 min)

technique for identification of an unknown mineral.

• In most cases, it provides a clear structural

determination. XRD units are widely available. Data
interpretation is relatively straight forward

140
Limitations:-
• Homogeneous and single phase material is best
for identification of an unknown.
• Requires tenths of a gram of material which must
be ground into a powder.
• For mixed materials, detection limit is ~ 2% of
sample. Peak overlay may occur and worsens for
high angle 'reflections’ .
• For unit cell determinations, indexing of patterns
for non-isometric crystal systems is complicated 

141
 Insert the values into a table and compute sin and sin2.
Since the lowest value of sin2 is 3A and the next is 4A the first
Entry in the Calc. sin2 column is (0.10854/3)*4 etc.

d/Å Sin Sin2 Calc. Sin2 (h, k, I)

2.338 0.32945 0.10854 (1,1,1)
2.024 0.38056 0.14482 0.14472 (2,0,0)
1.431 0.53826 0.28972 0.28944 (2,2,0)
1.221 0.63084 0.39795 0.39798 (3,1,1)
1.169 0.65890 0.43414 0.43416 (2,2,2)
1.0124 0.76082 0.57884 0.57888 (4,0,0)
0.9289 0.82921 0.68758 0.68742 (3,3,1)
0.9055 0.85063 0.72358 0.72360 (4,2,0)

The reflections have now been indexed.

 For the first
Calculation of a reflection (for which h2 + k2 + l2 = 3)
sin2 = 3A = 3 ( l2 / 4a2 )
a2 = 3l2 / 4sin2
a = 4.04946 Å = 4.04946 x 10-8 cm.

Calculation of the density of aluminium

a3 = 66.40356 Å3 = 66.40356 x 10-24 cm3.
If the density of aluminium is r (g. cm.-3), the mass of the unit cell is
 x 66.40356 x 10-24 g.
The unit cell of aluminium contains 4 atoms.
The weight of one aluminium atom is 26.98/(6.022 x 1023) = 4.48024 x
10-23
and the weight of four atoms (the content of the unit cell) is 179.209 x
10-24.
r x 66.40356 x 10-24 = 179.209 x 10-24
p = 2.6988 g.cm-3.
Example

The X-ray powder diffraction pattern of AgCl obtained using radiation of

wavelength 1.54Å is shown below. The peaks are labelled with 2θ values

Answer each of the following.

On the basis that the
structure is cubic and of
either the NaCl or CsCl type
1. Index the first six
reflections.
2. Calculate the unit cell
parameter
3. Calculate the density of
AgCl.

(Assume the following atomic weights: Ag,

107.868; Cl, 35.453; and Avogadro’s
number is 6.022 x 1023)
 Since  values are available sin2 values can be calculated and inserted
in a table.

2  Sin2 Calc. Sin2

27.80 13.90 0.0577
32.20 16.10 0.0769 0.07693
46.20 23.10 0.1539 0.1539
54.80 27.40 0.2118 0.2116
57.45 28.73 0.2310 0.2308
67.45 33.73 0.3083 0.3077

From Sin2 = A(h2 + k2 + l2) the possible values are:

1. for a face centred lattice 3A, 4A , 8A, 11A, 12A and 16A
2. for a primitive lattice 1A, 2A, 3A, 4A, 5A and 6A
The second option is not possible as the first 2 are not in the ratio of 1:2.
To test the first option, divide the first by 3 and multiply the result by 4, 8 etc.
Density of AgCl

Since sin2 = l2(h2 + k2 + l2)/4a2

a2 = (1.54)2.(16)/4(0.3083) using the largest (most accurate) 2
a2 = 30.7692

a = 5.547Ǻ (1Ǻ = 10-8 cm)

Formula wt. of unit cell = 4AgCl = 573.284g
This is the weight of 4 moles of AgCl.
The weight of 4 molecules is 573.284 / (6.02 x 1023)
Density = 573.284 / (6.02 x 1023)(5.547 x 10-8)3
A is in Ǻ thus the answer should be multiplied by 1 / 10-24

Density = 5.580 g/cm3

Preferred Orientation Effects in X-ray Powder Diffraction Patterns
It is possible to calculate the theoretical diffraction pattern if the
crystal structure is known.

Nifedipine
Calculated pattern

Observed pattern

There are no preferred orientation effects here as all reflections have their
expected intensity.
Benzoic acid

Calculated pattern

002
Observed pattern
004

There is clear preferred orientation here. The 002 is the

flat face exposed when the needles lie down on a flat
plate.
Lecture : X-ray Diffraction
(XRD)
 For electromagnetic radiation to be diffracted the spacing in the grating should be
of the same order as the wavelength.
 In crystals the typical interatomic spacing ~ 2-3 Å**  so the suitable radiation
for the diffraction study of crystals is X-rays.
 Hence, X-rays are used for the investigation of crystal structures.
 Neutrons and Electrons are also used for diffraction studies from materials.

Beam of electrons Target X-rays

An accelerating (or decelerating) charge radiates electromagnetic radiation

Mo Target impacted by electrons accelerated by a 35 kV
potential shows the emission spectrum as in the figure below
(schematic)
Intense peak, nearly X-ray sources with
K monochromatic
different  for doing XRD
studies
Target  Of K
White K Metal radiation (Å)
Intensity

radiation
Mo 0.71
Characteristic radiation → Cu 1.54
due to energy transitions
in the atom
Co 1.79
Fe 1.94
Cr 2.29

0.2 0.6 1.0 1.4

Wavelength ()

The high intensity nearly monochromatic K x-rays can be used

as a radiation source for
X-ray diffraction (XRD) studies  a monochromator can be
Diffraction
 Now we shall consider the important topic as to how X-rays interact with a
crystalline array (of atoms, ions etc.) to give rise to the phenomenon known as X-
ray diffraction (XRD).
 Let us consider a special case of diffraction → a case where we get ‘sharp
diffraction peaks’.
 Diffraction (with sharp peaks) requires two important conditions to be satisfied:
 Coherent, monochromatic, parallel waves (with wavelength ).
 Crystalline array of scatterers* with spacing of the order of (~) .

Coherent, monochromatic, parallel wave

Diffraction Aspects related to the wave

pattern with Aspects related to the material Crystalline

sharp peaks
Aspects related to the diffraction set-up
(diffraction geometry)
XRD  the first step
 A beam of X-rays directed at a crystal interacts with the electrons of the atoms in the crystal.
 The electrons oscillate under the influence of the incoming X-Rays and become secondary sources
of EM radiation.
 The secondary radiation is in all directions.
 The waves emitted by the electrons have the same frequency as the incoming X-rays  coherent.
 The emission can undergo constructive or destructive interference.

Secondary
Incoming X-rays emission

Oscillating charge re-radiates  In phase with

the incoming x-rays

Schematics

Sets nucleus into oscillation

Sets Electron cloud into oscillation
Small effect  neglected
Bragg Equation
• n l= 2 d sinΘ
• n must be an integer and is
assumed to be one unless Detector

or
otherwise stated. typically moves

det y
ect
a
over range of 2

X-r
• Below is a sketch of the
apparatus which we will not Θ angles
go into.
2Θ
2Θ
X-ray source
Typically a Cu or Mo target Sample holder
1.54 or 0.8 Å wavelength
Orientation of diffracting planes
 Planes in Lattices and Bragg’s Law
We are interested in the planes in a crystal lattice in the context of X-ray
diffraction because of Bragg’s Law:
nl = 2 d sin(q)
Where:
n is an integer

l is the wavelength of the X-

rays

d is distance between adjacent

planes in the lattice

q is the incident angle of the X-

ray beam
Bragg’s law tells us the conditions that must be met for the reflected X-ray
waves to be in phase with each other (constructive interference). If these
conditions are not met, destructive interference reduces the reflected
intensity to zero!

W.H.Bragg and son W.L.Bragg were awarded the Nobel prize in 1915.
 Diffraction from crystals
X-ray Detector
Tube
Incident radiation “Reflected” radiation 1

 

X Z
Y
d

? Transmitted radiation
 Incident radiation “Reflected” radiation 1

 

X Z
Y
d

Transmitted radiation

Beam 2 lags beam 1 by XYZ = 2d sin 

so 2d sin  = n Bragg’s Law

 Examples for Bragg Equation
If the wavelength striking a crystal at a 38.3° angle has a
wavelength of 1.54 Ǻ, what is the distance between the two
layers. Recall we assume n = 1.
You will need your calculator to determine the sine of the angle.

n λ = 2 d sin θ
1.54 Ǻ = 2 d sin 38.3°
this can be rearranged to d = λ / (2 Sin θB)
SO
= 1.54 Ǻ / ( 2 * Sin 38.3 )  = 1.24 Ǻ
X rays of wavelength 0.154 nm are diffracted
from a crystal at an angle of 14.170. Assuming
that n = 1, what is the distance (in pm) between
layers in the crystal?
The given information is n l = 2 d sin q
n=1
q = 14.170
l = 0.154 nm = 154 pm

nl 1 x 154 pm
d = = = 314.54 pm
2 sinq 2 x sin14.17
X-rays with wavelength 1.54Å are reflected from planes
with d=1.2Å. Calculate the Bragg angle, , for
constructive interference?

 = 1.54 x 10-10 m, d = 1.2 x 10-10 m, =?

2d sin   n
 n 
1 n=1 :  = 39.9°
  sin  
 2d 
2d sin  = n

We normally set n=1 and adjust Miller indices, to give

2dhkl sin  = 
Use Bragg’s law and the d-spacing
equation to solve a wide variety of
problems
2d sin  = n
or
2dhkl sin  = 

1 h k l
2 2 2

d 2
a 2
b c
2 2
 Combining Bragg and d-spacing equation
X-rays with wavelength 1.54 Å are “reflected” from the
(1 1 0) planes of a cubic crystal with unit cell a = 6 Å.
Calculate the Bragg angle, , for all orders of reflection, n.
2 2 2
1 h k l 11 0
2
   0.056
d a2 6 2

2
d  18  d = 4.24 Å 2dhkl sin  = 

 n 
1
n=1:  = 10.46° = (1 1 0)
  sin   n=2:  = 21.30° = (2 2 0)
 2d 
It’s Importance
• The Bragg equation enables us to find the dimensions
of a unit cell. This gives us accurate values for the
volume of the cell.
• As you will see in the following on unit cells and the
equations, this is how density is determined
accurately.
 When silver crystallizes, it forms face-centered
cubic cells. The unit cell edge length is 408.7 pm.
Calculate the density of silver. Though not shown
here, the edge length was determined by the Bragg
Equation.
m V = a3 = (408.7 pm)3 = 6.83 x 10-23 cm3
d=
V
Remember that there are 4 atoms/unit cell in a face-centered cubic cell

107.9 g 1 mole Ag
m = 4 Ag atoms x x = 7.17 x 10 -22
g
mole Ag 6.022 x 10 atoms
23

m 7.17 x 10-22 g
d= = = 10.5 g/cm 3
V 6.83 x 10-23 cm3

This is a pretty standard type of problem to determine

density from edge length.
Lecture (optional)
X-ray Crystallography (continued)
The reciprocal lattice and
Laue symmetry
Data collection
Space group determination
Structure solution
Powder X-ray diffraction

165
Reciprocal lattice and Laue symmetry

Through a geometrical construction it is possible to obtain a

lattice with points corresponding to individual reflections.

This lattice is known as the reciprocal lattice, so called

because of the reciprocal nature of the relationship between
the axes in the real lattice and the reciprocal lattice.

For example, a long b cell length in the crystal corresponds

to a small separation between lattice points in the reciprocal
lattice (in the corresponding direction).

166
A reciprocal lattice plane (h 0 l plane); h horizontal, l vertical

In this
representation
spot size is
related to X-
ray intensity.

301

-3 0 -4

167
The symmetry with respect to reflection intensity in a
reciprocal lattice is related to the symmetry in the real
crystal.

For example in a monoclinic crystal the diffraction (or

Laue) symmetry is 2/m i.e. 2-fold axis parallel to k
and mirror plane in the h-l plane.

Therefore the reflection 4 5 6 is symmetry related to

(i.e. will have the same intensity as):

4 -5 6; -4 5 -6; -4 -5 -6.

By considering the equivalency between reflections

we can determine the Laue symmetry.

168
If a crystal is orthorhombic then it is has Laue symmetry
of mmm.

Therefore the reflection 4 5 6 will be equivalent to:

-4 5 6
-4 -5 6
4 -5 6
4 -5 -6
4 5 -6
-4 -5 -6

If a crystal is tetragonal then it may have 4/m or 4/mmm

Laue symmetry.

Determining the Laue symmetry helps to narrow down the

choice of space groups.
169
 Data collection on a modern diffractometer

low T N2 video
camera

collimators

detector
crystal
goniometer

Once a suitable crystal has been found it is mounted normally

on the tip of a glass fibre that is attached to a goniometer. 170
Determining the unit cell and crystal class
First step involves determination of the unit cell.
X-rays are directed towards the crystal and the diffraction
spots are measured.
The diffractometer allows reflections to be measured over a
number of orientations over a range of angles.
This process of measuring the position of almost random
reflections allows the diffractometer computer to calculate
the reciprocal cell for the crystal.
From the reciprocal cell the direct cell may be calculated.

171
Once the reciprocal cell is obtained then it is possible to
calculate the position of every reflection in the reciprocal
lattice.

Measuring every reflection in the full reciprocal lattice

may take an unnecessarily long period of time.

We can take advantage of the Laue symmetry in the

diffraction pattern and measure only a fraction of the
reflections.

Consider the case where a monoclinic cell is indicated.

The reciprocal lattice has Laue symmetry of 2/m and

therefore we only need to collect 1/4 of the full sphere of
reflections.
172
Note the
symmetry in
the reciprocal
lattice –
we don’t have
to collect every
reflection

173
At this point the crystallographer aided by the computer
software will then select a data collection strategy.

This involves choosing appropriate exposure times and

ensuring that enough data is collected.

It is normal practice to collect some symmetry related

reflections in order to gauge the quality of the crystal and
help in the identification of the correct Laue symmetry.

Typically a data collection might run between 0.5 and 8

hours.

174
Space group determination

Once the reflection data has been collated we are then

in a position to decide upon the space group.

The first step involves determining the Laue symmetry.

At this point we look for systematic absences in the

data.

The presence of certain symmetry operations in a

crystal can result in some reflections suffering from
complete destructive interference.

175
Consider the following selected reflections from a
monclinic crystal.

h0l I (I) 0k0 l (I)

1 0 1 28.3 25.0 0 1 0 22.4 18.0

1 0 2 987.0 41.0 0 2 0 496.0 21.0
1 0 3 24.1 16.9 030 9.0 16.2
1 0 4 633.4 27.2 0 4 0 787.0 20.6
2 0 1 17.6 20.5 0 5 0 31.0 19.1
2 0 2 1445.1 52.6 0 6 0 145.6 15.1
203 5.2 14.3 070 6.1 14.8

I is the intensity
(I) is the standard uncertainty
176
Note that for reflections of the type h 0 l the reflection is
absent when l is an odd integer.
This systematic absence arises because of the presence
of c-glides.
For reflections of the type 0 k 0 the reflection is absent
when k is odd.
This systematic absence arises because of the presence
of 2-fold screws.
Thus if the Laue symmetry was shown to be 2/m the
systematic absences indicate that the space group is
P21/c.

177
While analysis of systematic absences can narrow down
the choice of space groups it does not always lead to a
single space group.
In many cases a number of space groups will have the
same systematic absences.
At this point it may be necessary to try to solve the
structure in a number of different space groups.
In such situations it is often possible to solve the
structure in more than one space group.
Under these circumstances we generally choose the
highest symmetry space group that provides a sensible
solution.

178
Structure solution

In order to solve a crystal structure we need, for each

reflection,

Reflection position (indicated by the Miller indices)

Intensity (measured by the detector)
Phase angle

The phase angle for a reflection is the shift in the wave

relative to the origin in the unit cell.

While the reflection position and intensity are measured

with relative ease we cannot measure the phase angle.

This is known as the phase problem.

179
Structure of simple Inorganic Compounds

Lecture
Ionic radii and the hard sphere model
Structures of AX solids
- Rock salt
- Cesium chloride
- Platinum sulfide

Structures of AX2 solids

- Cadmium iodide
- Cadmium chloride

180
THE “MOST IMPORTANT”
CRYSTAL STRUCTURES
 THE “MOST IMPORTANT”
CRYSTAL STRUCTURES
• Sodium Chloride Structure Na+Cl-
• Cesium Chloride Structure Cs+Cl-
• Diamond Structure

Structures of AX solids
Rock Salt Structure*
One of the simplest structures is the "NaCl" or "rock salt" structure.
NaCl is a convenient label for this type of structure.

182
 1 – Sodium Chloride Structure
• Sodium chloride also
crystallizes in a cubic lattice,
but with a different unit cell.
• The sodium chloride
structure consists of equal
numbers of sodium &
chlorine ions placed at
alternate points of a simple
cubic lattice.
• Each ion has six of the other
kind of ions as its nearest
neighbors.
NaCl Structure
• This structure can also be
considered as a face-centered-
cubic Bravais lattice with a basis
consisting of a sodium ion at 0 and
a chlorine ion at the center of the
conventional cell, at position

  
a / 2( x  y  z )
• LiF, NaBr, KCl, LiI, have this
structure.
• The lattice constants are of the
order of 4-7 Angstroms.
 NaCl Structure
• Take the NaCl unit cell & remove all “red” Cl ions,
leaving only the “blue” Na. Comparing this with the
FCC unit cell, it is found to be that they are
identical. So, the Na ions are on a FCC sublattice.
Alternatively one could view the structure as an FCC
arrangement of purple spheres with the green spheres in
octahedral sites.

In FCC the
octahedral sites are
also in a FCC
arrangement.

Each ion is in an octahedral environment of six ions of

the other type.

This is referred to as a 6:6 lattice – ie. C.N. of both ions

is 6.
188
NaCl Type Crystals
2-Cesium chloride CsCl

Primitive cubic arrangement of chloride anions with cesium

ions in cubic sites (and vice versa).

An 8:8 lattice.
C.N. of Cs = 8
C.N. of Cl = 8

Strong ionic influence in

the structure.

190
 2 - CsCl Structure
• Cesium Chloride, CsCl,
crystallizes in a cubic lattice. 
The unit cell may be depicted as
shown.
(Cs+  is teal, Cl- is gold)
• Cesium Chloride consists of
equal numbers of Cs and Cl
ions, placed at the points of a
body-centered cubic lattice so
that each ion has eight of the
other kind as its nearest
neighbors. 
 CsCl Structure
• The translational symmetry of this structure
is that of the simple cubic Bravais lattice, and
is described as a simple cubic lattice with a
basis consisting of a Cs ion at the origin 0
and a Cl ion at the cube center
  
a / 2( x  y  z )
• CsBr & CsI crystallize in this structure.The lattice
constants are of the order of 4 angstroms.
CsCl Structure

8 cells
CsCl Crystals
 3 - Diamond Structure
• The Diamond Lattice consists of 2 interpenetrating FCC
Lattices.
• There are 8 atoms in the unit cell. Each atom bonds
covalently to 4 others equally spaced about a given atom.
• The Coordination Number = 4.
• The diamond lattice is not a Bravais lattice.
C, Si, Ge & Sn crystallize in the Diamond structure.
Diamond Lattice

Diamond Lattice
The Cubic Unit Cell
Platinum Sulfide (PtS)*

Platinum(II) has a very strong preference for square

planar coordination.

S - yellow
Pt - blue

Sulfide has a tendency to

be tetrahedral.

If these ions are combined

in a 1:1 ratio, a tetragonal
structure results.

197
The Pt centre is
in a square
planar
environment.

The sulfide ion is

in a tetrahedral
environment.

198
The directional preference of the 2 ions exerts a dominant
influence on the structure.

Note: This structure is not related to any simple sphere

packing arrangement.

199
200
Structures OF AX2 SOLIDS

Fluorite Structure (CaF2)*

Radius of Ca2+ = 99 pm; radius of F- = 136 pm.

This structure can be

viewed as an FCC
arrangement of calcium
centers with ALL the
tetrahedral sites
occupied by fluorides.

201
Alternatively it can be viewed as related to CsCl with
a simple cubic arrangement of the anions but with
only half the cubic cavities occupied by cations.

C.N. of F- = 4 - tetrahedral
C.N. of Ca2+ = 8 - cubic
An 8:4 lattice.

Compounds adopting the fluorite structure:

MF2 (M = Ca, Sr, Ba, Ra, Pb, Cd, Hg, Eu)
MO2 (M = lanthanides, Th, Pa, U, Np, Pu, Am, Cm)
MMg2 (M = Ge, Sn, Pb); AuM2 (M = Al, Ga, In)
202