Relative Intensity of diffraction lines in a powder pattern

Structure Factor (F) Scattering from UC (has Atomic Scattering Factor included)

Polarization factor Effect of wave polarization

IP 
1
2
1  Cos 2 2 
Multiplicity factor (p) Number of equivalent scattering planes

Lorentz factor Combination of 3 geometric factors

 1   1 
Lorentz factor   Cos  
 Sin 2   Sin 2 

Absorption factor Specimen absorption

Temperature factor Thermal diffuse scattering

 Multiplicity Factor
• Consider the 100 reflection from a cubic lattice. In the powder specimen, some of
the crystals will be so oriented that 100 diffraction occurs. Other crystals of different
orientation may be in such a position that 010 or 001 diffraction can occur. Since d100
= d010 = d001 the diffracted beams form part of the same diffraction cone.

• Now consider the 111 reflection. There are four sets of planes of the form {111}
  
which have the same spacing but different orientation, namely,
(111),(111),(111), and (111),
whereas there are only three sets of the form {100}.

• Therefore, the probability that {111} will be correctly oriented for diffraction is 4/3
the probability that {100} will be correctly oriented. It follows that the intensity of
the 111 reflection will be 4/3 that of the 100 reflection, other things being equal.

• This relative proportion of hkl planes contributing to the same reflection enter the
intensity equation as the quantity p, the multiplicity factor, which may be defined
as the number of permutations of position and sign of ±h, ±k, ±l for planes having
the same d and F2.

• The value of p depends on the crystal system: in a tetragonal crystal, the (100)
and (001) planes do not have the same spacing, so that the value of p for {100}
planes is reduced to 4 and the value for {001} planes to 2.
Multiplicity factor
Lattice Index Multiplicity Planes
Cubic (100) 6 [(100) (010) (001)] ( 2 for negatives)
(with highest
symmetry) (110) 12 [(110) (101) (011), (110) (101) (011)] ( 2 for negatives)

(111) 8 [(111) (111) (111) (111)] ( 2 for negatives)

(210)  3! Ways, (210)  3! Ways,
(210) 24*
(210)  3! Ways, (210)  3! Ways
(211)  3! ways, (211)  3! ways,
(211) 24
(211)  3! ways, (211)  3! ways
(321) 48*
Tetragonal (100) 4 [(100) (010)] ( 2 for negatives)
(with highest
symmetry) (110) 4 [(110) (110)] ( 2 for negatives)

(111) 8 [(111) (111) (111) (111)] ( 2 for negatives)

(210) = 2 Ways, (210) = 2 Ways,
(210) 8*
(210) = 2 Ways, (210) = 2 Ways
(211) 16 [Same as for (210) = 8]  2 (as l can be +1 or 1)

(321) 16* Same as above (as last digit is anyhow not permuted)

* Altered in crystals with lower symmetry

 Certain trigonometrical factors which influence
the intensity of the diffracted beam.

The integrated intensity is of much more interest than the maximum intensity, since
the former is characteristic of the specimen while the latter is influenced by slight
adjustments of the experimental apparatus.
Consider an experiment where the x-ray intensity at exactly the Bragg
angle is monitored as a crystal is rocked through θB

There is some intensity even when the crystal is not at θB

Path length difference for scattering from atoms A and B when the crystal
is displaced by Δθ from the Bragg angle
The path difference between the rays scattered by atoms at either end of the
plane is simply N times this quantity.
When the rays scattered by the two end atoms are (N + 1) wavelengths out of
phase, the diffracted intensity will be zero.

(The argument here is exactly analogous to that used for diffraction under non-
ideal conditions, i.e. This means that midway in the crystal there is a plane
scattering a ray which is one-half wavelength out of phase with ray scattered
from the two end atoms.)

Scattered intensity will drop to zero when Δθ is such that the x-rays scattered
from atoms at either end of the illuminated region of the crystal is as per the
condition:
This equation gives the maximum angular range of crystal rotation over which
appreciable energy will be diffracted in the direction 2θB.

Since Imax depends on this range, we can conclude that Imax is proportional to
1/sinθB.

Other things being equal, Imax is therefore large at low scattering angles and small in
the back-reflection region.

The breadth of the diffraction curve varies in the opposite way, being
larger at large values of 2θB, where the half maximum breadth B was found
to be proportional to I/cosθB.

The integrated intensity of the reflection is given by the area under the
diffraction curve and is therefore proportional to the product Imax*B,

which is in turn proportional to (1/sin θB)(1/cos θB) = 1/sin 2θB.

This correction is appropriate for single crystal measurement and additional

geometrical term is needed for powder diffraction.
 Additional geometrical terms
In the powder method, a second geometrical factor arises when we consider that
the integrated intensity of a reflection at any particular Bragg angle θB depends on
the number of crystals oriented at or near that angle.
This number is not constant even though the particles are oriented completely at
random.
In the following Fig., a reference sphere of radius r is drawn around the powder
specimen located at O. For the particular hkl reflection shown, ON is the normal to
this set of planes in one crystal of the powder.

Suppose that the range of angles near the Bragg

angle over which reflection is appreciable is Δθ.
Then, for this particular hkl reflection, only those
crystals will be in a reflecting position which have
the ends of their plane normals lying in a band of
width rΔθ on the surface of the sphere.
Since the crystals are assumed to be oriented at random, the ends of their
plane normals will be uniformly distributed over the surface of the
sphere; the fraction favorably oriented for a reflection will be given by the
ratio of the area of the strip to that of the whole sphere.

If ΔN is the number of such particles and N the total number, then

In the most common arrangement of specimen and film, the Debye-
Scherrer method the film obviously receives a greater proportion of a
diffraction cone when the reflection is in the forward or backward
direction than it does near 2θ = 90°.
Inclusion of this effect, thus leads to a third geometrical factor affecting the
intensity of a reflection.

The length of any diffraction line being 2πRsin2θB, where R is the radius of the
camera,

the relative intensity per unit length of line is proportional to 1/sin2θB.

Polarization factor Lorentz factor


I P  1  Cos 2 2    1 
Lorentz factor  
 1 
Cos  
 Sin 2   Sin 2 

 1  Cos 2 2  
Lorentz Polarizati on factor   
 Sin  Cos 
2

XRD pattern from Po

All peaks present

Look at general trend line!

Example of effect of Polarization factor

on powder pattern
  1  Cos 2 2  
Lorentz Polarizati on factor   
 Sin  Cos 
2

30

25
Lorentz-Polarization factor

20

15

10

0
0 20 40 60 80
Bragg Angle (, degrees)
Intensity of powder pattern lines (ignoring Temperature & Absorption factors)
 Valid for Debye-Scherrer geometry
 1  Cos 2 2 
I  F p 
2
 I → Relative Integrated “Intensity”
 Sin  Cos 
2
 F → Structure factor
 p → Multiplicity factor

 POINTS
 As one is interested in relative (integrated) intensities of the lines constant factors are
omitted
 Volume of specimen  me , e  (1/detector radius)
 Random orientation of crystals  in which Texture intensities are modified
 I is really diffracted energy (as Intensity is Energy/area/time)
 Ignoring Temperature & Absorption factors  valid for lines close-by in pattern
In real crystals the periodic arrangement of atoms is somewhat
disrupted as the atoms are undergoing vibrational motion
– This loss of perfect order reduces the diffracted intensity
» Reduction of intensity is modelled by a temperature factor
e-2M , where M = B(sinθ/λ)2 = 8π2u2(sinθ/λ)2 and
u2 is the mean square displacement of the atom from its
average position
» As the mean square displacement can be large for
some materials (average displacement 0.17 Å for Al at
room temp), the temperature factor can lead to a dramatic
decrease in diffracted intensity, particularly when the
sample is at high temperature.
» Loss of intensity is most obvious at high angles
» As peaks are suppressed by thermal motion the background rises due
to thermal diffuse scattering;
It contributes only to the general background of the pattern and its
intensity gradually increases with 2θ.
Now the thickness of the plate like "planes” in which the vibrating atoms
lie is 2u (average), where u is the average displacement of an atom
from its mean position.

Under these conditions reinforcement is no longer perfect, and it

becomes more imperfect as the ratio u/d increases, i.e.,

(i) as the temperature increases u increases,

(ii) Or as θ increases, since high-θ reflections involve planes of

low d value.

For a constant temperature, thermal vibration causes a greater

decrease in the reflected intensity at high angles than at low angles
[reason (ii) above].

Temperature effect and the absorption effect in cylindrical specimens depend

on angle in opposite ways and, to a first approximation, cancel each other.
Thermal vibration of the atoms of a crystal does not cause any
broadening of the diffraction lines; they remain sharp right up to
the melting point, but their maximum intensity gradually decreases.

The mean amplitude of atomic vibration also depends on the elastic

constants of the crystal.

At any given temperature, the less "stiff“ the crystal, the greater
the vibration amplitude u.

Substances with low melting points have quite large values of u even
at room temperature and therefore yield rather poor back-reflection
photographs.