Diffraction Intensities and Structure

5.1 Introduction
In this chapter we will study a specific and detailed examination of the intensities of diffraction
and to the way in which they are related to the structure of crystals.

5.1.1 Intensity Diffracted by a Crystal

The determination of the appropriate crystal lattice requires information of the intensities of the
diffracted beams. More importantly, in order to proceed with a determination of the complete
crystal structure, it is vital to understand the relationship between the intensity of a beam
diffracted from a set of ( ) planes and the atoms that make up the planes themselves the
intensities of diffracted beams vary from one radiation type to another, and are found to depend
upon the following factors:
( ) The nature of the radiation.
( ) The Bragg angle of the diffracted beam.
( ) The diffracting power of the atoms present the atomic scattering factor.
( ) The arrangement of the atoms in the crystal the structure factor.
( ) The thermal vibrations of the atoms.

5.2 Atomic Scattering Factor

When considering the scattering of X-rays by an atom, one must take into account the fact that
the scattering is actually done by the cloud of electrons which surrounds the nuclei. The total
scattering from an atom depends on the distribution of the electron cloud. If an atom scatters X-
rays uniformly, then it is said to have a scattering power of which is equal to the atomic
number, of the atom. However, the scattering of the X-ray beam increases as the number of
electrons, or equally, the atomic number of the atom, Z, increases. The reason is that the atom
has a size comparable to the wavelength of the X-rays, and scattered X-rays leaving different
parts of the atomic charge cloud are not exactly in phase. The difference in phase is zero at zero
diffraction angle, but increases markedly as varies from The scattering power of
an atom for a beam of X-rays is called the atomic scattering factor, . It is defined as the ratio
of amplitude of radiations scattered by an atom to the amplitude of the radiation scattered by the
electron and depends on the number and distribution of atomic electrons and the wavelength and
angle of scattering of the radiation.
 Fig 5.1: Phase difference in scattering from different parts of an atom.

5.2.1 Classical Expression For

The atomic scattering factor is defined as,

⃗ ⃗
∫ ( ⃗) (5.1)

With the integral extended over the electron concentration, ( ⃗) associated with the single atom.
Also, ⃗ is the reciprocal lattice vector. Let ⃗ make an angle with ⃗ , then

⃗ ⃗ (5.2)

If the electron distribution is spherically symmetric about the origin, then the expression for
after integrating becomes,

∫ ( ) (5.3)

If the same total electron density were concentrated at , then we have,

∫ ( ) (5.4)

So, for uniform scattering of X-rays by an atom, is equal to the number of atomic electrons[7].

5.3 The Structure Factor ( )

To obtain the total intensity of radiation scattered by a unit cell, the scattering of all of the atoms
in the unit cell must be combined. This is carried out by adding together the waves scattered
from each set of ( ) planes independently, to obtain a value called the structure factor, ( ) ,
for each ( ) plane. The amplitude of the resultant wave is termed as the scattering amplitude
| ( )| and the intensity of a diffracted beam is defined as | ( )| . The structure factor can
be calculated in the following way:
Consider two volume elements separated by ⃗ inside a crystal as shown in Fig. below.
A plane wave ⃗⃗ ⃗ incident on the two elements is scattered in the direction ⃗⃗⃗⃗. The difference in
phase factors is [ ( ⃗⃗ ⃗⃗⃗⃗) ⃗] between beams scattered from volume elements ⃗ apart.
Now the amplitude of the wave scattered from the volume element is proportional to the local
electron concentration ( ⃗) The total amplitude of the scattered wave is proportional to the
integral over the crystal of ( ⃗) times the phase factor [ ( ⃗⃗ ⃗⃗⃗⃗) ⃗]. Thus the scattering
amplitude is given by

(⃗⃗ ⃗⃗ ) ⃗
∫ ( ⃗) (5.5)

⃗⃗ ⃗
or ∫ ( ⃗) (5.6)

Here ⃗⃗ measures the change in wave vector and is called the scattering vector. Now introducing
Fourier components,

⃗ ⃗
⃗ ∫ ( ⃗) (5.7)

Of ( ⃗) into equation (5.6) to obtain the expression for scattering amplitude as

(⃗ ⃗⃗ ) ⃗
∑ ∫ (5.8)

⃗⃗ ⃗ , then (⃗ ⃗⃗ ) ⃗
If so that

∑ ∫ (5.9)

However, if ⃗⃗ differs significantly from ⃗ , then

is negligibly small. Thus the necessary
condition for diffraction maxima to be observed in a particular direction ⃗⃗ is ⃗⃗ ⃗ which
represents Bragg’s law. In deriving equation (5.8), it has been assumed that the diffracting
system is a Bravais lattice occupied by one kind of atom. However, a real crystal may contain the
repetitive unit which may consist of more than one atom i.e; the repetitive unit may be the basis.
Taking the scattering by basis into account, we can write the expression for structure factor as,

( ) ∑ [ ( )] (5.10)

Where are the Miller indices of the diffracting plane, and the summation is carried out over
all atoms in the unit cell, each of which has an atomic scattering factor [8].
5.3.1 Significance of Structure Factor

There are many factors affecting the intensity of X-rays in the diffraction pattern. The one that
depends only upon the crystal structure is called the structure factor. Structure factors give a
mathematical description of the diffraction pattern. Each structure factor represents a diffracted
beam that has an amplitude, | ( )|, and a relative phase ( ). Mathematically, these are
combined as | ( )| [ ( )] and can be written as ( ). Experimentally, it is the
intensity and position of each diffraction spot which is measured. The intensity scattered into the
beam by all of the atoms in the unit cell, ( ), is given by | ( )| i.e; ( )
| ( )| ( ) {∑ [ ( )]} .

5.4 Electron Density and Structure Factor

An image of the crystal structure can be calculated from the X-ray diffraction pattern. Since it is
the electrons that scatter the X-rays, it is the electrons that we see in the image, giving the value
of the electron density at every point in a single unit cell of the crystal. The electron density is
expressed in terms of the structure factors as:

( ) ∑ ( ) [ ( )] (5.11)

Where the summation is over all the structure factors ( ) and is the volume of the unit cell.
In equation (1),the structure factors include the phases ( ) and not just the experimentally
measured amplitudes | ( )|.Since the X-rays are diffracted from the whole crystal, the
calculation yields the contents of the unit cell averaged over the whole crystal and not the
contents of any individual cell.