The intensities of diffracted beams

Introduction

The positions of the atoms in the unit cell affect the intensities but
not the directions of the diffracted beams.

(a) Base-centered and (b) body-centered orthorhombic unit cells

 Diffraction from the
(001) planes of
(a) base-centered and
(b) body centered
orthorhombic lattices

 This example shows how a simple rearrangement of atoms within the unit
cell can eliminate a reflection completely.

 More generally, the intensity of a diffracted beam is changed, not

necessarily to zero, by any change in atomic positions, and,

 conversely, we can only determine atomic positions by observations

of diffracted intensities.

To establish an exact relation between atom position and intensity is

the main purpose of this chapter.
 Scattering by a single electron

Oscillating electric field of an x-ray beam will set any

electron it encounters into oscillatory motion about its
mean position.

Accelerating or decelerating electron emits an electromagnetic

wave and an electron is said to scatter x-rays.

Scattering by an electron occurs in all directions

The scattered beam has the same wavelength and frequency

as the incident beam, if it is coherent.
It is said to be coherent with it, since there is a definite
relationship between the phase of the scattered beam and
that of the incident beam

Coherent scattering occurs when an incident photon bounces off

an electron which is so tightly bound that it receives no
momentum from the impact,

The scattered photon therefore has the same energy, and

hence wavelength, as it had before.
 Scattering of X-rays by a Single Electron

so represents the direction and momentum of the incident X-ray

photon (i.e. before it is scattered) and s represents the direction and
momentum of the X-ray photon after being scattered

s = so + S

Momentum of a wave is proportional to the inverse of its wavelength

An important aspect of diffraction is that we only consider elastic
scattering;

by that we mean that there is no loss of X-ray photon energy

through scattering so that the energy (and absolute momentum) of
the X-ray photon remains unchanged.

This is why the length of s in the diagram (1/λ) has been made the
same as the length of so.

Finally the vector S, which bridges s and so, represents the net
change as a result of the scattering process and is an important item,
often referred to as the scattering vector S; its length is equal
to 2sinθ/λ
 Scattering of X-rays by Two Electrons

Two waves end up being about one and a quarter wavelengths apart so we
would say in this case that the phase difference is λ/4 in distance, or 90
degrees or π/2 radians,

since the whole wavelength part on its own would have no net effect
whereas the additional quarter does matter.

What the "detector then sees" depends critically on the precise value
of this phase difference.
Types of scattering of x-rays

1. Thomson scattering

2. Compton scattering
 Thomson scattering

Thomson found that the intensity of the beam scattered by a single

electron of charge e and mass m, at a distance r from the electron, is
given by

α = angle between the scattering direction and the direction of

acceleration of the electron.

This scattering is a coherent scattering which occurs due to collision of x-

rays with tightly bound electrons.
 Electron at O

e moving

An unpolarized incident beam, such as that issuing from an x-ray tube, has its
electric vector E in a random direction in the yz plane. This beam may be
resolved into two plane polarized components, having electric vectors Ey and
Ez where
 since the direction of E is perfectly random, on the average, Ey will
be equal to Ez.

Therefore

(Since, the intensity of a wave is proportional to the square of its amplitude)

The y component of the incident beam accelerates the electron in
the direction Oy. It, therefore, gives rise to a scattered beam whose
intensity at P is found

Here, α = < yOP = 90°

Similarly, the intensity of the scattered z component is given

by

Since, α = < zOP = 90°-2θ

 is called the polarization factor

This factor enters the equation simply because the incident beam is
unpolarized.
 Compton scattering

Compton scattering is an elastic scattering of a photon by a

free charged particle, usually an electron.

It can be realized when incident beam is considered as a stream of x-ray

quanta

a photon strikes a loosely bound electron, the collision is an elastic one

like that of two billiard balls

It results in a decrease in energy (increase in wavelength) of the photon

of an X-ray, called the Compton effect.

Part of the energy of the photon is transferred to the scattering

electron.
Elastic collision of photon and electron (Compton effect).
 h
2  1  (1  cos 2 )
me c

The increase in wavelength depends only on the scattering

angle, and
it varies from zero (0) in the forward direction (2θ = 0) to 0.05A
in the extreme backward direction (2θ = 180°).

Radiation so scattered is called Compton modified radiation.

It has the important characteristic that its phase has no fixed relation
to the phase of the incident beam as its wavelength increased.

For this reason it is also known as incoherent radiation.

It cannot take part in diffraction because its phase is only randomly

related to that of the incident beam and cannot therefore produce
any interference effects.

Compton modified scattering cannot be prevented, however, and it

has the undesirable effect of darkening the background of diffraction
patterns.
Scattering of X-rays by an Atom
For zero angles the, coherent scattering is a maximum and equal to
the total number of electrons within the electron cloud.

As the scattering angle, 2θ, increases there is increasing destructive

interference between the X-rays scattered by different parts (e.g. the
three points illustrated) of the electron cloud.

This gives rise to the very characteristic shape, f, in the above

figure. f is often referred to as the atomic scattering factor or form
factor

amplitude of the wave scattered by an atom

f 
amplitude of the wave scattered by one electron
The nucleus has an extremely large mass relative to that of one
electron and cannot be made to oscillate to any appreciable extent

Value of f has been tabulated for most of the atoms and ions
in the International Tables for Crystallography.

Data are normally tabulated against (sinθ)/λ (S/2) rather than

against 2θ,

and for just one half of the function since the two sides are
identical.
Atomic scattering factor ‘f’ of some common atoms/ion
If we look at the f-curve for the oxygen atom we see that it starts ("starts"
means (sinθ)/λ = 0, which also means the scattering angle 2θ = 0) at 8 and
decreases thereafter.
This means that all 8 of the oxygen's electrons are scattering in phase at zero
scattering angle (the maximum point in the above diagram) but,
as (sinθ)/λ (and therefore 2θ) increases the scattering from all 8 electrons
becomes progressively out of phase.
We can see that this is a plausible result considering the three representative
scattering points in the figure (next slide), since they each represent very different
associated path lengths as 2θ increases.

The net effect is that coherent scattering by an atom is due only to the
electrons contained in that atom.
The waves scattered in the forward direction by electrons A and B
are exactly in phase on wave front such as XX', because each wave
has travelled the same distance before and after scattering.

The other scattered waves shown in the 'figure, however, have a path
difference equal to (CB - AD) and are thus somewhat out of phase
along a wave front such as YY', the path difference being less than
one wavelength.

X-ray scattering by an atom.

Partial interference occurs between the waves scattered by A and B, net
amplitude of the wave scattered in this direction is less than that of the wave
scattered by the same electrons in the forward direction.

The atomic scattering factor also depends on the wavelength of the

incident beam : at a fixed value of θ, f will be smaller for shorter
wavelength, since the path differences will be larger relative to the
wavelength, leading to greater interference between the scattered
beams.

The actual calculation of f involves sinθ rather than θ, so that the net
effect is that f decreases as the quantity (sinθ)/λ increases.
Incoherent, or Compton modified scattering occurs at the
same time as coherent scattering.

Its intensity relative to that of the unmodified radiation

increases as the proportion of loosely bound electrons
increases.
Thus intensity of Compton modified radiation increases as the
atomic number Z decreases.

Good diffraction photographs are not obtained for organic

materials. Why?

It is also found that the intensity of the modified (Compton)

radiation increases as the quantity (sinθ)/λ increases.

The intensities of modified scattering and of unmodified

scattering therefore vary in opposite ways with Z and with
(sinθ)/λ.
 (Coherent)

The incident x-rays are assumed to be of high enough energy, i.e., of short
enough wavelength, to cause the emission of photoelectrons and
characteristic fluorescent radiation.

The Compton recoil electrons shown in the diagram are the loosely bound
electrons knocked out of the atom by x-ray quanta, the interaction giving rise
to Compton modified radiation.