Diffraction

International union of crystallography

http://www.iucr.org/education/resources
Advanced Certificate in Powder Diffraction on the Web
http://pd.chem.ucl.ac.uk/pdnn/pdindex.htm
University of Cambridge Teaching and Learning package
http://www.doitpoms.ac.uk/tlplib/xray-diffraction/index.php
Matter.org
http://www.matter.org.uk/diffraction/
Some aspects
X-rays are electromagnetic radiation of wavelength in the
range of 0.5-2.5
Dual nature as any other electro-magnetic radiation
v

c
=
Wave nature
v h E =
Particle nature
Velocity of light = 3.0010
8
m/sec
Plancks constant = 6.62610
-34
joule sec

ch
E =
In an X-ray tube electrons are accelerated toward anode by maintaining high
voltage (tens of thousands of volts) across electrodes

High velocity electrons at the point of impact produce X-rays
Continuous spectrum or white radiation or bremsstrahlung - X-rays
are produced when any electrically charged particle of sufficient kinetic
energy is rapidly decelerated
Kinetic energy of an electron having charge e (1.610
-19
coulomb)
and accelerated by voltage V across the electrodes
2
2
1
mv eV KE = =
Less than 1 % of the energy of electrons striking the target converts into
X-rays
SWL
Continuous radiation
Characteristic radiation
Short-wavelength limit Photons of maximum energy,
emitted by electrons stopped in one impact
eV
hc c
SWL
= = =
max
min
v

V
3
10 4 . 12
=

Characteristic x-ray radiation
Similarity - from prior knowledge
Diffraction of visible light by a ruled grating
Wave encounter set of regularly spaced scattering objects
Wavelength of wave in question has same order of magnitude as of
spacing between scattering centers
German physicist von Laue reasoned

If crystals are composed of regularly spaced atoms - can act as
scattering centers for x-rays
If x-rays have wavelength about equal to interatomic distance in
crystal

It should be possible to diffract x-rays by means of crystals
Bragg Law

Geometry of diffraction
Wave 1
Wave 2
Resultant wave
Constructive Destructive Interference

Differences in the length of the path traveled lead to differences in phase

The introduction of phase differences produces a change in amplitude
Wave 3
Crystal planes-
imaginary
d = interplanar spacing

Diffraction
Simplification given W. H. Bragg and W. L. Bragg
u sin 2d n =
Bragg law
Essential condition for diffraction
A diffracted beam may be defined as a beam composed of
scattered rays mutually reinforcing one another
Intensity of diffracted beams
s = s
o
+ S
Scattering of X-rays by a Single Electron
s
o
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
Scattering of X-rays by Two Electrons
Scattering of X-rays by an Atom
Atomic scattering factor f
Forward scattered x-rays all in phase
Equal to Z
f(S) =



whole
atom

(r) e
2 i S.r
V
Scattering by a unit cell

Structure factor
F(S) =


n
f
n
e
2 i (hx + ky + lz )

Calculating the Intensity of Diffraction Using the Structure Factor Equation
Intensity as a function of atom position (arrangement)
The resultant wave scattered by all atoms of the unit cell is called the
structure factor (F)
) ( 2
3
) ( 2
2
) ( 2
1
3 3 3 2 2 2 1 1 1
lw kv hu i lw kv hu i lw kv hu i
e f e f e f F
+ + + + + +
+ + =
t t t

+ +
=
N
lw kv hu i
n
n n n
e f F
1
) ( 2t
Summation extending over all the atoms of the unit cell
1
1
6 4 2
5 3
+ = = =
= = =
i i i
i i i
e e e
e e e
t t t
t t t
Also
Intensity is proportional square of amplitude

2
F
For example,
structure factor of BCC cell

This cell has two atoms of the same kind located at
0 0 0 and
odd is l) k (h n whe 0
4 F
even; is l) k (h when 2
] 1 [
2 2
) (
) 2 / 1 . 2 / 1 . 2 / 1 . ( 2 ) 0 . 0 . 0 . ( 2
+ + =
=
+ + =
+ =
+ =
+ +
+ + + +
F
f
f F
e f F
f e f e F
l k h i
l k h i l k h i
t
t t
Bravais lattice Reflection
present
Reflection
absent
Simple all None
Base centered h and k
unmixed
h and k mixed
Body centered (h+k+l) even (h+k+l) odd
Face centered h k and l
unmixed
h k and l mixed
0 0 0 0 0 0
0 0 0 0 0 0
Crystal structure of NaCl

multiplicity, j
the polarisation factor, P
the Lorentz factor, L
X-ray absorption, A
temperature

Other factors to consider to get measured intensity
2
hkl hkl
cjPLAF I =
1, 1, 1; 1, 1, 1; 1, 1, 1; 1, 1, 1;
1, 1, 1; 1, 1, 1; 1, 1, 1; 1, 1, 1.
The multiplicity j
111
is 8 in this cubic case, meaning that in reality we
would measure an intensity that was 8 times larger due to the 111
Multiplicity, j
There are in fact 8 equivalent sets of planes to 111, all with the same d spacing,
Powder diffraction depends on the random orientation of crystallites
Polarization, P
Case (1): Polarisation in plane of scattering, P = cos
2
2
Case (2): Polarisation perpendicular to plane of scattering, P = 1
Case (3): Unpolarised X-rays, P = (1 + cos
2
2 )/2
Case (1) Case (2)
1
2
3
L = c / (sin sin2)
L = c / (sin
2
cos)
Generally c or c is unity
Powder patterns of materials with large d spacings are likely to have very
intense reflections at low diffraction angles due to the Lorentz factor
Lorentz Factor, L
Diffraction occurs in practice over a small range of angles around the mean, 2
Bragg-Brentano:
Reflection
at a low "glancing" () angle, the depth below the sample is small; at
higher angles the same path length requires deeper penetration into the
sample. However the surprising result is that when all the possible path
lengths are taken in to account, the net absorption remains constant
with . This means that the effect of absorption can effectively be
ignored in this case since it affects all reflections equally.
X-ray absorption, A
Transmission
Diffraction under non-ideal conditions
Ideal conditions:
Perfect crystal (Real crystal have imperfection, also have
finite size)
Incident beam composed of;
Perfectly parallel rays
Strictly monochromatic radiation
Cu K

line has width of 0.001

B
B
t
u

cos
9 . 0
=
Scherrer formula
Estimation of particle size of very small crystals from the measured width
of the diffraction curve
B in radians measure of peak width (Full width half maximum, FWHM)

Any queries