Assignment #1

Muhammad Umer Zahid

Advance Concepts of NSE
PhD Chemical Engineering
202589
Structural Factor: Why some peaks appear and some not i.e 0001 don’t
appear and 0002 appear

Diffraction: X-rays interacting with matter can undergo three processes; transmission,
Diffraction and Reflection.

It is known that for =wavelength and a=Distance between scattering centers

  < a  transmission dominated.

  ~ a  diffraction dominated.
  > a  reflection dominated.

For Diffraction the wavelength of the incident light has to be on the same order as the spacing of
the atoms.

Difference in path length = BC + CD; BC = CD = dhklsinθhkl. Additional path length =

2dhklsinθhkl must be an integral number of wavelengths, nλ = 2dhklsinθhkl (n = 1, 2, 3, …). Hence
diffraction is only possible under certain conditions which allow constructive interference as
explained by Bragg’s Law. In short diffraction is coherent reinforced scattering, given as

λ = 2d sin(θ )

If wavelength is not of the order of the spacing of the scatterers, then the number of peaks
obtained may be highly restricted (i.e. we may even not even get a single diffraction peak!) as in
case of amorphous solids.

Diffraction should not be confused with reflection some basic difference between them can be
stated as;
Reflection Diffraction

Occurs throughout the bulk

Occurs from surface (though often the penetration of x-rays in only
of the order of 10s of microns in a material)

Takes place at any angle Takes place only at Bragg angles

~100 % of the intensity may be reflected Small fraction of intensity is diffracted

Real Life Example: If you look at a CD when exposed to white light you can see it diffracted
into varies wavelengths of color. The pits (or grooves) in the CD are the regularity of the
material that causes the diffraction.

Missing Reflections or Absence of Peak: For simple perfect cubic structure all peaks are
present, for any other crystal structure some peaks can be absent most commonly known as
systematic absences.

This is due to the presence of additional atoms or atomic plane within unit cell of crystal
structure. So if ‘a’ is the cell dimension, the additional planes will have spacing a/2. As a result
2d sin(θ) will no longer be equal to integer value of wavelength and hence destructive
interference will take place. Therefore the peak due to that particular plane will be absent.

For example for FCC structure; the reflection from the 200 plane is exactly out of phase with the
100 reflection and destructive interference occurs hence no 100 reflection is observed.
For BCC structure atom at center results in reflection which is exactly out of phase and therefore
gives absence of peak due to destructive interference

It is therefore general rule for BCC structure that only peaks which give (h+k+l=even number)
are shown.
Similarly for much other crystalline structure some general rules can be used to predict
disappearance of peaks.

An x-ray diffraction pattern of α-iron showing only (h+k+l=even) peaks.

For FCC structure peaks to be present H,K,L should be all even or all odd as mentioned in table
below.

Allowed list of h2 + k2 + l2 for cubic crystals

Forbidden Primitive, P Face Centered, F Body Centered, I Corresponding hkl

numbers
1 100
2 2 110
3 3 111
4 4 4 200
5 210
6 6 211
7
8 8 8 220
9 221, 300
10 10 310
11 11 311
12 12 12 222
13 320
14 14 321
15
16 16 16 400
For hexagonal systems allowed reflection rule is L should be even and H+2K 3

Therefore one can easily calculate that in HCP structure 0002 will appear while 0001 will not.