X-ray diffraction and Bragg’s law:

The inter-atomic spacing in crystals is of the order of 1Å. Because of the short wavelength
(comparable to the inter-planer distance), X-rays are scattered by adjacent atoms in crystals which
can interfere and give rise to diffraction effects. When X-rays enter into a crystal, each atom acts as
a diffraction centre and crystal as a whole acts like a three dimensional diffraction grating. The
diffraction pattern so produced can tell us much about the internal arrangement of atoms in crystal.

Let us consider a crystal made up of equidistant parallel planes of atoms with the inter-planer
spacing dhkl. Further, consider a
monochromatic x-ray beam of wavelength 
having a common wave front, falls at an
angle  on the planes as shown in Figure.
Each atom scatter the x-rays more or less
uniformly in all directions, but because of
the periodic arrangement of atoms, the
scattered radiation from all atoms in a set of
planes is in phase where they interfere
constructively. In all other directions, there
is destructive interference.
Consider two of the incoming x-ray OA and O′E inclined at an angle  with the topmost plane of
the crystal and are scattered in the directions AP and EP′, also at an angle  with that plane. Since
the path length of the rays OEP′ and O′AP are the same, they arrive at P and P′ respectively in phase
with each other and again form a common wavefront. This is the condition for scattering in phase
by single plane of the crystal.

Now, let us consider X-ray scattering from two adjacent planes (hkl) 1 and (hkl)2 as shown in Figure.
If EB and ED are parallel to the incident and scattered wavefront respectively, the total path O′CP 
is longer than the path OEP′ by an amount

 = BCD = BC + BD (1)
Now, from the right angle triangle EBC and EDC, we have

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 BC = dsin = BD
So,  = 2d sin (2)
If two consecutive planes scattered in phase with each other then we know that the path difference 
must be equal to an integral multiple of wavelength, i.e.  = n , where n = 0, 1, 2 ... gives the order
of reflection. Thus the condition for constructive interference (in-phase scattering) by a set of
equidistant parallel planes in a crystal is given by
2d sin = n (3)
This is the well known Bragg’s law, which was first derived by the English physicists Sir W.H.
Bragg and his son Sir W.L. Bragg in 1913. Thus diffraction (constructive) occurs for certain
discrete values of  for which the Bragg’s condition is fulfilled.

As (sin)max = 1, we get, .

That is,  must not be greater than twice the interplaner spacing, otherwise no diffraction will occur.

This observation is an example of X-ray wave interference, commonly known as X-ray diffraction
(XRD), and was direct evidence for the periodic atomic structure of crystals postulated for several
centuries. The Braggs were awarded the Nobel Prize in physics in 1915 for their work in
determining crystal structures beginning with NaCl, ZnS and diamond. Although Bragg's law was
used to explain the interference pattern of X-rays scattered by crystals, diffraction has been
developed to study the structure of all states of matter with any beam, e.g., ions, electrons, neutrons,
and protons, with a wavelength similar to the distance between the atomic or molecular structures of
interest.

William Henry Bragg and William Lawrence Bragg were the first and (so far) the only father-
son team to have jointly won the prize. Other father/son laureates include Niels and Aage
Bohr, Manne and Kai Siegbahn, J. J. Thomson and George Thomson, Hans von Euler-
Chelpin and Ulf von Euler, and Arthur and Roger Kornberg, who were all awarded the prize
for separate contributions. W. L. Bragg was 25 years old at the time, making him the youngest
Nobel laureate to date.

For certain specific wavelengths and incident angles, intense peaks of reflected radiation (known as
Bragg peaks) were produced. The concept of Bragg diffraction applies equally to neutron
diffraction and electron diffraction processes. When x-rays are incident on an atom, they make the

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electronic cloud move as does any electromagnetic wave. The movement of these charges re-
radiates waves with the same frequency (blurred slightly due to a variety of effects); this
phenomenon is known as Rayleigh scattering (or elastic scattering). The scattered waves can
themselves be scattered but this secondary scattering is assumed to be negligible. A similar process
occurs upon scattering neutron waves from the nuclei or by a coherent spin interaction with an
unpaired electron. These re-emitted wave fields interfere with each other either constructively or
destructively (overlapping waves either add together to produce stronger peaks or subtract from
each other to some degree), producing a diffraction pattern on a detector or film. The resulting wave
interference pattern is the basis of diffraction analysis.
When the energetic electrons strike the target, which is a pure metal such as copper or molybdenum,
and remove inner (K) shell electrons. When this happens, other electrons from higher level shells
drop into the vacant K-shell and in so doing emit a photon (X-ray) whose wavelength (energy) is
characteristic of the metal target material. In order to remove the inner shell electron, the incoming
electron must have an energy greater than the difference in energy between the inner (K) shell
electron and a free electron in the conduction band of the target metal. This energy difference is
referred to as the absorption edge energy.
Both KCl and KBr have sodium chloride structure
shown in the figure. In this structure the two types
of atoms are arranged alternatively at the lattice
sites of a simple cubic lattice. The space lattice is
fcc with a basis of two non-equivalent atoms at 000
and ½½½.
In KCl the number of electrons of K + and Cl- ions
are equal and the charge distribution is similar.
Therefore, the form factors for K+ and Cl- are almost
exactly equal, so that the crystal looks to x-rays as if
it were a monatomic simple cubic lattice of lattice
constant a/2. Only even integers occur in the
reflection indices when these are based on a cubic
lattice of lattice constant a. In KBr the form factor
of Br- is quite different than that of K+, and all Figure: Comparison between X-ray
reflections from KCl and KBr.
reflections of the fcc lattice are present.

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Exercise: Determine the angle through which an X-ray of wavelength 0.440Å be reflected from the
cube face of a rocksalt crystal (d = 2.814Å).

Solution: Given  = 0.440Å. d = 2.814Å

1st order reflection, n = 1,

2nd order reflection, n = 2,

3rd order reflection, n = 3, , etc.

Exercise: Determine the wavelength of the diffraction beam, when a beam of X-ray having
wavelengths in the range 0.2Å to 1Å incident at an angle of 9 ° with the cube face of a rocksalt
crystal (d = 2.814Å)
Solution: n = 1 11 = 2(2.814) Sin 9°  1 = 0.8804 Å
n = 2 22 = 0.8804Å  2 = 0.4402 Å
n = 3 33 = 0.8804Å  3 = 0.2935 Å
n = 4 44 = 0.8804Å  4 = 0.2201 Å
n = 5 55 = 0.8804Å  5 = 0.1760 Å < 0.2 Å
which shows the wavelength of the X-rays are 0.8804, 0.4402, 0.2935 and 0.2201 Å.

Experimental x-ray diffraction Methods:

To satisfy Bragg’s law, it is necessary to vary either the angle of inclination of the specimen to the
beam or the wavelength of the radiation. The three standard methods of X-ray crystallography are
a) Laue Method: A stationary single crystal is irradiated by a range of X-ray wavelengths.
b) Rotating crystal Method: A single crystal specimen is rotated in a beam of
monochromatic X-rays.
c) Powder Method: A polycrystalline powder specimen is kept stationary in a beam of
monochromatic radiation.
Of these techniques, Laue method is used only for known crystal orientation measurement.

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The powder method assumes that all orientations are present in the sample, so that regardless of the
angle of incidence, there will be a grain in the proper orientation for each reflection (diffraction).
The patterns are very useful for identification of unknowns. There are compiled indexes of powder
diffraction data for minerals, as well as inorganic compounds and organic compounds.

If the Miller indices of the diffraction peaks are known, it is possible to determine the unit cell
parameters of the material from the peak positions. Cell parameters can then be used to determine
composition if the cell variation with composition is known.

If more than one mineral is present in the sample it is possible, although not easy, to determine the
relative proportions of the minerals. To do this one must have a standard pattern for each pure
mineral to obtain the relative intensities of the peaks form each mineral. It is then possible to use the
relative intensities of non-overlapping peaks to give an estimate of the mineral proportions, called a
mode".

Exercise:

Compute the lattice spacing for the (211) reflection of olivine with a = 4.830 Å b= 10.896 Å and c=
6.288 Å:

1/d2 = h2/a 2 + k2/b2 + l2/c2 1/d2= (2/4.830)2 + (1/10.896)2 + (1/6.288)2 d = 2.2077 Å

What is the angle for this reflection using Cu k-alpha radiation ( lambda = 1.5405 Å)

nlambda = 2d sin theta

theta = sin-1 (lambda /2d)
theta = 20.413º
2theta = 40.825º

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Compute the spacing for (131) garnet with a = 11.46Å and Cu k-alpha radiation ( l = 1.5405 Å)

d = a / ( h2 + k2 + l2)1/2
d = 11.46/(11)1/2 = 3.455 Å
n lambda = 2d sin theta
theta = sin-1(n lambda /2d)
= sin-1(1.54/2(3.455))
theta = 12.876º
2theta =25.754º

What is the energy, in joules, of an X-ray photon of Cu k-alpha radiation ( lambda = 1.540 Å)?

E = h nu n = c/l h = Planck's Constant = 6.6 x 10-34 j sec

E = hc / l c = speed of light = 3 x 108
m/sec
1 ev = 1.6019 x 10-19
E = (6.6 x 10-34) j s (3 x 108 m/sec)
/ 1.5405 x 10-10m
E = 1.286x10-15 j /1.6019x10-19
j/ev
in electron volts E = 8026 ev

What frequency is Mo k-alpha radiation ( lambda= 0.70926 Å)?

n = c / lambda
n = (3.0 x 108)m/sec / (.70926 x
10-10))m
n = 4.2297 x 1018sec-1
= 4.2297x1018 htz (htz = hertz = sec-1)

The absorption edge of Cu k-series radiation is 1.380 Å. What is the minimum KV setting on the X-
ray generator required to produce Cu k-series radiation?

E = hc / l = (6.6x10-34 jsec)(3.0x10 8 m/sec) (1.380 x 10-1))m / (1.6019x10-19 ) j/ev E = 8956 ev E =

8.956 Kev = 8.9 KV 5.4. X-ray Powder Diffraction Instruments