Bragg’s Law and Diffraction:
Bragg's law is the result of experiments into the diffraction of X-rays or neutrons off
crystal surfaces at certain angles, derived by physicists Sir W.H. Bragg and his son Sir
W.L. Bragg in 1912. Bragg's law confirmed the existence of real particles at the atomic
scale, as well as providing a powerful new tool for studying crystals in the form of X-ray
and neutron diffraction. The Braggs were awarded the Nobel Prize in physics in 1915 for
their work in determining crystal structures beginning with NaCl, ZnS, and diamond.
When X-rays hit an atom, they make the electronic cloud move as does any
electromagnetic wave. The movement of these charges re-radiate waves with the same
frequency (blurred slightly due to a variety of effects); this phenomenon is known as the
Rayleigh scattering (or elastic scattering). 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. Both
neutron and X-ray wavelengths are comparable with inter-atomic distances (~1.5
angstroms) and thus are an excellent probe for this length scale.
Interference is the superposition of two or more waves resulting in a new wave pattern.
As most commonly used, the term usually refers to the interference of waves which are
correlated or coherent with each other, either because they come from the same source or
because they have the same or nearly the same frequency. Two non-monochromatic
waves are only fully coherent with each other if they both have exactly the same range of
wavelengths and the same phase differences at each of the constituent wavelengths.
The interference is constructive when the phase shift is proportional to 2π; this condition
can be expressed by Bragg's law:
where
n is an integer,
λ is the wavelength of x-rays, and moving electrons, protons and neutrons,
d is the spacing between the planes in the atomic lattice, and
θ is the angle between the incident ray and the scattering plane
Deriving Bragg's Law
Bragg's Law can easily be derived by considering the conditions necessary to make the
phases of the beams coincide when the incident angle equals and reflecting angle. The
rays of the incident beam are always in phase and parallel up to the point at which the top
beam strikes the top layer at atom z (Fig. 1). The second beam continues to the next layer
where it is scattered by atom B. The second beam must travel the extra distance AB + BC
if the two beams are to continue traveling adjacent and parallel. This extra distance must
be an integral (n) multiple of the wavelength () for the phases of the two beams to be
the same:
n = AB +BC (2).
Fig. 1 Deriving Bragg's Law using the reflection geometry and applying trigonometry.
The lower beam must travel the extra distance (AB + BC) to continue traveling parallel
and adjacent to the top beam.
Recognizing d as the hypotenuse of the right triangle Abz, we can use trigonometry to
relate d and to the distance (AB + BC). The distance AB is opposite so,
AB = d sin(3).
Because AB = BC eq. (2) becomes,
n = 2AB (4)
Substituting eq. (3) in eq. (4) we have,
n = 2 d sin(1)
and Bragg's Law has been derived. The location of the surface does not change the
derivation of Bragg's Law.
Diffraction:
Diffraction refers to the various phenomena associated with wave propagation, such as
the bending, spreading and interference of waves emerging from an aperture. It occurs
with any type of wave, including sound waves, water waves, electromagnetic waves such
as light and radio waves, and matter displaying wave-like properties according to the
wave–particle duality. While diffraction always occurs, its effects are generally only
noticeable for waves where the wavelength is on the order of the feature size of the
diffracting objects or apertures.
Explanation:
The most conceptually simple example of diffraction is single-slit diffraction in which the
slit is narrow, that is, significantly smaller than a wavelength of the wave. After the wave
passes through the slit, a pattern of semicircular ripples is formed, approximately equally
strong in all directions, as if there were a simple wave source at the position of the slit.
This semicircular wave is a diffraction pattern.
When the slit is significantly more than a wavelength wide, the wave propagates more
nearly straight through, but a diffraction pattern at the edges of the wave can be seen. The
center part of the wave travels through largely unaffected at short distances, but the wave
forms a stable diffraction pattern at longer distances. This pattern is most easily
understood and calculated as the interference pattern of a large number of simple sources
spaced closely and evenly across the width of the slit.
In multiple-slit experiments, narrow enough slits can be analyzed as simple wave sources.
A slit is an opening that is infinitely extended in one dimension, which has the effect of
reducing a wave problem in 3-space to a simpler problem in 2-space. All the same effects
can be seen and analyzed for small round holes and other shapes, in 3D, but they're
harder to describe, compute, and illustrate.
X-ray crystallography
X-ray crystallography is a technique in crystallography in which the pattern produced by
the diffraction of X-rays through the closely spaced lattice of atoms in a crystal is
recorded and then analyzed to reveal the nature of that lattice. This generally leads to an
understanding of the material and molecular structure of a substance. The spacing in the
crystal lattice can be determined using Bragg's law. The electrons that surround the
atoms, rather than the atomic nuclei themselves, are the entities which physically interact
with the incoming X-ray photons. This technique is widely used in chemistry and
biochemistry to determine the structures of an immense variety of molecules, including
inorganic compounds, DNA and proteins. X-ray diffraction is commonly carried out
using single crystals of a material, but if these are not available, microcrystalline
powdered samples may also be used, although this requires different equipment, gives
less information, and is much less straightforward.
Single Crystal Diffraction
Many complicated inorganic and organometallic systems have been analyzed using single
crystal methods, such as fullerenes, metalloporphyrins, and many other complicated
compounds. Single crystal is also used in pharmaceutical industry, due to recent problems
with polymorphs. The major limitation to the quality of single-crystal data is crystal
quality.
Inorganic single-crystal x-ray crystallography is commonly known as small molecule
crystallography, as opposed to macromolecular crystallography.
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Powder Diffraction
X-ray powder diffraction finds frequent use in materials science because sample
preparation is relatively easy, and the test itself is often rapid and non-destructive. The
vast majority of engineering materials are crystalline and even those which are not, yield
some useful information in diffraction experiments.
The pattern of powder diffraction peaks can be used to quickly identify materials (thanks
to the JCPDS pattern database), and changes in peak width or position can be used to
determine crystal size, purity, and texture.
