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X-Ray Diffraction and the Bragg Equation

Christopher G. Pope
Chemistry Department, University of Otago, Dunedin, New Zealand

A typical derivation of the Bragg equation (1) is easy mance of a X-ray powder diffractometer. A schematic dia-
to understand but leaves a good deal unexplained. A gram of the device is shown in Figure 3.
slightly more critical approach, although a little more The curved crystal focuses radiation onto the detec-
demanding, is more interesting and provides a better in- tor just as a curved mirror would be expected to focus
troduction to the use of X-ray diffraction in structure visible light, and so increases the signal received. Be-
determination. cause the “mirror” action of the crystal occurs only at
Usually, the treatment begins with a diagram that the precisely required angle for X-rays of a single wave-
shows a regular array of scattering points, drawn so that length, it only reflects selected monochromatic radiation,
they lie on a set of parallel lines, distance d apart. In-
terference between parallel beams of X-rays, reflected
as if from a mirror from these lines of points, is then
considered. The condition for constructive interference,
that the rays reflected from adjacent lines should differ
in path length by an integral number, n, of wavelengths,
then easily leads to the Bragg equation.
n λ = 2d sinθ (1)
However, in this derivation it is not explained why the
angles of incidence and reflection should be equal. For
example, why should a diagram such as Figure 1 not
have been used? Here, the condition for constructive in-
terference between the parallel rays scattered from X
and Y is easily seen to be
n λ = d (sinθ1 + sinθ2) (2)
It is clearly not necessary for θ 1 to equal θ2, and it Figure 1. Alternative diagram, showing the path difference between
is easy to see that the same reflection condition will ap- parallel rays.
ply to the whole set of scattering centers that lie on the
line XY or its extension, and are placed d apart. How-
ever, it is important to realize that in X-ray diffraction
experiments we are relying on a cooperative effect, and
that we will only observe intense diffracted X-ray beams
at sharply defined angles if very large numbers of scat-
tering centers (typically more than 107) are producing
radiation that is in phase. We therefore need to estab-
lish what is required to achieve this condition for all the
centers in a regular three-dimensional array.
The easiest way to begin this problem is to look at
the path difference that exists between rays scattered
from centers that lie a distance , apart in a line in the
top plane, as shown in Figure 2. The path difference be-
tween rays AB and CD is
path difference = , (cosθ 1 { cosθ 2) (3)
Constructive interference between all the scattering Figure 2. Reflection from points in the top Bragg plane.
points at any spacing in such a line is only possible if θ1
= θ2. If the argument is extended to consider scattering
points that exist in different parallel lines drawn across
the surface—that is, to consider all the scattering points
in the plane—it can be seen that the incident and scat-
tered beams must both lie in a plane perpendicular to
the surface.
Of course, vector algebra (2) can be used to give
these results more succinctly and elegantly, but there is
a danger that a clear physical understanding of the
Bragg conditions for reflection will then be lost.
A rather useful way to illustrate both the similar-
ity and difference between X-ray reflections from a crys-
tal and the reflection of light by a mirror is to examine Figure 3. Curved crystal monochromator. A is the X-ray source, B
the behavior of a curved crystal focusing monochroma- the sample, C the curved crystal, and D the detector. S are slits
tor (3), which is sometimes used to improve the perfor- limiting the width of the X-ray beam.

Vol. 74 No. 1 January 1997 • Journal of Chemical Education 129

Information • Textbooks • Media • Resources

and X-rays of a different wavelength (due for example for reflection to occur is also the same for (a) and (b).
to X-ray fluorescence) do not get focused onto the detec- However, the atoms B (large circles) are now in positions
tor. This can significantly improve the signal-to-noise exactly halfway between the Bragg planes, so that if
ratio in the observed X-ray diffraction pattern. there is a one-wavelength difference in path length be-
As X-ray scattering is caused by the extranuclear tween rays reflected from the atoms A (small circles) in
electrons in the atoms of the sample being examined, the top and second layers, there must be a half-wave-
the diagrams used often lead to the misconception that length difference between rays reflected from the A and
the points shown must represent the positions of the cen- B atoms. Hence the contributions from A and B will in-
ters of the atoms in the structure of the solid. It is most terfere destructively. As the scattering powers of atoms
important to establish why this is not true, as unless A and B will generally be different, we expect still to
this is done, it is not possible to appreciate how the in- observe a reflection, as the cancellation of the waves will
tensities of the diffracted beams can be used to deter- not be complete, but the amplitude and hence the inten-
mine crystal structures. sity of the beam will be altered.
Fortunately, it is only necessary to think about the Notice that each reflection has to be considered in-
diffraction pattern we would expect to observe from a dividually. For example, if the Bragg equation were sat-
schematic two-dimensional crystal, to see what prin- isfied with n = 2 (a second order reflection from the same
ciples are involved. Extension of these ideas to the real set of planes in which the new angle θ is such that the
three-dimensional case is easy once this has been done. path difference between rays reflected from A atoms in
Suppose that the center of a particular atom is ar- the top and second layer is now two wavelengths), then
bitrarily chosen as the position of one of the lattice the rays scattered from A and B atoms would be one
points. This is always legitimate, as there is no special wavelength different in phase, and hence interfere con-
a priori reason for using any specific location in space structively.
as the position of a given lattice point. Of course, once Figure 4(c) represents a solid with the same chemi-
this initial choice has been made, the repeating pattern cal composition as the one shown in Figure 4(b), but with
must be such that the center of an atom of the same kind, a different atom arrangement. It also has the same unit
with an exactly similar environment of surrounding at- cell size and shape as structures 4(a) and 4(b), so the
oms, must be at all the other lattice points. For example, Bragg condition for reflection must result in reflected
if the “atom” in question is a cesium ion in cesium chlo- beams at exactly the same angles for each of them, but
ride, there must be cesium ions centered at all the other of course, the relative intensities of the beams from each
lattice points, and the arrangement of chloride ions structure will differ.
around each cesium ion must look the same from the
center of any one of the cesium ions in the crystal. All
this follows from the definition of a lattice point—a point
chosen so that the environment of each such point is
identical—and has nothing specifically to do with the fact
that the regular patterns we are concerned with are
made up from atoms or ions.
Figure 4 shows three different two-dimensional ar-
rangements of “atoms” having regularly repeating patterns.
For most purposes, to understand what determines the
relative intensities of the different possible X-ray reflec-
tions allowed by the Bragg equation, we only need to con- Figure 4. Three schematic two-dimensional solid structures.
sider the scattering effect associated with each unit cell,
as the complete description of one cell defines the exact
geometric pattern that is repeated an enormous num-
ber of times to produce a picture of the complete crystal.
Clearly, in general, all the atoms in the unit cell
must be expected to contribute to the amplitude of the
reflected beam. The relative size of the contribution is
determined mainly by the kind of atom involved and the
position of the atom in the cell that controls the perpen-
dicular distance of the atom from the nearest Bragg
plane giving rise to the reflection being considered. When
the contributions from all the atoms in the unit cell are
added, we get the net scattering effect which can be as-
sociated with each lattice point. This depends on the re-
flection being considered and on the structure of the
solid, and is called the structure factor.
In Figure 4(a), which might represent a solid ele-
ment, the atoms are all the same, and are all located at
lattice points in a very simple arrangement. In this case
the contributions of each atom to the reflected beam are
in phase when the Bragg condition for reflection from
the layers shown a distance d apart is satisfied.
Figure 4(b) represents a compound AB containing
equal numbers of two kinds of atoms, shown as the larger
and smaller circles. This structure has the same unit cell Figure 5. Powder XRD patterns for KBr and KCl. Lines 1–6 appear
size and shape as structure 4(a), so the Bragg condition in both patterns, but lines A, B, and C appear only in the pattern for KBr.

130 Journal of Chemical Education • Vol. 74 No. 1 January 1997


Comparison of the powder XRD patterns produced
by samples of potassium bromide and potassium chlo-
ride illustrates some of the points just discussed (Fig.
5).
These two solids have the same shape (cubic) unit
cell and the same relative positions for the ions in the
cell, but the larger ionic radius of Br{ compared with Cl{
causes KBr to have the larger unit cell. The similarity
in structure results in the similarity in both relative po-
sition and relative intensity in the diffraction patterns,
as far as peaks 1–6 are concerned. The extra peaks A, B,
and C in the KBr pattern arise because whilst K+ and
Cl{ are isoelectronic ions and so scatter X-rays almost
equally well, the ions K+ and Br{ do not. For the peaks
corresponding to the Bragg angles A, B, and C, the scat-
tering contributions for cations and anions are exactly
half a wavelength out of phase with each other, and so
cancel out for KCl but not for KBr. The contributions of
cations and anions are in phase for the peaks 1–6, and
so these reflections appear in the patterns for both sol-
ids and are characteristically more intense.
To summarize so far, it can be said that if you only
want to know the size and shape of the unit cell for a
solid phase (which seems unlikely), all you need to know
are the angles at which Bragg reflection occurs as a crys-
tal is moved through all possible orientations with respect
to a monochromatic X-ray beam of known wavelength.
This is most easily achieved in an experiment in which
a single crystal is mounted so that it can be rotated about
its three symmetry axes in turn. In principle, of course,
only six independent Bragg angles are needed to deter-
mine the three unit cell edge lengths, and three angles
between the cell axes, but as every reflection must be
consistent with these same six parameters, the extra
reflections observed provide a very useful check that the
unit cell geometry has been correctly established.
If you wish to identify a solid phase, this can be
achieved by using the angles and relative intensities of
a fairly small number of the stronger reflections to “fin-
gerprint” the sample. This is usually done using the pow-
der technique and is analogous to using an infrared spec-
trum to identify an organic compound, although the X-
ray method is usually much more specific. In this tech-
nique, the sample consists of very many small crystals,
oriented at every angle with respect to the X-ray beam
throughout the experiment, so that all Bragg planes with
a particular spacing give rise to a reflection at a single
observed angle of deflection, and some information is
lost. Despite this, used in conjunction with standard sets
of tables, powder diffraction can discriminate positively
between tens of thousands of known solids.
If you need to know exactly what the arrangement
of atoms in a solid structure is, you then need accurate
information about the intensities of a large number of
X-ray reflections, and the problem can usually be solved
only if you have a suitable single crystal of the material
you wish to examine. A considerable amount of compu-
tation is also required. However, in many cases the com-
plete process can now be carried out almost routinely
Vol. 74 No. 1 January 1997 • Journal of Chemical Education
Information • Textbooks • Media • Resources
and without an extensive knowledge of the theory of X-
ray crystallography.
As well as explaining in outline why the amplitudes
and hence intensities of reflected X-ray beams depend
on how atoms are arranged within the unit cell, an in-
troduction to the Bragg equation can also be used to ex-
plain why solids consisting of very small crystallites or
imperfectly crystallized materials in which there is some
disorder in the positions of the atoms in the structure
produce rather broad, weak diffraction lines. This follows
directly from diffraction theory, which shows that as the
number of regularly spaced scattering centers increases,
the angles at which diffracted beams are observed be-
come more and more sharply defined. Thus, the angular
spread of reflected X-ray beams can give a useful mea-
sure of the particle size of very finely divided solids (5).
The semiempirical Scherrer equation
t = Kλ (4)
B cos θ
describes this effect. K is a constant, which depends
somewhat on particle shape, but is usually about 0.90;
λ is the wavelength of the X-rays; B is the angular width
of the beam at which the intensity falls to half its maxi-
mum value; and t measures the average dimension of
the particles in a direction perpendicular to the Bragg
planes giving rise to the reflection. Line broadening due
to instrumental factors must of course be subtracted
from the observed beam width before the equation is
applied, and this prevents the method being useful once
the regions of crystallinity exceed about 50 nm. Particles
smaller than about 5 nm usually lead to reflected beams
too broad and diffuse for accurate measurement, so in
fact the equation can be applied successfully only over
a rather limited size range. However, it is possible to dis-
tinguish between ordering in different directions in a
crystal. This is apparent, for example, in the diffraction
patterns obtained from samples of carbon black, which
usually show only reflections that arise from approxi-
mately evenly spaced graphite layers, and no other detail.
The approach in this note is aimed at making bet-
ter use of a piece of theory that is introduced into a large
number of courses, without demanding much extra
teaching time. The excellent Symposium on Teaching
Crystallography (6) shows many ways in which this ma-
terial could be followed up.
Literature Cited
1. Atkins, P. W. Physical Chemistry, 5th ed.; Oxford University: Oxford,
1994; p 728.
2. Moore, W. J. Physical Chemistry, 5th ed.; Longman: London, 1972;
p 841.
3. Bertin, E. P. Introduction to X-ray Spectrometric Analysis; Plenum:
New York, 1978; p 152.
4. For example, Willard, H. H.; Merritt, L. L., Jr.; Dean, J. A. Instru-
mental Methods of Analysis, 5th ed.; van Nostrand: New York, 1974;
p 291.
5. Anderson, J. R. Structure of Metallic Catalysts; Academic: London,
1975; p 365.
6. Symposium on Teaching Crystallography. J. Chem. Educ. 1988, 65,
472.
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