Electromagnetic Spectrum

Generation of X-rays
X-rays are electromagnetic radiation of wavelength ∼1 A° (10−10 m).
X-rays are produced when high-energy charged particles, e.g. electrons
accelerated through 30 kV, collide with matter.
▪ Electrostatic potential 20 to 60 kV
▪ Anode current 10 to 50 mA
Input power ~ 0.5 to 3 kW
Only 0.1% transforms into X-ray
beam
▪ The wavelengths, most commonly
used in crystallography: 0.5-2.5 Å
X-ray spectra usually have two
components:
▪ A broad spectrum of
wavelengths known as white
radiation
▪ A number of fixed, or
Figure: Conventional X-ray laboratory source
monochromatic, wavelengths 2
 (b)
(a)

Figure-1: (a) Generation of Cu Kα X-rays. A 1s electron is ionized; a 2p

electron falls into the empty 1s level and the excess energy is released as
X-rays. (b) X-ray emission spectrum of Cu.
For Cu, the 2p → 1s transition, called Kα, has a wavelength of 1.5418 °A
and the 3p → 1s transition, K, 1.3922 A°. The electronic transitions
involved in both the ionization of inner shell electrons and emission of X-
rays are shown in Fig.(1b).
3
 Characteristic X-ray line

The Kα transition occurs much more

frequently than the K transition and the
more intense Kα radiation is used in
diffraction experiments.
4
In fact, the Kα radiation is a doublet, Kα1 = 1.54051 °A and Kα2 = 1.54433 A°
, because the 2p → 1s transition has a slightly different energy for the two
possible spin states of the 2p electron which makes the transition,
relative to the spin of the vacant 1s orbital. More specifically, the 2p
electron has total angular momentum given by the quantum number j = l
± s, where l is the orbital quantum number and s is the spin quantum
number; for a 2p electron l = 1 and therefore j = 3/2 or 1/2 and the two
possible transitions are

Figure-2 Use of Ni to filter

out Cu K and white
radiation.

5
Table: X-ray wavelengths (A˚ ) of commonly used target materials

The energy required to ionize 1s electrons of Ni corresponds to a

wavelength of 1.488 A° , which lies between the values for the Kα and K
lines of the Cu emission spectrum. Cu K radiation, therefore, has sufficient
energy to ionize 1s electrons of Ni whereas Cu Kα radiation does not. Ni foil
is effective in absorbing the Cu K radiation and most of the white
radiation, leaving a monochromatic, reasonably clean beam of Kα
radiation.
6
 Diffraction
Diffraction is the slight bending of light as it passes around the edge of an
object. The amount of bending depends on the relative size of the
wavelength of light to the size of the opening.

Gap-maximum diffraction occurs when the wavelength is equal to the

size of the gap.
7
Interference

8
 X-Ray Diffraction
Max von Laue demonstrated the wave nature of X-ray by the diffraction
effects using a crystal of copper sulfate as the diffraction grating.
Nobel Prize in Physics: 1914.
Prize motivation: "for his discovery of the diffraction of X-rays by crystals’’

9
William Henry and William Lawrence Bragg (father and son) immediately
started experiments on using X-ray crystal diffraction as a means of
structure determination.
In 1913, they first determined the crystal structure of NaCl and then went
on to determine many structures, including those of KCl, ZnS, CaF2, CaCO3
and diamond.
W. L. (Lawrence) Bragg noted that X-ray diffraction behaves like a
‘reflection’ from the planes of the atoms within the crystal and that only
at specific orientations of the crystal with respect to the source and
detector are X-rays ‘reflected’ from the planes.

1915: The Nobel prize for physics

Prize motivation: "for their services in the analysis of crystal structure by
means of X-rays"

10
It is not like the reflection of light from a mirror, as this requires that the
angle of incidence equals the angle of reflection, and this is possible for
all angles.
With X-ray diffraction, the reflection occurs only when the conditions for
constructive interference are fulfilled.

Figure-3: Bragg reflection from a set of crystal planes with a spacing dhkl.
11
 Figure-3 illustrates the Bragg condition for the reflection of X-rays by a
crystal.
The array of black points in the diagram represents a section through a
crystal and the lines joining the dots mark a set of parallel planes with
Miller indices hkl and interplanar spacing dhkl.
A parallel beam of monochromatic X-rays ADI is incident on the planes at
an angle θhkl. The ray A is scattered by the atom at B and the ray D is
scattered by the atom at F.
To emerge as a single beam of reasonable intensity, the reflected beams
must reinforce or arrive in phase with one another by constructive
interference.
For constructive interference to take place, the path lengths of the
interfering beams must differ by an integral number of wavelengths.
If BE and BG are drawn at right angles to the beam, the difference in
path length between the two beams is given by
12
 difference in path length = EFG = EF + FG
but EF = FG = dhklsinhkl
EFG = 2 EF = 2dhklsinhkl --------(1)
This must be equal to an integral number, n, of wavelengths. If the
wavelength of the X-rays is , then
n = 2dhklsinhkl --------------(2)
This is known as the Bragg equation, and it relates the spacing between
the crystal planes (dhkl) to the particular Bragg angle (θhkl) at which
reflections from these planes are observed (mostly the subscript hkl is
dropped from the Bragg angle θ without any ambiguity as the angle is
unique for each set of planes).
When n = 1, the reflections are first-order, and when n = 2 the
reflections are second-order and so on.

13
 First order:  = 2dhklsin1 Second order: 2 = 2dhklsin2
By convention, we set the diffraction order = 1 for XRD.
For instance, when n=2 (as above), we just halve the d-spacing to make
n=1. 𝒅
2  = 2dhklsin2  = 2 𝒉𝒌𝒍 sin2
𝟐

e.g. the second order reflection of d100 occurs at same θ as first order
reflection of d200
If a first-order reflection occur from a set of planes with interplanar
spacing dhkl/2, the Miller indices for the set of planes with interplanar
spacing dhkl/2 will be 2h 2k 2l.
So, the second-order reflection from hkl is indistinguishable from the
first-order reflection from 2h 2k 2l, and the Bragg equation may be
written more simply as
 = 2dhklsin ------------------(3)

14
➢ For large interplanar spacing the angle of reflection tends towards
zero → as d increases, Sin decreases (and so does ).
➢ The smallest interplanar spacing from which Bragg diffraction can be
obtained is /2 → maximum value of  is 90, Sin is 1  from Bragg
equation d = /2.

Order of the reflection (n)

▪ For Cu K radiation ( = 1.54 Å) and d110= 2.22 Å

n Sin = n/2d 
1 0.34 20.70 • First order reflection from (110)
• Second order reflection from (110) planes
2 0.69 43.920 • Also considered as first order reflection from
(220) planes

15
Relation between dnh nk nl and dhkl In XRD nth order reflection from (h k l) is
𝒂 considered as 1st order reflection from (nh
𝑪𝒖𝒃𝒊𝒄 𝒄𝒓𝒚𝒔𝒕𝒂𝒍
𝒅𝒉𝒌𝒍 = nk nl).
𝒉𝟐 + 𝒌𝟐 + 𝒍𝟐
𝒂
𝒅𝒏𝒉𝒏𝒌𝒏𝒍 =
(𝒏𝒉)𝟐 + (𝒏𝒌)𝟐 + (𝒏𝒍)𝟐
𝒂 𝒅𝒉𝒌𝒍
𝒅𝒏𝒉𝒏𝒌𝒏𝒍 = =
𝒏 𝒉𝟐 + 𝒌𝟐 + 𝒍𝟐 𝒏

𝒅𝒏𝒉𝒏𝒌𝒏𝒍 𝟏
=
𝒅𝒉𝒌𝒍 𝒏
𝒅𝟐𝟎𝟎 𝟏
=
𝒅𝟏𝟎𝟎 𝟐
e.g.
𝒂
𝒅𝟏𝟏𝟎 =
𝟐 All these form the (200) set
𝒅𝟐𝟐𝟎 𝟏
=
𝒂 𝒅𝟏𝟏𝟎 𝟐
𝒅𝟐𝟐𝟎 = Hence, (100) planes are a subset of (200) planes
𝟖
16
 X-ray Diffraction (XRD)
The atomic planes of a crystal cause an incident beam of X-rays to
interfere with one another as they leave the crystal. The
phenomenon is called X-ray diffraction.

17
Why X-ray?
An electromagnetic radiation can be diffracted by atomic planes
only when the half of its wavelength is less than the inter atomic
distance (D).

D
𝟐
X-rays are used over visible light for crystal diffraction because of its
shorter wavelength.

Why XRD?
➢ Measure the average spacing between layers or rows of atoms
➢ Determine the orientation of a single crystal or grain
➢ Find the crystal structure of an unknown material
➢ Measure the size, shape and internal stress of small crystalline
regions
18
 Diffraction methods
Method Wavelength Angle Specimen
Laue Variable Fixed Single Crystal
Rotating Fixed Variable Single Crystal
Crystal (in part)
Powder Fixed Variable Powder

LAUE METHOD
▪ In this method, continuous radiation is used.
▪ This radiation falls on a stationary crystal. The crystal diffracts the X-
ray beam and produces a pattern of spots which conform exactly
with the internal symmetry of the crystal.

19
▪ The Laue method can be used in two ways:
Transmission method (Figure 2a)
Back-reflection method (Figure 2b)
• Uses Single crystal
• Uses white radiation
• Used for determining crystal orientation and assessment of crystal
quality .

(a) Transmission method (b) Back-reflection method

Figure 2: Laue methods 20
 Single crystals produce “spot”
patterns similar to that shown to
the figure.

(a)

Figure 4: Laue diffraction patterns (a)

Transmission method and (b) Back
(b) reflection method.
Figure 3: Location of Laue spots (a) on
ellipses in transmission method and (b) on
hyperbolas in back-reflection method.
21
 The Powder Method
An X-ray powder diffraction pattern is a plot of the intensity of X-rays
scattered at different angles by a sample.

▪ In this method, characteristic X-ray radiation of fixed wavelength

(monochromatic) is used.
▪ The material to be studied is in the form of a very fine powder, each
particle of the powder is a very small crystal.
22
▪ If one plane is set at exactly the correct value of  for diffraction, then
we observe one and only one reflected (diffracted) beam from that
crystal.
▪ The detector moves in a circle around the sample
❖ The detector position is recorded as the angle 2theta (2θ).
❖ The detector records the number of X-rays observed at each angle 2θ.
❖ The X-ray intensity is usually recorded as “counts” or as “counts per
second”.
• Many powder diffractometers use the Bragg-Brentano parafocusing
geometry

23
❖ To keep the X-ray beam properly focused, the incident angle omega
changes in conjunction with 2theta.
❖ This can be accomplished by rotating the sample or by rotating the X-
ray tube.
❖ The incident angle, , is defined between the X-ray source and the
sample.
❖ The diffraction angle, 2, is defined between the incident beam and
the detector.
❖ The incident angle  is always ½ of the detector angle 2 .

A sample of some hundreds of crystals (i.e. a powdered sample) show that

the diffracted beams form continuous cones. A circle of film is used to
record the diffraction pattern as shown in figure-5. Each cone intersects
the film giving diffraction lines. The lines are seen as arcs on the film.

24
 Detection of Diffracted X-rays by Photographic film

Figure-5 : Formation of a diffracted cone of radiation in the powder method

25
XRD Pattern of NaCl Powder

Diffraction angle 2 (degrees)

26
 X-rays scatter from atoms in a material and therefore contain information about
the atomic arrangement.

• The three X-ray scattering patterns above were produced by three chemically identical
forms SiO2
• Crystalline materials like quartz and cristobalite produce X-ray diffraction patterns
– Quartz and cristobalite have two different crystal structures
– The Si and O atoms are arranged differently, but both have long-range atomic order
– The difference in their crystal structure is reflected in their different diffraction patterns
❖ The amorphous glass does not have long-range atomic order and therefore produces only
broad scattering features.
27
A single crystal specimen in a Bragg-Brentano diffractometer would produce only
one family of peaks in the diffraction pattern.

28
A polycrystalline sample should contain thousands of crystallites. Therefore, all possible
diffraction peaks should be observed.

▪ For every set of planes, there will be a small percentage of crystallites that are properly
oriented to diffract (the plane perpendicular bisects the incident and diffracted beams).
▪ Basic assumptions of powder diffraction are that for every set of planes there is an
equal number of crystallites that will diffract and that there is a statistically relevant
number of crystallites, not just one or two.
29
Peak Position n = 2dsin
(11) Fix  (Cu Kα) = 1.54 Å
dhkl = 1.54 Å/2sin
When d increases, 𝒂𝟎
Sin decreases (and 𝒅𝒉𝒌𝒍 =
so does ). 𝒉𝟐 + 𝒌𝟐 + 𝒍𝟐
(10)

30
 Peak Intensity
Why some peaks in XRD pattern have high intensity than others?
➢ Some peaks are high in intensity due to the fact that there is more
periodicity than other directions.
➢ The height of the peak will be high if there is a preferred crystal
orientation, however, if crystals are arranged in a chaotic or
random order then the height of the peak will be low.
➢ Higher the electron density variation, higher the intensity for that
plane reflected in the XRD pattern.
➢ Peak intensity represents the atomic position in the crystal
structure. For instance, if an atom in the FCC crystal structure
moves to BCC crystal so that the intensity will disappear.

31
Peak intensities are determined by position of atoms within a unit cell.
Let’s take an example

FCC BCC

32
Conclusively, it can be stated that the overall intensity of a peak is
because of the superposition of all the constructive and destructive
contributions which is obviously guided by the position of atoms. 33
 Indexing the peaks
Which planes are responsible for each reflection?
-need to index the reflections (assign the correct hkl)
-difficulty may range from simple to extremely difficult
The planes giving rise to the smallest Bragg angle will have the largest
d-spacing.
-consider a primitive cubic system, with the 100 planes having the
largest separation (the 010 and 001 planes also reflect at this position)

34
35
The pattern of observed lines for the two other cubic crystalline
systems, body-centered and face-centered is different from primitive.

36
 Indexing Example – SrTiO3

Diffractometer equipped with a copper X-ray source.

-copper sources emit X-rays with a wavelength,  = 1.5406 Å.
37
 Let Z = 0.0654 Miller indices

The (300) and (221) peaks fall at the same location, both give
h2 + k2 + l2 = 9.

38
39
40
41
42
43
44
Problem: Below are listed diffraction angels for the first three peaks (first
order) of the diffraction pattern for a metal. Monochromatic radiation
having a wave length of 0.1542 nm was used in the experiment.
Peak order Diffraction angle (2)
1st 38.6o
2nd 55.7o
3rd 70.0o

Determine whether this metal’s crystal structure is FCC, BCC, or neither

FCC or BCC and explain the reason for your choice.
Solution:
We can use the following steps to determine the crystal structure:
Step 1: determine dhkl for each of these reflections;
Step 2: use dhkl to calculate lattice parameter for first three FCC & BCC
reflections
Step 3: see whether lattice parameter is constant or changing 45
 Step 1: determine dhkl for each of these reflections;
Bragg law :  = 2dhklsin (First order, n =1)

dhkl =
𝟐𝒔𝒊𝒏

Peak order Diffraction angle (2) dhkl (nm)

1st 38.6o 0.233
2nd 55.7o 0.165
3rd 70.0o 0.134

Step 2: use dhkl to calculate lattice parameter for first three FCC & BCC
reflections
FCC : h, k, l need to be all even or all odd
BCC : (h + k + l) should be even Principle diffraction planes

Example
FCC : (111), (200), (220)
BCC : (110), (200), (211) 46
  = 2dhklsin Determine which peak comes first
constant minimize
maximize
𝒂
𝐅𝐨𝐫 𝐜𝐮𝐛𝐢𝐜 𝐬𝐲𝐬𝐭𝐞𝐦, 𝒅𝒉𝒌𝒍 =
𝒉𝟐 + 𝒌𝟐 +𝒍𝟐

a = dhkl × 𝒉𝟐 + 𝒌𝟐 + 𝒍𝟐

We know for FCC :

The first three peaks are (111) , (200), (220)

a1 = d1 × 𝟏𝟐 + 𝟏𝟐 + 𝟏𝟐 = 0.233  √𝟑 = 0.403 nm

a2 = d2 × 𝟐𝟐 + 𝟎𝟐 + 𝟎𝟐 = 0.165  √𝟒 = 0.33 nm

a3 = d3 × 𝟐𝟐 + 𝟐𝟐 + 𝟎𝟐 = 0.1344  √𝟖 = 0.38 nm

a1  a2  a3 ; so, metal is not FCC

47
 We know for BCC :
The first three peaks are (110) , (200), (211)

a1 = d1 × 𝟏𝟐 + 𝟏𝟐 + 𝟎𝟐 = 0.233  √2 = 0.3295 nm

a2 = d2 × 𝟐𝟐 + 𝟎𝟐 + 𝟎𝟐 = 0.165  √𝟒 = 0.33 nm

a3 = d3 × 𝟐𝟐 + 𝟏𝟐 + 𝟏𝟐 = 0.1344  √4 = 0.329 nm

a1  a2  a3 ; Therefore, metal is BCC

Problem:
The first three diffraction peaks of a metal are 2 = 44.4o, 64.6o and
81.7o obtained using CuK radiation (  = 0.1542 nm). Is the metal
Cr, Ni, Ag or W? Given that atomic radius of Cr, Ni, Ag and W are
0.1249, 0.1246, 0.1445 and 0.1371 nm respectively.

48
 Solution: First three peaks
Cubic rules: SC- (100), (110), (111), (200), (201), (211), (220), (221), (222)
FCC- (111), (200), (220), (222)
BCC- (110), (200), (211), (220), (222)
 = 0.1542

d=  = 22.2o
Applying Bragg Law on the first peak : 𝟐𝒔𝒊𝒏
d = 0.204 nm (General value)
𝒂𝟎
𝒅𝒉𝒌𝒍 =
𝒉𝟐 + 𝒌𝟐 + 𝒍𝟐
𝒂𝒐
𝐅𝐨𝐫 𝐒𝐂, 𝒅𝟏𝟎𝟎 = = ao = 0.204 nm ; r = 0.102 nm ao = 2r
𝟏𝟐 + 𝟎𝟐 +𝟎𝟐
𝒂𝒐 𝒂𝒐
𝐅𝐨𝐫 𝐅𝐂𝐂, 𝒅𝟏𝟏𝟏 = = ; ao = 0.346 nm; r = 0.1223 nm ao = 2 𝟐r
𝟏𝟐 + 𝟏𝟐 +𝟏𝟐 𝟑
𝒂𝒐 𝒂𝒐 𝟒𝒓
𝐅𝐨𝐫 𝐁𝐂𝐂, 𝒅𝟏𝟏𝟎 = = ; ao = 0.283 nm; r = 0.1225 nm ao =
𝟐 𝟐
𝟏 + 𝟏 +𝟎 𝟐 𝟐 𝟑
Cr, Ni, Ag, W 49
For second peak:
  = 0.1542
d=
𝟐𝒔𝒊𝒏
 = 32.3o
d = 0.1443 nm
𝒂𝒐 𝒂𝒐
𝐅𝐨𝐫 𝐅𝐂𝐂, 𝒅𝟐𝟎𝟎 = = ; ao = 0.2886 nm; r = 0.1020 nm
𝟐 𝟐
𝟐 + 𝟎 +𝟎 𝟐 𝟒

𝒂𝒐 𝒂𝒐
𝐅𝐨𝐫 𝐁𝐂𝐂, 𝒅𝟐𝟎𝟎 = = ; ao = 0.2886 nm; r = 0.1250 nm
𝟐 𝟐
𝟐 + 𝟎 +𝟎 𝟐 𝟒

Cr, Ni, Ag, W

  = 0.1542
For third peak: d=
𝟐𝒔𝒊𝒏
 = 40.85o
d = 0.1179 nm
𝒂𝒐 𝒂𝒐
𝐅𝐨𝐫 𝐁𝐂𝐂, 𝒅𝟐𝟏𝟏 = = ; ao = 0.2888 nm; r = 0.1250 nm
𝟐 𝟐
𝟐 + 𝟏 +𝟏 𝟐 𝟔

Answer: Cr
50
 XRD Pattern of NaCl and KCl

Figure: A comparison of the X-ray powder diffraction patterns of NaCl (bottom)

and KCl (top). The KCl peaks are shifted to lower angles relative to the NaCl
pattern due to the larger cubic unit cell of KCl
51
 X-Ray Diffraction Pattern of polycrystalline -iron
z z z
c c c

y y y
a b (110) a b a b
x x x
Intensity (relative)

(211)

(200)

Diffraction angle 2

Figure: Diffraction pattern for polycrystalline -iron (BCC)

52
The diffraction pattern of a mixture is a simple sum of the scattering from each
component phase.

Databases such as the Powder Diffraction File (PDF) contain dI lists for thousands of
crystalline phases.
The PDF contains over 300,000 diffraction patterns.
53
 A powder pattern of a crystalline phase is its ‘fingerprint’
There are two main factors which determine XRD patterns: (i) the size
and shape of the unit cell and (ii) the atomic number and position of
atoms in the cell.
Thus, two materials may have the same crystal structure but almost
certainly will have distinct powder patterns. For example, KF, KCl and KI
all have the rock salt structure and should show the same set of lines in
their powder patterns, but, as can be seen from Table both the positions
and intensities of the lines are different in each.
Table: X-ray powder diffraction patterns for potassium halides

54
The positions or d-spacing vary because the unit cells are of different
size and, therefore, the a parameter in the d-spacing equation varies.
Intensities differ because different anions with different atomic numbers
and therefore different scattering powers are present in the three
materials, even though the atomic coordinates are the same for each
(i.e. cations at corner and face center positions, etc.).
Problem:
Each crystalline solid gives a characteristic X-ray powder diffraction
pattern which may be used as a fingerprint for its identification.’ Discuss
the reasons for the validity of this statement and indicate why two solids
with similar structures, e.g. NaCl and NaF, may be distinguished by their
powder patterns.

55
 Neutron Diffraction
❑ According to the wave-particle dualism (λ = h/mv, de Broglie) neutrons
have wave properties
❑ As X-rays and neutrons have a wavelength on the order of the atomic
scale (Å), a similar interaction strength with matter (penetration depth
from μm to many cm) occurs.
❑ Neutrons generate interference patterns and can be used for Bragg
diffraction experiments
❑ Same scattering theory for neutrons and X-rays (n = 2d Sin)
Generation of neutrons
Neutron must be released from the atomic nuclei, two possibilities:
(i) Fission
A high continuous flux of neutrons is produced in the core of a
conventional fission reactor (235U nuclei break into lighter elements and
liberate 2 to 3 neutrons).
56
(ii) Spallation source
By bombarding a target of heavy elements with high-energy particles
(typically protons), neutrons can be produced (proton bombardment of
lead nuclei, releasing spallation neutrons).

57
 Properties of neutrons
❖ Fission process: 1 MeV – too high for practical use
❖ Neutrons are slowed down (moderated in water or carbon)
(i) Hot neutrons:
▪ moderated at 2000°C
▪ 0.1-0.5 eV, 0.3-1 Å, 10000 m/s
(ii) Thermal neutrons:
▪ moderated at 40°C
▪ 0.01-0.1 eV, 1-4 Å, 2000 m/s
(iii) Cold neutrons:
❖ moderated at -250°C
❖ 0-0.01 eV, 0-30 Å, 200 m/s

58
 Neutron vs XRD
Neutrons X-rays
Particle wave Electromagnetic wave
Mass, Spin 1/2, Magnetic dipole No mass, spin 1, no magnetic dipole
moment moment
Neutrons interact with the nucleus X-ray photons interact with the electrons
Scattering power independent of 2θ Scattering power falls off with 2θ
Lower absorption Stronger absorption
Large amounts of sample needed Less amounts of sample needed
Neighbors and isotopes can be Neighbors and isotopes cannot be
discriminated discriminated
Light elements can be seen Light elements hard to detect
Low availability (nuclear reactor) High availability (lab instrument)
Magnetic structures can be investigated Magnetic structures cannot be
investigated
Neutron diffraction is a very expensive Less expensive than neutron diffraction
technique.
59
The neutron beam has a larger penetration depth than an electronic beam and an
X-ray with similar energy.
Neutron diffraction can observe light elements such as H, C, N, and O, which are
undetectable in X-ray diffraction. Therefore, neutron diffraction has been applied
to studies on hydrogen storage alloys, oxygen atomic coordinates in high-
temperature superconductivity, and organic materials.
60
Figure: Antiferromagnetic superstructure in MnO, FeO and NiO, showing
pseudocubic unit cell for which a (supercell) = 2a (subcell). Oxygen positions are
not shown.
The unit cell of ‘antiferromagnetic’ NiO, which is stable below 2500C, has eight
times the volume of paramagnetic NiO, stable above 2500C.
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 *These extra lines are
associated with the
antiferromagnetic
superstructure.

Figure: Schematic neutron and powder XRD patterns for MnO for λ =
1.542 A˚ . Peaks are assigned Miller indices for the cubic unit cells
given.
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Electrons scatter X-rays, whereas neutrons are scattered by the nucleus.
▪ With X-rays, the scattering factor increases linearly with the number
of electrons around the nucleus. Heavy atoms scatter more
effectively.
▪ Since the scattering of X-rays from different parts of the electron
cloud are not always in phase, the scattering factor decreases with
sinθ/λ.
▪ Neutron scattering factors are randomly affected by resonance
scattering, which occurs when a neutron is absorbed by the nucleus
and later released.
▪ Nuclear scattering factors do not decrease with sinθ/λ.
▪ Nuclei are similar in size and scattering factors are similar for nearly
all the elements.
▪ Low Z (light) atoms scatter as effectively as high Z (heavy) atoms.
This enables one to accurately locate atoms such as oxygen in the
presence of heavy metal atoms. 63
▪ Crystals do not absorb neutrons, so they are useful for studying compounds
that contain heavy atoms that strongly absorb X-rays.
▪ Similar atoms are difficult to distinguish using X-ray diffraction (O2−and F−;
Zr4+ and Nb5+ ), however a neutron structure determination may be able to
distinguish between the two.
▪ Neutron diffraction is also used to distinguish atoms that have similar X-ray
scattering powers, such as Mn, Fe, Co and Ni.

64
 Electron diffraction
Louis de Broglie developed the idea that electrons exhibit both particle and wave
properties. He proposed that, analogous to photons, the wavelength of the
electron wave is given by

where h is Planck’s constant and p is the electron momentum which is given by

p = mv in the non-relativistic limit.

65