Lecture 13

30/01/2024
Hand of Anna Bertha Ludwig
 X-ray Diffraction
First question to ask about an inorganic substance is:
‘What is it?’

Methods are of two main categories, depending on whether

the substance is molecular or non-molecular

Combination of Powder X-ray

spectroscopic methods diffraction, XRD and
and chemical analysis chemical analysis
▪ Molecular weight, ▪ Unit cell or average
functional group crystal structure
 What is X-ray?

➢ X-rays are electromagnetic radiation of wavelength ∼1 Å

(10−10 m)
 How to generate X-ray?
➢ Monochromatic X-rays are used for all laboratory-based diffraction
experiments
 How to generate X-ray?
➢ Monochromatic X-rays are used for all laboratory-based diffraction
experiments
 Interaction of X-rays with matter
➢ Two general ways: scattering and absorption.
➢ If there is no loss of energy on scattering → Coherent X-rays → used
for diffraction experiments
➢ Absorbed by matter → ionization of electrons/to promotion of
electrons to higher, unoccupied energy levels → not intended
 Diffraction
Diffraction: the spreading of waves around obstacles.
Diffraction
 Diffraction

➢ Consider the diffraction of light by

an optical grating
➢ Optical grating : A piece of glass
with many accurately parallel
and closely spaced lines;
separation of the lines is slightly
larger than the wavelength of light
➢ In the grating the lines act as
secondary point sources of light
and re-radiate light in all
directions
➢ Interference then occurs
between the waves originating
from each line source
Grating is shown in
projection as a row of points
 Diffraction
➢ If adjacent beams are in-phase with each other, and
constructive interference occurs to give a resultant diffracted
beam in that direction
➢ In direction 2, the beams are also in-phase although beam B
is now exactly one wavelength behind beam A
➢ For directions between 1 and 2, B lags A by a fraction of one
wavelength, and destructive interference occurs.
 Diffraction
➢ For a certain direction, diffracted wave is exactly half a
wavelength behind other → complete destructive
interference, or cancellation occurs
➢ Thus, directions 1 and 2 have maximum light intensity and this
falls off gradually to zero as the angle changes to direction 3.

www.doitpoms.ac.uk/tlplib/diffraction
 Diffraction
➢ The directions, such as 2, in which constructive interference
occurs are governed by the wavelength of the light, λ, and
the separation, a, of the lines on the grating.
➢ If 1 and 2 are in-phase, the distance AB must equal a whole
number of wavelengths
 Crystals and diffraction of X-rays
➢ Two parallel planes of atoms with same h, k, l values
➢ For 1 and 2 to be in-phase, the distance xyz must equal a whole
number of wavelengths
➢ When Bragg’s law is satisfied, the reflected beams are in-phase and
interfere constructively

William Henry Bragg (1862-1942), William

Lawrence Bragg(1890-1971) Nobel Prize (1915)
 Crystals and diffraction of X-rays
➢ Two things will be key to explain the phenomenon:
1. Model atoms as mirrors: Laws of specular reflection can
be applied
2. Apply interference criteria
• In-phase rays Amplify
• Out-of-phase Dampens
• Constructive and destructive interference

For every diffracted beam

there exists a set of crystal
lattice planes such that the
diffracted beam appears to
be reflected from this set of
planes
X-ray diffraction methods
 Crystals and diffraction of X-rays

Specular reflection: Angle of

incidence = Angle of reflection (both
measured from the plane and not
from the normal) The incident beam,
the reflected beam and the plane
normal lie in one plane

Interference criteria + crystal structure

= set of expected reflections
= Fingerprint of the crystal structure
Crystals and diffraction of X-rays
 Solving X-Ray pattern

Cu target, Wavelength = 1.5418 Angstrom

2θ
44.48
51.83 Unknown sample, cubic
76.35
Determine:
92.90
1) The crystal structure
98.40 2) Lattice parameter
121.87
144.54
 5 steps for the determination of crystal structure
1) Start with 2θ values and generate a set of sin2θ values

2) Normalize the sin2θ values by dividing it with first entry

3) Clear fractions from normalized column: Multiply by

common number

4) Speculate on the hkl values that, if expressed as

h2+k2+l2, would generate the sequence of the “clear
fractions” column

5) Compute for each sin2θ /(h2+k2+l2) on the basis of the

assumed hkl values. If each entry in this column is identical, then
the entire process is validated.
 Solving X-Ray pattern

2θ Sin2θ Sin2θ/Sin2θ1 Clear (hkl)? sin2θ

fractions /(h2+k2+l2)

44.48 0.143 1.00 3 111 0.0477

51.83 0.191 1.34 4 200 0.0478
76.35 0.382 2.67 8 220 0.0478
92.90 0.525 3.67 11 311 0.0477
98.40 0.573 4.01 12 222 0.0478
121.87 0.764 5.34 16 400 0.0477
144.54 0.907 6.34 19 420 0.0477
 Tutorial
Molybdenum has a BCC structure and atomic radius of it is
0.1363 nm. Compute the interplanar spacing for the (111)
set of planes.

The lattice
parameter a may
be computed as
 Tutorial
Determine the expected diffraction angle for the first-order
reflection from the (113) set of planes for FCC platinum when
monochromatic radiation of wavelength 0.1542 nm is used.
The lattice
parameter a may
be computed as,
Lecture 14
31/1/2024
 So Far …
❖ X-ray diffraction
❖ Basics of diffraction
❖ Generation of X-ray
❖ Bragg’s Law
❖ Specular reflection
 X-Ray

One wants to detect the (422) plane of BCC iron (a=0.286

nm), however, can’t find it with regular X-ray diffractometer.
What can be the reason? (Cu K is the source)
 X-Ray
Detectable Lattice planes and d-spacing – how many are
possible?
 X-Ray
Detectable Lattice planes and d-spacing – how many are
possible?
➢ The number is large but finite
➢ Two reasons:
▪ The wavelength of a particular X-
ray source is fixed
▪ Miller indices can only have
integral values (h, k, l = 0,1,2…)

dhkl = n/2sin

dhkl = /2 (sin = 1; maximum value)

Lower limit for d-value
For Cu K, /2 = 0.77 Å Minimum d-value
 X-Ray

If we need to observe peaks for

d < 0.77 Å planes, should use Mo or Ag
 X-Ray
Any upper limit for dhkl values?

Integer value of Miller indices; The inverse relation between d-

spacing and Miller indices
• Largest d-spacing with (100)/(010)/(001) etc.

h2 + k2 + l2 hkl d/Å
1 100 5.00
2 110 3.53
3 111 2.89
4 200 2.50
For cubic cell with a = 5 Å
5 210 2.24
➢ List can be extended till the
d-value reaches detection
limit for X-ray
 X-Ray

One wants to detect the (212) plane of BCC iron (a=0.286

nm), what should be the source?

dhkl = 0.095 nm
X-Ray
Scattering of X-rays by a crystal – Systematic absences
➢ Within the detection limit, in principle, each set of lattice
planes can give rise to a diffracted beam.

➢ In practice, the intensity of the beams diffracted by

certain sets of lattice planes may be zero: Systematic
absences.
▪ if the lattice type is non-primitive (I, F, etc.)
▪ if elements of space symmetry (screw axes, glide
planes) are present
 Systematic absences: Example

Let’s consider -Fe: BCC crystal

Diffraction from the (100) planes has zero intensity and is

systematically absent.
 Systematic absences: Example

▪ The body center atoms lie midway between adjacent (100)

planes
▪ These diffract X-rays exactly 180 out-of-phase relative to the
corner atoms which lie on the (100) planes
 Systematic absences: Example

▪ Averaged over the whole crystal, there are equal numbers of

corner and body center atoms and the beams diffracted by
each cancel completely
▪ Strong 200 diffraction is observed → no atoms lying between
(200) planes to cause destructive interference
▪ Systematic absences are an extreme case of destructive
interference between X-ray beams diffracted by individual
atoms.
 Systematic absences: Example

▪ The (110) reflection is

observed whereas (111) is
systematically absent in
BCC crystals
 Systematic absences: The Equation

For each non-primitive lattice type there is a simple

characteristic equation for systematic absences.

Two conditions must be met for systematic absences:

Equal numbers of diffracted beams must be
(i) out-of-phase (by λ/2 or π)
(ii) diffracted beams are of the same amplitude
 Systematic absences: The Equation

Some types of unit cell give characteristic

and easily recognizable patterns of lines.
In a cubic lattice of unit cell dimension a the
spacing,

A simple comparison of the observed

ratios of sin2 values with the above is then
sufficient to identify the crystal structure.
 Problem
Elemental silver reflects X-rays of wavelength 154.18 pm
at angles of 19.076°, 22.171°, and 32.256°. However, there
are no other reflections at angles of less than 33°.
Assuming a cubic unit cell, determine its type and
dimension. Calculate the density of silver (R = 144pm).
sin21 = 0.107
sin22 = 0.1423
sin23 = 0.285
Ratio → 3:4:8

If FCC → (111), (200),

(220)
 Systematic absences: Partially destructive interference

FCC: h, k, l are either all odd or all even may be observed

➢ (110) → systematically absent; have Na+ and Cl− ions on
the planes but equal numbers of the same ions are
midway between the planes
➢ (111) → Cl− ions lie on the planes and Na+ ions lie exactly
midway between them; partial destructive interference
Systematic absences: Partially destructive interference
 Multiplicities

A general observation → crystals with higher symmetry have

simpler powder patterns, i.e., with fewer lines, than samples
with lower symmetry
▪ In cubic, each line represents the overlap of several lines
▪ For lower symmetry, these lines do not overlap if they have
different d-spacings
▪ The number of lines that overlap because of crystal
symmetry is the multiplicity

Line with indices h00

Crystal Multiplicity No. of Lines
Cubic 6 1
Tetragonal 4, 2 2
Orthorhombic 2, 2, 2 3
 Multiplicities

Different polymorphs of BaTiO3

Lecture 15
02/02/2024
 So Far …
❖ X-ray diffraction
❖ Detectable Range
❖ Systematic Absence
❖ Multiplicity
 X-Ray: Intensities

X-ray diffraction
spectrum of
germanium (diamond
cubic crystal lattice)
➢ Intensities are
different for different
peaks
 X-Ray: Intensities

• Quantitative measurements of
intensity are necessary in order
to solve crystal structures
• Qualitative or semi-
quantitative intensity data are
needed in using the powder
fingerprint method to
characterize materials
 Scattering of X-rays by an atom: atomic scattering
factors or form factors
▪ The X-rays scattered by an
atom are the result of the
waves scattered by each
electron in the atom.
▪ Electrons may be regarded as
particles that momentarily
occupy different positions
▪ Interference occurs between
their scattered waves

▪ Scattering in the direction of the incident beam : For beams 1

and 2, all electrons scatter in-phase → the scattered intensity
is the sum of the individual intensities
▪ The scattering factor, or form factor, f, of an atom is
proportional to its atomic number, Z, or to the number of
electrons possessed by that atom
 Scattering of X-rays by an atom: atomic scattering
factors or form factors

For scattering at some angle 2θ

• a phase difference, corresponding to the distance XY exists
between beams 1 and 2
• This phase difference is usually much lesser than one
wavelength (i.e. XY << 1.5418 Å for Cu K X-rays)
• Distances between electrons within an atom (~pm) are
much shorter and only partial destructive interference
occurs 1 and 2
 Scattering of X-rays by an atom: atomic scattering
factors or form factors

The atomic scattering factor → It

reaches a maximum in the same
direction of the incident X-rays and
decreases as a function of the
angle of departure
 The scattering
Factor of an atom
A quantity f, the atomic scattering factor, is used to describe
the “efficiency” of scattering of a given atom in a given
direction. It is defined as a ratio of amplitudes:

f = Z for any atom scattering in the forward direction

 Scattering of X-rays by an atom: atomic scattering
factors or form factors
Two consequences of the dependence of f on sin θ/λ and Z:
▪ XRD patterns at high angles (above ∼60–70 2θ) are usually
weak
▪ Difficult to locate light atoms because their diffracted
radiation is so weak; H cannot usually be located unless all
the other elements present are also extremely light
 Partially destructive interference: atomic scattering
factors

▪ The intensity of the (111) reflection for rock salt structure is,
related to the difference in atomic number of anion and
cation
▪ For potassium halides, (111) has essentially zero intensity for
KCl, since K+ and Cl− are isoelectronic (18), and the intensity of
(111) should increase in the order
 Partially destructive interference
▪ X-ray powder diffraction patterns for potassium halides
 Scattering by a Unit Cell: Structure Factor
Assuming that Bragg’s law is satisfied, the goal is to find the
intensity of the beam diffracted by a crystal as a function of
atom position.
Determining how the phase difference depends on the
arrangement of the atoms is the problem at hand.

https://www.youtube.com/watch?v=Z5aCuGxUPpI&t=120s
 Structure Factor
The unit cell: an A atom at the origin and a B atom at the
coordinates (xa,yb,zc); x, y, and z lie in the range 0 to 1.
▪ The reflection of two waves from
adjacent A planes → the phase
difference of the waves being 2π
▪ B atom at a fraction x of the distance
between the two A planes → phase
difference 2πx relative to an A
reflection
▪ Consider, x = 0 → no phase difference
x = ½ → phase difference 
x = 1 → phase difference 2
 Structure Factor

▪ Consider a (200) reflection:

The reflection of two waves from adjacent
A planes → the phase difference 2×2π
▪ B atom at x=½ differed in phase by 2π
from the wave from the upper A layer
▪ For a general fractional position x,
▪ the phase difference for a
(200) reflection 2 × 2πx
For a general (h00) reflection, the phase
difference is therefore h × 2πx.

For three dimensions,

 Structure Factor

If the phase difference is π → The A and

B reflections interfere destructively →
total intensity is zero if the atoms have
the same scattering power.
 Structure Factor

• The amplitude of the waves scattered from A

is fA
• The waves scattered from B is

hkl → the phase difference

The total amplitude,

The intensity is proportional to the square modulus of the

amplitude of the wave,
 Structure Factor

Structure factor

The structure factor represents Very important relation →

the resultant amplitude and permits a calculation of the
phase of scattering from all the intensity of any hkl reflection
electron density distribution of from a knowledge of the
one unit cell. atomic positions

The amplitude is calculated The phase is calculated relative

as the number of times to a phase of zero for
greater it is than the hypothetical scattering by a
amplitude of scattering from point at the origin of the unit
an isolated electron. cell
Structure Factor: SC
Structure Factor: BCC

(Monoatomic)
Structure Factor: FCC
Structure Factor
Structure Factor: CsCl
Structure Factor: CsCl
Structure Factor: NaCl
Summary