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Chapter 02 - B

Chapter 2 discusses the reciprocal lattice, including concepts such as Bragg's law, X-ray properties, and the production of X-rays. It explains the relationship between diffraction patterns and reciprocal lattices, as well as methods for crystal structure determination using X-ray diffraction techniques. Additionally, it introduces quasicrystals as ordered structures that lack periodicity, highlighting their significance in crystallography.

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Umair Khan
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18 views30 pages

Chapter 02 - B

Chapter 2 discusses the reciprocal lattice, including concepts such as Bragg's law, X-ray properties, and the production of X-rays. It explains the relationship between diffraction patterns and reciprocal lattices, as well as methods for crystal structure determination using X-ray diffraction techniques. Additionally, it introduces quasicrystals as ordered structures that lack periodicity, highlighting their significance in crystallography.

Uploaded by

Umair Khan
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Chapter 2.

Reciprocal Lattice

Issues that are addressed in this chapter


include:
 Bragg law
 Scattered wave amplitude
 Brillouin Zones
 Fourier analysis of the basis
 Quasicrystals
Reciprocal lattice
• The set of all waves vectors k that yield plane wave with
the periodicity of a given Bravais lattice.
• A diffraction pattern is not a direct representation of
the crystal lattice
• The diffraction pattern is a representation of the
reciprocal lattice
X-RAY
• X-rays were discovered in
1895 by the German
physicist Wilhelm Conrad
Röntgen and were so
named because their
nature was unknown at
the time.

• He was awarded the


Wilhelm Conrad Röntgen
Nobel prize for physics in (1845-1923)
1901.
X-RAY PROPERTIES
• X ray, invisible, highly penetrating electromagnetic
radiation of much shorter wavelength (higher frequency)
than visible light. The wavelength range for X rays is
from about 10-8 m to about 10-11 m, the corresponding
frequency range is from about 3 × 1016 Hz to about 3 ×
1019 Hz.
X-RAY ENERGY
• Electromagnetic radiation described as having
packets of energy, or photons. The energy of the
photon is related to its frequency by the following
formula: E= hν
c
E=
hc ν =
λ λ

λ =Wavelength , ‫ = ע‬Frequency , c = Velocity of light hc


E =
λ

λx-ray ≈ 10-10 ≈ 1A° E ~ 104 ev


PRODUCTION OF X-RAYS
• Visible light photons and X-ray photons are both
produced by the movement of electrons in atoms.
Electrons occupy different energy levels, or
orbitals, around an atom's nucleus.

• When an electron drops to a lower orbital, it needs


to release some energy; it releases the extra
energy in the form of a photon. The energy level of
the photon depends on how far the electron
dropped between orbitals.
X-RAY TUBE
• X rays can be produced in a highly evacuated glass
bulb, called an X-ray tube, that contains essentially two
electrodes—an anode made of platinum, tungsten, or
another heavy metal of high melting point, and a
cathode. When a high voltage is applied between the
electrodes, streams of electrons (cathode rays) are
accelerated from the cathode to the anode and produce
X rays as they strike the anode.
Evacuated glass bulb

Cathode
Anode
Bragg’s Law
nλ = 2 d sin θ
• Constructive interference only occurs for certain θ’s
correlating to a (hkl) plane, specifically when the
path difference is equal to n wavelengths.
Bragg Diffraction: Bragg’s Law
Bragg condition’s

The diffraction condition can be written in vector


form
2k∙G + G2 = 0
∆k = G
k - is the incident wave vector
k’ - is the reflected wave vector
G - is a reciprocal lattice vector such that where
G = ∆k = k - k’
the diffraction condition is met
Laue Conditions
The Bragg condition considers lattice objects that are grouped in
families of planes, and the incident radiation is specularly reflected. The
Laue condition doesn't require the assumption of particular planes and
spacings, and doesn't require that reflection be specular.
The three Laue equations give the conditions to be satisfied by an incident
wave to be diffracted by a crystal.

a1∙∆k = 2πυ1 a2∙∆k = 2πυ2


a3∙∆k = 2πυ3
• Each of the above describes a cone in reciprocal space about the lattice vectors a1,
a2, and a3.
– the υi are integers
• When a reciprocal lattice point intersects this cone the diffraction condition is met,
this is generally called the Ewald sphere.
Ewald Sphere
The aim of the Ewald sphere is to
determine which lattice planes (represented
by the grid points on the reciprocal lattice)
will result in a diffracted signal for a given
wavelength, of incident radiation.
λ 2 1 d hkl
The Ewald Sphere n λ = 2 d hkl Sinθ hkl Sinθ hkl = =
Bragg’s equation revisited d hkl 2λ
 Draw a circle with diameter 2/λ
 Construct a triangle with the diameter as the hypotenuse and 1/dhkl as a side (any
triangle inscribed in a circle with the diameter as the hypotenuse is a right angle
triangle): AOP
 The angle opposite the 1/d side is θhkl (from the rewritten Bragg’s equation)

* 1
*
g hkl = g hkl =
d hkl
The Ewald Sphere construction

Crystal related information is present in the reciprocal crystal

λ 2 1 d hkl
Sinθ hkl = = The Ewald sphere construction generates the diffraction pattern
d hkl 2λ

Radiation related information is present in the Ewald Sphere


Ewald sphere → X-rays
Crystal structure determination

Many θs (orientations) POWDER


Monochromatic X-rays Powder specimen METHOD

Single θ
LAUE
Panchromatic X-rays
TECHNIQUE

ROTATING
Monochromatic X-rays θ Varied by rotation CRYSTAL
METHOD
Construction of Reciprocal Lattice

For an infinite three dimensional lattice, defined by its


primitive vectors a1, a2 and a3, its reciprocal lattice can
be determined by generating its three reciprocal primitive
vectors, through the formulae
Summary of Bragg & Laue

• When a diffraction
condition is met there nλ
can be a reflected X-ray d=
– Extra atoms in the basis can
suppress reflections
2 sin θ
• Three variables λ, θ, and d
– λ is known
– θ is measured in the a = d h +k +l
2 2 2
experiment (2θ)
– d is calculated
• From the planes (hkl)
– a is calculated
θ - 2θ Scan
The θ - 2θ scan maintains these angles with the
sample, detector and X-ray source
Normal to surface

Only planes of atoms that share this normal will be seen in the θ - 2θ Scan
θ - 2θ Scan
The incident X-rays may reflect in many directions
but will only be measured at one location so we
will require that:

Angle of incidence (θi) = Angle of reflection (θr)

This is done by moving the detector twice as fast


in θ as the source. So, only where θi = θr is the
intensity of the reflect wave (counts of photons)
measured.
θ - 2θ Scan
Smaller Crystals Produce Broader XRD Peaks
Scherrer’s Formula
The Scherrer equation, in X-ray diffraction and crystallography, is a formula that
relates the size of sub-micrometre particles, or crystallites, in a solid to the
broadening of a peak in a diffraction pattern. It is named after Paul Scherrer.

K ∗λ
t=
B ∗ cos θ B
t = thickness of crystallite
K = constant dependent on crystallite shape (0.89)
λ = x-ray wavelength
B = FWHM (full width at half max) or integral
breadth
θB = Bragg Angle
Bragg Example
Bragg Example

d = λ / (2 Sin θB) λ = 1.54 Ǻ


= 1.54 Ǻ / ( 2 * Sin ( 38.3 / 2 ) )
= 2.35 Ǻ

Simple Right!
Scherrer’s Example
Au Foil

10000

9000

8000

98.25 (400)
7000

6000
Counts

5000

4000

3000

2000

1000

0
95 95.5 96 96.5 97 97.5 98 98.5 99 99.5 100 100.5 101 101.5 102
2 Theta
Scherrer’s Example
0.89 ∗ λ
t=
B ∗ cos θ B
t = 0.89*λ / (B Cos θB) λ = 1.54 Ǻ
= 0.89*1.54 Ǻ / ( 0.00174 * Cos (98.25/ 2 ) )
= 1200 Ǻ

B = (98.3 - 98.2)*π/180 = 0.00174

Simple Right!
The diffraction pattern of copper metal was measured with x-ray radiation of
wavelength of 1.315 Å. The first order Bragg diffraction peak was found at an
angle 2θ of 50.5 degrees. Calculate the spacing between the diffracting planes
in the copper metal.
Quasicrystal
 A quasiperiodic crystal, or, in short, quasicrystal, is a structure that
is ordered but not periodic. A quasicrystalline pattern can
continuously fill all available space, but it lacks translational
symmetry.
 A material with sharp diffraction peaks with a forbidden symmetry
by crystallography.
 They have long-range positional order without periodic
translational symmetry.
 Shechtman was awarded the Nobel Prize in Chemistry in 2011 for
his work on quasicrystals. “His discovery of quasicrystals revealed a
new principle for packing of atoms and molecules.”
ORDERED PERIODIC
CRYSTAL QC ARE
HOW IS A QUASICRYSTAL S   ORDERED
DIFFERENT FROM A STRUCTUR
CRYSTAL?
QC  × ES WHICH
ARE NOT
AMORPH PERIODIC
OUS × ×

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