X-ray Crystallography

CHE 4314

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Objectives

To teach,
Unit cell and crystal systems

Miller indices

X-rays and their generation

Bragg’s law

Powder method
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References
Physical chemistry –P. W. Atkins
Physical chemistry –Donald A Macquarie

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Introduction

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 Crystals
 Are solid substances composed of atoms,
molecules, or ions in a definite repeating
pattern.

 Crystals have ordered arrangement in 3D space.

 Oppositeof the crystalline is amorphous and do

not have any regular interior arrangement of
atoms.

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Crystallography

“The study of crystal and law that govern

their growth, external shape and internal
structure is called crystallography”.

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Properties of Waves
 Waves interfere with one another.
 Gives a greater displacement when peaks or
troughs coincide.
 A smaller displacement when peaks
coincide with troughs.

There are two types of interferences

(1) Constructive interference
(2) Destructive interference
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Constructive interference
Constructive interference leads to an increase
in intensity (or amplitude) of which waves
are said to be “in-phase”

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Destructive Interference
Destructive interference leads to a decrease
in intensity (or amplitude). Then wave are
said to be “out of phase”.

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These two are two extreme situations. But,
generally there are situations that are not
fully destructive.

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 Diffraction
 The phenomenon of diffraction is the
interference that is caused by an object or
slit in the path of waves.

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 The pattern of varying intensity that is
called the diffraction pattern.

 Diffraction occurs when the dimensions

of the diffracting object are comparable to
the wavelength of the radiation.

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Space lattice
 The collection of all the points, within a
crystal that have an identical
environment is called a space lattice.

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 Unit Cell
 The fundamental or basic region (unit)
of which the entire crystal lattice is
built.
 A crystal therefore, can be considered
as to be built up by regular repeating
unit called the unit cell.

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Unit Cell Dimensions
The unit cell is described by six parameters;
a, b, c, α, β and γ.

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 Primitive unit cell (P)
A unit cell containing one lattice points is
called a primitive cell and here points with
identical surroundings are found only at the
corners of the unit cell.

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Each lattice points shared by eight unit cell.
Therefore, each lattice point contribute
1/8th to a unit cell.
8 x 1/8 = 1
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Non primitive unit cells

A unit cell that contains more than one

lattice point is referred to as non-
primitive unit cells.

Body centered (I)

A body centered unit cell has lattice
points shared at the corners and one at
the center giving a total of two lattice
points to the unit cell.
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8 x 1/8 + 1 = 2

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Exercise

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Face centered (F)
Face centered unit cell has lattice points
shared at the corners and on all faces of
the unit cell, giving rise to four lattice
points.
(8 x 1/8) + (1/2 x 6) = 4

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The following rules must be kept in mind to
determine the number of lattice points in a
unit cell.

1. A point or atom lying completely within

a unit cell belongs to that unit cell and is
therefore count as 1 when totaling the
number of points or atoms in the unit
cell.

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3. A point or atom lying on a face of a cell
is shared equally by two unit cells and is
therefore, counted as ½ when totaling the
number of points or atoms in a unit cell.

4. A point or atom lying on an edge is

shared by four unit cells and is therefore, is
counted as ¼.

5. A point or atom lying at a corner is

shared by eight unit cells and is therefore,
counted as 1/8.
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Summery
Amorphous vs. Crystalline
Crystallography
Properties of waves
- Interference and Diffraction
Unit Cell
Type of unit cell

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Unit cells are classified into seven crystal
systems by noting the rotational symmetry
elements they possess.

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Crystal planes
The spacing of the lattice points in a
crystal is an important quantitative aspect
of it’s structure and it’s investigation.

However, there are many different sets of

planes and we need to be able to label
them.

A shorthand procedure is used for

describing a particular plane in a crystal
and it is called as a miller indices. 28
The (200) planes of The (220) planes of
atoms in NaCl atoms in NaCl

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The procedure to determine Miller indices of
a plane

(1) Choose an origin.

(2) Read off the intersects along the x, y, and z
axis in terms of the unit spacing in the
crystal
- a along the x axis
- b along the y axis
- c along the z axis
the intersect is infinity if the plane does
not cut the axis of concerned.
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3. Take reciprocals, dropping any reference
to a, b, and c.
4. If the reciprocals for a given plane
include a fraction or fractions, express
the reciprocals as their simple integral
ratio.

Write the Miller indices which are then

referred to as h, k, l values and also
enclosed within standard brackets() for one
plane.
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Examples

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The separation of planes
The Miller indices are very useful for
expressing the separation of planes. The
separation of (hkl) planes of a
orthorhombic lattice is given by,

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Exercise

Calculate the separation of the (133) and

(399) planes of an orthorhombic cell with a
= 0.82 nm, b=0.94 nm and c = 0.75 nm.

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Cubic Unit Cell
For the cubic unit cell,
a=b=c
Therefore the equation further reduces for
cubic unit cell as,

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 X-ray diffraction
 X-rays
are electromagnetic radiation with
wavelengths of the order of 100 pm.

 X-raysare produced by bombarding a

metal with high energy electrons.

 Superimposed on the continuum are a few

high intensity sharp peaks.

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X-rays are generated by
directing an electron
beam on to a cooled
metal target.
Beryllium is transparent
to X-rays (on account of
the small number of
electrons in each atom)
and is used for the
windows.

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 The electrons decelerate as they plunge
into the metal and generate radiation with
a continuous range of wavelengths.

 These peaks arise from interaction of the

incoming electrons with the electrons in
the inner shell of the atom.

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 A collisionexpels electrons and an electron
of higher energy drops into the vacancy,
emitting the excess energy as an X-ray
photons.

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 An incoming electron collide with an
electrons (k shell) of metal and eject it.
 Another electron from the outer shell falls
into the vacancy and emits its excess
energy as X-ray.
 These radiations are called as K
radiations.

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 Intensity
of X-ray at different
wavelengths emitted from a copper target.

K X-rays could be isolated by using Ni

sheet with copper.

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 The Bragg’s Law

When X-rays impinge on a crystal some are

reflected from the atoms in the top layer,
whereas, others penetrate through that layer
and are reflected off the next layer and so on.

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This condition is equivalent to say that the sum of the FG and
GH segments corresponds to an integer (n) times the
wavelength (λ):

FG + GH = n. λ (1)

but FG = GH and sin θ = FG / d that is: FG

= d sin θ, and therefore expression (1) becomes:

2 d sin θ = n. λ 48
Problem
1. The glancing angle of a Bragg’s
reflection from a set of crystal planes
separated by 128.2 pm is 19.76°.
Calculate the wavelength of the X-rays.

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Ifwe know the angle of the reflection, we
can find dimension of the crystal and the
type of crystal.

To determine the angle of reflection,

(1) Powder diffraction method (Debye-
Scherrer method)
(2) Single crystal method

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The powder diffraction method
This method could be used for powder
samples.
In mineralogy, this is used as a technique
to identify.
Cubic crystals are easy to see and can be
easily identified.
Therefore, this method can be used to
identify minerals/crystals.

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Technique
In order to see diffractions Bragg’s law
should be satisfied.

In this method, λ is fixed and θ is a

variable.

Sample preparation
Mineral is grinded into fine powder and fill
it into a capillary tube. 53
Pass a broad band beam of X-rays into a
single crystal and record the diffraction
pattern photographically.
For this method we used powdered sample
and a camera called as Guinier camera.

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Possible values for h2 + k2 + l2

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Reason for systematic absences
Constructive interference,
Phase difference = 2П
( multiples of 2П …2П, 4П…etc)

Destructive interference,
Phase difference = П
( multiples of even numbers of П …П, 3П…etc)

Phase difference (Φ) = 2П(hx + ky + lz)

Where, hkl – a set of lattice planes
x,y,z – coordinates of lattice point (atom) in the unit
cell )
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The powder diffraction
patterns and the
systematic absences of
three versions of a
cubic cell. Comparison
of the observed
pattern with pattern
like these enables the
unit cell to be
identified. The
locations of the lines
give the cell
dimensions.
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Not all Planes Produce Peaks
Peak Intensity
I hkl  I 0pCLP Fhkl 
2

where
◦ Io = Intensity of the incident X-ray beam
◦ p = Multiplicity factor (a function of the
crystallography of the material)
◦ C = Experimental constant (related to temperature,
absorption, fluorescence, and crystal imperfection).
Temperature factor=e-2M; Absorption factor = A(θ).
◦ LP = Lorentz-Polarization factor.
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Structure Factors

 Only if [Fhkl]2 ≠0 does a peak appear

N
Fhkl   f n exp2π i hu n  kvn  lw n 
n 1

◦ ƒn = atomic scattering factor of atom ‘n’ is a measure of

the scattering efficiency
◦ u,v,w are the atomic positions in the unit cell
◦ h,k,l are the Miller indices of the reflection.
◦ N is number of atoms in the unit cell
The summation is performed over all atoms in the unit
cell.
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Structure Factors: Useful Knowledge
(1)

Atomic scattering factors vary as a function of

atomic number (Z) and diffraction angle (θ)
Values can be looked up in tables

◦ Linear extrapolations are used for

calculating the values between those listed. 64
 (2)

Calculating structure factors involves complex exponential functions. Use the following
relationships to determine the values of the exponential:

expi   exp3i   exp5i   1

exp2i   exp4i   exp6i   1
exp( ni )   1 , where n is an integer
n

expni   exp ni , where n is an integer

expix   exp ix   2 cos x

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2. BCC Structure

Consider the BCC lattice with single atoms at each lattice point; its unit cell can be reduced to
two identical atoms. Atom #1 is at 0,0,0 and atom #2 is at ½, ½, ½.

For this case we have

  h k l 
Fhkl  f1 exp2i 0  f 2 exp 2i     f 1  expi h  k  l  . . . (5)
  2 2 2 

Note: For atoms of the same type, f1 = f2 = f.

Observations:
(i) 2
If the sum (h + k + l) = even in Equation (5), Fhkl = 2f and Fhkl 4f 2

(ii) 2
If the sum (h + k + l) = odd in Equation (5), Fhkl = 0 and Fhkl 0
Thus, diffractions from BCC planes where h + k + l is odd are of zero intensity. They are
forbidden reflections. These reflections are usually omitted from the reciprocal lattice.

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3. FCC Structure

The FCC unit cell has four atoms located at (0,0,0), (½,½,0), (½,0,½), and (0, ½,½).

It follows that, for the same kind of atoms, the structure factor the FCC structure is given by the
expression

  h k    h l    k l 
Fhkl  f exp2i 0  f exp 2i    f exp 2i    f exp 2i  
  2 2    2 2    2 2 

 Fhkl  f 1  expih  k   expih  l   expik  l  . . . . . (6)

If h, k, and l are all even or all odd (i.e. unmixed) then the sums h + k, h + l, and k + l are all
even integers, and each term in Equation (6) equals 1. Therefore, Fhkl = 4f. However, if h, k, and l
are mixed integers, then Fhkl = f(1+1-2) = 0.

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