In these set of slides we shall consider:

 scattering from an electron

 scattering from an atom
 structure factor calculations (scattering from an unit cell)
 the relative intensity of ‘reflections’ in power patterns

You may find the first

Click here to directly jump to
set of slides a little structure factor calculations MATERIALS SCIENCE
difficult and hence Part of & AALearner’s Guide
Learner’s Guide
ENGINEERING
AN INTRODUCTORY E-BOOK
Anandh Subramaniam & Kantesh Balani
Materials Science and Engineering (MSE)
Indian Institute of Technology, Kanpur- 208016
Email: anandh@iitk.ac.in, URL: home.iitk.ac.in/~anandh
http://home.iitk.ac.in/~anandh/E-book.htm

Elements of X-Ray Diffraction

B.D. Cullity & S.R. Stock
Prentice Hall, Upper Saddle River (2001)
Intensity of the Scattered electrons
Scattering by a crystal  To understand scattering from a crystal, we have to
understand scattering from 3 levels: (i) electron, (ii) atom,
(iii) unit cell.
 For crystals the unit cell repeats to give us the crystal and
A
hence all the information required can be obtained at the
Electron Polarization factor unit cell level.
 Usually materials scientists need to start understanding
from the atomic scattering factor. Most students can jump
directly to structure factor calculations.

B
Atom Atomic scattering factor (f)

C
Unit cell (UC) Structure factor (F)

Click here to jump to structure factor calculations

A Scattering by an Electron

Incoming radiation

Scattered beams
Em
is sio
(0 , 0 )
n in
‘all
’ d ir e
c ti o
ns
Sets electron into oscillation

Coherent
(definite phase relationship)
(0 , 0 )

 The electric field (E) of the incoming radiation (with wavelength 0 and frequency 0) is the
main cause for the acceleration (& deceleration) of the electron (in an atom) i.e. the
oscillating magnetic field component can be ignored. The effect on the nucleus can be
ignored.
 The oscillating electron is a source of electromagnetic radiation and radiates most strongly in
a direction perpendicular to its motion.
 Hence, the radiation emitted will be polarized along the direction of its motion.
 There is fixed phase relationship between the incoming radiation and the scattered wave.
 The incoming wave may be polarized on un-polarized. We consider the intensity in these two
situations next.
Case A: intensity of the scattered wave for an polarized wave z P
For a wave oscillating in z direction r

x

Intensity of the scattered beam due to an electron (I) at a point P such that r >>  is given by:
e 4  Sin 2 
I  I 0 2 4  2 
mc  r 

The reason we are able to neglect

scattering from the protons in the nucleus

The scattered rays are also plane polarized

1

0.8

0.6

0.4

0.2
Cos(t)

0 t
0 30 60 90 120 150 180 210 240 270 300 330 360
-0.2

-0.4

-0.6

-0.8

-1
Case B: intensity of the scattered wave for an un-polarized wave

E 2  E y2  E z2
I0
 I0 y  I0z
2

IPy = Intensity at point P due to Ey

E is the measure of the amplitude of the wave & E 2 = Intensity
e 4  Sin   y  
2

I Py  I 0 y  
m2c 4  r2 
 
IPz = Intensity at point P due to Ez
e 4  Sin  z 

2

I Pz  I 0 z 2 4  
mc  r2 
Total Intensity at point P due to Ey & Ez
e4  Sin   y   Sin  z  
2 2

I P  I0 2 4  
mc  r 2

 
 e 4  Sin   y   Sin   z  
2 2

I P  I0 2 4  
mc  r2 
 
 Sin 2   y   Sin 2  z    1  Cos 2   y   1  Cos 2   z     2  Cos 2   y   Cos 2   z  
     

Cos 2  x   Cos 2   y   Cos 2   z    1 Sum of the squares of the direction cosines =1

 

Hence  2  Cos 2   y   Cos 2  z     2   1  Cos 2 ( x )     1  Cos 2 ( x )  

     

e
I P  I0 2 4


4
 1  Cos 2
(x )  


mc  r2 
 
In terms of 2

e 4   1  Cos (2 )  
2

I P  I0 2 4  
mc  r2 
 
 e 4  I 0 y  I 0 z Cos  2  
1

2 0.8

I P  I Py  I Pz  2 4
0.6

m c  
0.4

r2
0.2

Cos(t)
0 t
0 30 60 90 120 150 180 210 240 270 300 330 360
-0.2

I 0 e 4  1  Cos 2  2  
-0.4

-0.6

IP     Scattered beam is not unpolarized

-0.8

2 4 
-1

2
2 mc  r  Polarization factor
Comes into being as we used unpolarized beam
Very small number 1.2

0.8
(1+Cos(2t)^2)/2

0.6

0.4

0.2

2t
0
0 30 60 90 120 150 180 210 240 270 300 330 360

 Forward and backward scattered intensity higher than at 90.

 Scattered intensity minute fraction of the incident intensity.
 B Scattering by an Atom Atomic Scattering Factor or Form Factor (f)
 The scattering by an atom is the sum (vectoral sum, including phase) of the waves scatted by
the electrons. Angular differences involved in scattering leads to path differences.
 In the forward direction all scattered waves are in phase.
 The scattering from an atom is captured in the atomic scattering factor (f), which is the ratio of
the amplitude of the wave scattered by the atom to that scattered by a single electron. It shows
the amplification obtained by the presence of multiple electrons in an atom.
 Scattering by an atom is proportional to the atomic number (the number of electrons). The
natural coordinates to plot the variation of ‘f’ is not  or 2, but Sin()/. At 0 the curve starts
at the atomic number as in the schematic below.
f  Atomic Scattering Factor
Sin( )
Scattering by an atom  [Z, (, )]
Amplitude of wave scattered by an atom 
 30
Amplitude of wave scattered by an electron Equals number of electrons, say
for f = 29, it should Cu or Zn+
Scattering by an atom  [Atomic number, (path
difference suffered by scattering from each e−, )]
20 Schematic showing variation in
atomic scattering factor with

f →
Coherent Incoherent (Compton) Sin()/
scattering scattering
Z   10
Sin() /     Sin( ) −1
(Å ) →

As θ↓, path difference ↓  constructive interference
As λ↓, path difference ↑  destructive interference 0.2 0.4 0.6 0.8 1.0
 B Scattering by an Atom

BRUSH-UP
 The conventional UC has lattice points only at the vertices/corners.
 Additional lattice points may be present within the unit cell, if the unit cell is non-
primitive.
 Needless to say, lattice in itself cannot scatter and atoms are required.
 Motif is associated with lattice and motif may consist of one or more atoms, ions,
molecules (or combinations).
 There may or may not be atoms located at the lattice points.
 The shape of the UC is a parallelepiped (Greek parallēlepipedon) in 3D.
 There may be additional atoms in the UC due to two reasons:
 The chosen UC is non-primitive (hence additional lattice points exist within the cell, which are associated with atoms).
 The additional atoms may be part of the motif.
 We use the Bragg’s viewpoint to derive the general structure factor equation.
C Scattering by the Unit cell (uc)
 We use the following points to derive the scattering from a unit cell (which is captured in the
structure factor (F)): (i) the scattering is coherent, (ii) Unit Cell (UC) is representative of the
crystal structure, (iii) scattered waves from various atoms in the UC interfere to create the
diffraction pattern.
 The essential feature of the need for structure factor calculation can be understood from the
figure below. Let us assume a BCC crystal. If the waves are in phase for the ‘reflection’ from
the green planes, then the presence of the additional atom in the orange plane will lead to
scattering of waves, which are exactly out of phase with that scattered from the green planes
and hence the 100 reflection will ‘go missing’. Note that the atomic density of both the planes
(green and orange) is the same (one atom per a2) and hence the scattering power of these
planes is the same.
 If we consider a simple cubic crystal with a two atom motif with atoms as: A at (0,0,0) and B
at (½, ½, ½), then the atomic scattering factor of the two atoms will not be the same (i.e. f A 
fB) and hence there will be a ‘residual’ intensity from the 100 planes (i.e. 100 reflection will
‘not go totally missing’, but will be weak called a superlattice reflection).

The wave scattered from the middle plane is out of phase

with the ones scattered from top and bottom planes. I.e. if
the green rays are in phase (path difference of ) then the
red ray will be exactly out of phase with the green rays
(path difference of /2).
 Let us consider scattering of waves (or “rays”) R1 and R2 from planes P1 and P2 (belonging to
the (h00) set of planes. The scattered rays are denoted by ‘primes’.
 Let there be an additional atom located at a distance ‘x’ along x-axis (on plane P 3).
 The rays R2 and R3 travel longer distances than R1 and hence accrue path () & phase
differences ().

Ray 1 = R1 R1'

Ray 3 = R3 R3'
B A 
P1
x
R S
P3
Ray 2 = R2 B R2'
d(h00)
M N a
P2 (h00) plane
C
Unit Cell
 2
a  
AC  d h 00  
h
MCN :: AC ::  
 
2
RBS :: AB :: x
AB x x
 
AC  a
h

To satisfy Bragg’s equation the path

difference between rays R1 & R2 has to be   R1R2  MCN  2d h 00 Sin( )  

Correspondingly the path difference between AB x

 R1R3  RBS   
rays R1 and R3 will be AC a
h
The phase 2 x x x
 fractional coordinate  x
difference R1R3    2 h Using fractional coordinates (x’) the
a
can be  a a phase difference becomes
written as h R1R3  2 hx

Extending to 3D   2 ( h x  k y  l z ) Independent of the shape of UC

Note: R1 is from corner atoms and R3 is from atoms in additional positions in UC

The phase difference gives rise to the amplitude (which can be written in complex notation as)

  2 ( h x  k y   l z ) E  Aei  fei[2 ( h x k yl z)]

 If atom B is different from atom A  the amplitudes must be weighed by the respective
atomic scattering factors (f).
 The resultant amplitude of all the waves scattered by all the atoms (say ‘n’ atoms) in the UC
gives the scattering factor for the unit cell Fnhkl .
 The unit cell scattering factor is called the Structure Factor (F).
 The intensity of the ‘diffracted’ wave is proportional to the square of F.
2
IF
 Once we have the structure factor then the intensity obtained from a set of planes (hkl) is
known.

Scattering by an unit cell = f(position of the atoms, atomic scattering factors)

Amplitude of wave scattered by all atoms in uc
F  Structure Factor 
Amplitude of wave scattered by an electron
n n
 f j e    f j e
i [2 ( h x j  k y j  l z j )]
F hkl
 i j
   For n atoms in the UC
n
j 1 j 1

Structure factor is independent of the shape and size of the unit cell!
F → Fhkl If the UC distorts so do the planes in it!!
 Some useful relations
Evaluation of the equation
ni
n n e  (1) n

  fj e   fj e
hkl i j i [2 ( h xj  k y j  l z j )]
F n
j 1 j 1 e ( odd n ) i  1
 The summation ‘j’ is done over the ‘n’ atoms in the UC. e ( even n ) i  1
 In a primiteve unit cell (e.g. in the SC crystal) there is just one atom ni  ni
(in the UC). e e
 x’ (y’ & z’) refer(s) to the fractional coordinates of each atom. e i   e  i
 Cos ( )
 The fj is the atomic scattering factor for each atom. If there is just 2
one type of atom (say Po then fj = fPo). If there is more than one type
of atom, the fractional coordinates should match with the atom type.
Note: e n i  (1) n
 The intensity is an actual observable (if sampled in an experiment) and hence
e n i  e  n i
structure factor is a real quantity. n is an integer
 A set of useful equations to evaluate the F is given on the right side.
 How to understand the structure factor? Is there a simpler way so as to avoid
Funda Check calculations?

 Structure factor (F) tells us that which planes in the crystal scatter from an unit cell and what
is the resultant intensities.
 I.e. which hkl reflections are present and which ones are absent?
‘Which ‘hkl’ has what intensities?’ (which have higher intensities and which have lower
intensities).
 The ‘F’ has each term weighed by the atomic scattering factor (f) and hence (we will see soon) that
intensities are weighed by some function of the ‘f’ of atoms in the unit cell.
 Using the ‘F’ calculations we can construct the reciprocal crystal. And we will see later that diffraction
patterns are nothing but selective sampling of this reciprocal crystal (displayed/plotted in 2 axis or 1/x axis).
 The structure factor calculation is performed by evaluating the sum for all “non-equivalent”
(this term will become clear from the examples considered soon) atoms in the unit cell.

 What is the source of these additional atoms*?

Ans:
(i) The unit cell may be non-primitive and hence there might be additional lattice points
associated with additional atoms.
(ii) The motif may have many atoms.

* “Atoms” is used in a general sense here, it includes neutral atoms, ions, molecules etc.
Plotting Structure Factor calculations Please refer to topic on Reciprocal Lattice to know all the details

 A set of planes (hkl) in real space becomes a point in reciprocal space (labeled without the
brackets as hkl ).
 These points define the reciprocal lattice (a purely geometrical construction).
 Structure factor calculations give us the intensity associated with each of these points. We
use a sphere to designate the intensity, with the diameter of the sphere proportional to the
intensity.
 On decorating the reciprocal lattice with intensities, we get the reciprocal crystal.

Real Space Reciprocal Space

Lattice decorated with
Reciprocal lattice decorated with Intensities as motif
Motif
Points
Planes
(planes in real space become points in reciprocal space)
Intensities
Motif (motif in real space determines the intensities in reciprocal
space)

Needless to point out the reciprocal of the reciprocal lattice is the real lattice.
Structure factor calculations
 Now we perform calculation of structure factor calculations for some simple crystal structure
unit cells.
 We basically perform the summation of the function f exp(i) for the different atoms ions in
the unit cell and work out the restrictions on the allowed values of hkl (and the corresponding
intensities).
Let us start with the simple cubic crystal. The first step is to construct the reciprocal lattice from the real
lattice. The real lattice is simple cubic and so is the reciprocal lattice.

1 Atom at (0,0,0) and equivalent positions Simple Cubic Crystal

UC of SC lattice
a
1/a
UC of reciprocal
a 1/a
lattice (primitive)
a 1/a
Underlying
lattice: SC

 Each of the points in the reciprocal lattice corresponds to a set of planes in real space.
 The dimensions are reciprocal to that in real space. Hence, lattice parameter ‘a’ in real space becomes
‘1/a’ in reciprocal space.
 Now we have to perform structure factor calculations to determine the intensities which decorate this
lattice.
 i [2 ( h x j  k y j  l z j )] We note that in simple cubic crystals
 f j e   f j e 
hkl i j
F 
there is no restrictions on the allowed
values of hkl (i.e. for all values of hkl
reflections are present).
F  f ei[2 ( h 0 k  0l  0)]  f e0  f
 All reflections are
F  f
2 2
 F is independent of the scattering plane (h k l) present

The diameter of the

sphere scales with the
intensity of the ‘spot’.
1/a
UC of reciprocal crystal
(intensities decorating the reciprocal lattice)
(also primitive) 1/a

1/a

In the reciprocal crystal, intensities decorate the lattice points (shown in orange colour). The magnitude of the
intensity (as determined from the structure factor calculation) is f2.
2 Atom at (0,0,0) & (½, ½, 0) and equivalent positions Face Centred Cubic (CCP crystal)
i j i[2 ( h xj  k y j  l z j )]
F  fj e  fj e (½, ½, 0), (½, 0, ½), (0, ½, ½)

 i[ 2 ( 0)] i[ 2 ( h 2 k )] i[ 2 ( k 2l )] i[ 2 ( l 2h )] 

F  f e e e e 
 Real

 f [1  ei ( h  k )  e i ( k l )  e i (l  h ) ]

CCP (“FCC crystal”)

becomes “BCC crystal” in
reciprocal space

F  f [1  e i ( h  k )  e i ( k l )  e i ( l  h ) ]
UC of reciprocal crystal: non-primitive

(h, k, l) unmixed F 4f F  16 f

2 2
111, 200, 220, 333, 420
h,k,l → all even or all odd

(h, k, l) mixed F 0 F2  0 100, 211; 210, 032, 033

Two odd and one even (e.g. 112); two even and one odd (e.g. 122) Continued…
 Face Centred Cubic
Mixed indices Two odd and one even (e.g. 112); two even and one odd (e.g. 122)

Mixed indices CASE h k l

A o o e
B o e e

CASE A : [1  ei ( e)  ei ( o )  ei ( o ) ]  [1  1  1  1]  0

CASE B : [1  ei ( o )  ei ( e )  ei ( o ) ]  [1  1  1  1]  0

(h, k, l) mixed F 0 F 02 e.g. 100, 211; 210, 032, 033.

Unmixed indices All odd (e.g. 111); all even (e.g. 222)

Unmixed indices CASE h k l

A o o o
B e e e
CASE A : [1  ei ( e )  ei (e )  ei ( e ) ]  [1  1  1  1]  4  This implies that in FCC only h,k,l
‘unmixed’ reflections are present.
CASE B : [1  ei ( e )  ei ( e )  ei ( e ) ]  [1  1  1  1]  4

(h, k, l) unmixed F 4f F 2  16 f 2

e.g. 111, 200, 220, 333, 420.
3 Atom at (0,0,0) & (½, ½, ½) and equivalent positions Body centred Orthorhombic
i j i [2 ( h x j  k y j  l z j )]
F  fj e  fj e
1 1 1
i[2 ( h   k   l  )]
F  f ei[2 ( h 0 k  0 l  0)]  f e 2 2 2 UC in real
Real space (crystal)
h  k l
i[ 2  ( )]
 f e0  f e 2
 f [1  ei ( h  k l ) ]

F 2f F2  4 f 2
l ) e ve n
(h + k + e.g. 110, 200, 211; 220, 022, 310.
i ( h  k  l )
F  f [1  e ] (h + k +
l ) odd
F 0 F2  0
e.g. 100, 001, 111; 210, 032, 133.

 This implies that (h+k+l) even reflections are only present.

 The situation is identical in BCC crystals as well.

Continued…
 Underlying
UC in real lattice: BCO
space (crystal)

UC of the
reciprocal lattice
(primitive)

UC of reciprocal crystal

UC of reciprocal crystal: non-primitive

4 Atoms at (0,0,0) & (½, ½, 0) and equivalent positions C- centred Orthorhombic Crystal
 For this case there is one additional lattice point with an associated atom. Hence, there will
be two terms in the summation for the structure factor.
i j i [2 ( h x j  k y j  l z j )]
F hkl  f j e  fj e

Ball & stick model of UC in real space

UC in real
space (crystal)

 This is a UC of the reciprocal lattice. The UC

corresponds to a simple orthorhombic lattice
UC of the in reciprocal space.
reciprocal lattice  Note the basis vectors.
(primitive)
 The magnitude of the basis vectors are 1/a,
* 1
| b1 | 1/b & 1/c.
a  However, the reciprocal crystal has a
* 1 different unit cell.
| b2 |
b  Unit cell of the reciprocal crystal (as we shall see)
* 1 is a c-centred orthorhombic UC (i.e. UC usually
| b3 | chosen for the c-centred orthorhombic lattice).
c
 Missing reflections C-centred orthorhombic UC Unit cell of reciprocal
C-centred orthorhombic UC
lattice (primitive)

1/c

1/a 1/b

UC of reciprocal crystal: non-primitive

1 1
i [2 ( h   k   l  0)] Important note:
i [2 ( h 0  k  0  l  0)]
F hkl
 f e f e 2 2  The 100, 101, 210, etc. points in
the reciprocal lattice exist (as the
h k Real corresponding real lattice planes
i[ 2  ( )] exist), however the intensity
 f e0  f e 2
 f [1  ei ( h  k ) ] decorating these points is zero.

ve n
(h + k) e
b o th odd
F  2 f F 2
4 f2
o r
Both even e.g. 001, 110, 112; 021, 022, 023.
i ( h  k )
F f [1  e ] Mixture
of od
( h + k ) d a nd e ve n F 0
odd F2  0
 F is independent of the ‘l’ index e.g. 100, 101, 102; 031, 032, 033.
 The result derived (i.e. the effect of lattice centring) can be understood by a simple geometric consideration. This is
illustrated for the C-centred OR crystal considered before, but is valid for all crystals.
 Let us view the [001] projection of the crystal and consider two sets of planes: (210) and (310) planes.
 On introducing a centring a new set of lattice planes between the original (210) planes have to be introduced, which
scatter exactly out of phase with the original planes and hence the 210 reflection goes missing on introducing a C-
centring. In the case of the (310) planes no new planes need to be introduced and this reflection survives.

 If the blue planes are scattering in phase then on C-

centering the red planes will scatter out of phase (with
the blue planes- as they bisect them) and hence the
(210) reflection will become extinct
 This analysis is consistent with the extinction rules: (h
+ k) odd is absent
 In case of the (310) planes no new translationally
equivalent planes are added on lattice centering  this
reflection cannot go missing.
 This analysis is consistent with the extinction rules: (h
+ k) even is present
Funda Check How come the unit cell for the reciprocal lattice is different from that of the
reciprocal crystal (for the case of the c-centred orthorhombic crystal*)?

 The reciprocal lattice is a pure geometric construct from the real lattice; wherein, planes are
transformed into points.
 The physics is introduced into the problem via the presence of atoms, which may scatter in
phase according to Laue’s or Braggs’ equations. This results in intensities decorating the
reciprocal lattice.
 Due to presence of additional atoms in the UC (arising from additional lattice points in a
non-primitive UC or as a part of the motif) some of these intensities are zero.
 Thus the UC (according to the picture: crystal = lattice + motif) is altered.

Lattice: C-centred orthorhombic

UC of reciprocal
lattice (primitive)
Motif: Intensity (4f2)

UC of the reciprocal
crystal

UC of crystal in
UC of reciprocal crystal: non-primitive
reciprocal space
* I.e. c-centred orthorhombic lattice decorated with a single ‘atom’ motif.
F SC, Al at (0, 0, 0), Ni at (½, ½, ½) NiAl: Simple Cubic (B2- ordered structure)
Click here to know more about ordered structures

1 1 1
i[2 ( h   k   l  )] SC
i[2 ( h 0  k  0  l  0)]
F  f Al e  f Ni e 2 2 2
Real
h  k l
i[ 2  ( )]
 f Al e0  f Ni e 2
 f Al  f Ni ei [ h  k l ]

F  f Al  f Ni F 2  ( f Al  f Ni ) 2
l) even e.g. 110, 200, 211, 220, 310.
(h + k +
F  f Al  f Ni ei [ h  k  l ]
(h + k +
l ) odd
F  f Al  f Ni F 2  ( f Al  f Ni )2
e.g. 100, 111, 210, 032, 133.

This term is zero for BCC

 When the central atom is identical to the corner ones we have the BCC case.
 This implies that (h+k+l) even reflections are only present in BCC.
 Click here to know more about
Reciprocal lattice/crystal of NiAl
e.g. 110, 200, 211, 220, 310.

I  ( f Al  f Ni ) 2

UC in reciprocal
space&

I  ( f Al  f Ni )2

e.g. 100, 111, 210, 032, 133.

UC of reciprocal crystal: non-primitive

Reciprocal Lattice: FCC.

Crystal Motif: fundamental reflection at (0,0,0) & superlattice reflection at (½,0,0).
* Coordinates in reciprocal space.
&
B2 gives NaCl in reciprocal space !!
G FCC, C at (0,0,0) & (¼, ¼, ¼) Diamond Cubic

i [2 ( 0)]  i [2 ( h 4k l )] 

F  f C  e   f C e 
  Ni
i ( h  k ) i ( k  l ) iReal
 f Al  f Ni [e e  e (l h ) ]
Al
i ( h  k ) i ( k  l ) i ( l  h )
F  f Al  f Ni [e e e ]

(h, k, l) unmixed F  f Al  3 f Ni F 2  ( f Al  3 f Ni )2 (111), (200), (220), (333), (420)

h,k,l → all even or all odd

(h, k, l) mixed F  f Al  f Ni F 2  ( f Al  f Ni )2 (100), (211); (210), (032), (033)

Two odd and one even (e.g. 112); two even and one odd (e.g. 122)
 Click
Click here
here to
to know
know more
more about
about ordered
ordered structures
structures

G SC, Al at (0,0,0), Ni at (½, ½, 0) and equivalent positions

Simple Cubic (L12 ordered structure)
(½, ½, 0), (½, 0, ½), (0, ½, ½)

 i[2 ( h 2 k )] i[2 ( k 2l )] i[2 ( l 2h )] 

F  f Al e   f Ni e
i [2 ( 0)]
e e 
  Ni
i ( h  k ) i ( k  l ) i ( l  h )
Real
 f Al  f Ni [e e e ]
Al
i ( h  k ) i ( k  l ) i ( l  h )
F  f Al  f Ni [e e e ]

(h, k, l) unmixed F  f Al  3 f Ni F 2  ( f Al  3 f Ni )2 (111), (200), (220), (333), (420)

h,k,l → all even or all odd

(h, k, l) mixed F  f Al  f Ni F 2  ( f Al  f Ni )2 (100), (211); (210), (032), (033)

Two odd and one even (e.g. 112); two even and one odd (e.g. 122)
 Click here to know more about
Reciprocal lattice/crystal of Ni3Al

F 2  ( f Al  3 f Ni )2

e.g. (111), (200), (220), (333), (420)

F 2  ( f Al  f Ni )2

e.g. (100), (211); (210), (032), (033).

UC of reciprocal crystal: non-primitive

E Na+ at (0,0,0) + Face Centering Translations  (½, ½, 0), (½, 0, ½), (0, ½, ½)
Cl− at (½, 0, 0) + FCT  (0, ½, 0), (0, 0, ½), (½, ½, ½)
NaCl: FCC lattice
 i[ 2 ( 0 )] i[ 2 ( h 2 k )] i[ 2 ( k 2l )] i[ 2 ( l 2h )] 
F  f Na  e e e e 
 
 i[ 2 ( h2 )] i[ 2 ( k2 )] i[ 2 ( 2l )] i[ 2 ( h 2k l )] 
f Cl   e e e e 
 
F  f Na  [1  ei ( h  k )  ei ( k l )  ei ( l  h ) ] 
f Cl  [e i ( h )  ei ( k )  ei ( l )  ei ( h  k l ) ]

F  f Na  [1  ei ( h  k )  e i ( k l )  e i (l  h ) ] 
f Cl  ei ( h  k l ) [e i (  k l )  ei (  l  h )  e i (  h  k )  1]
F  [ f Na   f Cl  e i ( h  k l ) ][1  e i ( h  k )  e i ( k l )  e i ( l  h ) ]
F  [ f Na   f Cl  e i ( h  k l ) ][1  e i ( h  k )  e i ( k l )  e i (l  h ) ]
NaCl: FCC lattice

F  [Term  1][Term  2] Zero for mixed indices

Mixed indices CASE h k l

Mixed indices A o o e
B o e e
CASE A : Term  2  [1  ei ( e )  ei ( o )  ei ( o ) ]  [1  1  1  1]  0
CASE B : Term  2  [1  ei ( o )  ei ( e )  ei ( o ) ]  [1  1  1  1]  0

(h, k, l) mixed F 0 F 02 100, 211; 210, 032, 033

Unmixed indices CASE h k l

Unmixed indices A o o o
B e e e

CASE A : Term  2  [1  e i ( e )  e i ( e )  e i ( e ) ]  [1  1  1  1]  4
CASE B : Term  2  [1  ei ( e )  ei ( e )  e i ( e ) ]  [1  1  1  1]  4

Continued…
 NaCl: FCC lattice

(h, k, l) unmixed F  4[ f Na   f Cl  e i ( h  k l ) ] 111, 222; 133, 244

h,k,l → all even or all odd

F  4[ f Na   f Cl  ] If (h + k + l) is even F 2  16[ f Na   fCl  ]2  I 

222, 244

F  4[ f Na   f Cl  ] If (h + k + l) is odd F 2  16[ f Na   f Cl  ]2  I 
111, 133

UC in reciprocal
space*

* NaCl gives B2 in reciprocal space !!

UC of reciprocal crystal: non-primitive
 Presence of additional atoms/ions/molecules in the UC can alter the intensities of
some of the reflections

Reflections which may be Reflections necessarily

Selection / Extinction Rules

Bravais Lattice
present absent
Simple all None

Body centred (h + k + l) even (h + k + l) odd

Face centred h, k and l unmixed h, k and l mixed

h and k unmixed h and k mixed
End centred
C centred C centred

Bravais Lattice Allowed Reflections

SC All
BCC (h + k + l) even
FCC (CCP) h, k and l unmixed

DC h, k and l are all odd

Or
(Rules for CCP + all are even
additional condition & (h + k + l) divisible by 4
List of observed reflections h2 + k2 + l2 SC FCC BCC DC
SC, FCC, BCC & DC 1 100
crystals 2 110 110
3 111 111 111
4 200 200 200
5 210
6 211 211
Cannot be expressed as a sum 7
of the square of 3 integers 8 220 220 220 220
9 300, 221
10 310 310
11 311 311 311
12 222 222 222
13 320
14 321 321
15
16 400 400 400 400
17 410, 322
18 411, 330 411, 330
19 331 331 331
Relative intensity of peaks in powder patterns
 We have already noted that absolute value of intensity of a peak (which is the area under a
given peak) has no significance w.r.t structure identification.
 The relative value of intensities of the peak gives information about the motif.
 One factor which determines the intensity of a hkl reflection is the structure factor.
 In powder patterns (& other experimental conditions) many other factors come into the
picture as in the next slide. Some of these have origin in crystallography (like the
multiplicity factor), some have origin in the powder diffraction geometry (like the Lorentz
factor), some are related to the radiation (polarization factor), etc.
 The multiplicity factor relates to the fact that we have 8 {111} planes giving rise to single
peak, while there are only 6 {100} planes (and so forth). Hence, by this very fact the
intensity of the {111} planes should be more than that of the {100} planes.
 A brief consideration of some these factors are in upcoming slides. The reader may consult
Cullity’s book for more details.
Relative Intensity of diffraction lines in a powder pattern
Scattering from UC (Atomic Scattering Factor is included
Structure Factor (F)
in this term)

Multiplicity factor (p) Number of equivalent scattering planes

Polarization factor Effect of wave polarization


I P  1  Cos 2  2  
Lorentz factor Combination of 3 geometric factors

 1   1 
Lorentz factor    Cos   
 Sin2   Sin2 

Absorption factor Specimen absorption

Temperature factor Thermal diffuse scattering

Multiplicity factor Actually only 3 planes ! (as (hkl)  (h k l)

Lattice Index Multiplicity Planes

Cubic (100) 6 [(100) (010) (001)] ( 2 for negatives)
(with highest
symmetry) (110) 12 [(110) (101) (011), (110) (101) (011)] ( 2 for negatives)
(111) 12 [(111) (111) (111) (111)] ( 2 for negatives)
(210)  3! Ways, (210)  3! Ways,
(210) 24*
(210)  3! Ways, (210)  3! Ways
(211)  3 ways, (211)  3! ways,
(211) 24
(211)  3 ways
(321) 48*
Tetragonal (100) 4 [(100) (010)] ( 2 for negatives)
(with highest
symmetry) (110) 4 [(110) (110)] ( 2 for negatives)

(111) 8 [(111) (111) (111) (111)] ( 2 for negatives)

(210) = 2 Ways, (210) = 2 Ways,
(210) 8*
(210) = 2 Ways, (210) = 2 Ways
(211) 16 [Same as for (210) = 8]  2 (as l can be +1 or 1)
(321) 16* Same as above (as last digit is anyhow not permuted)

* Altered in crystals with lower symmetry

 Multiplicity factor

hkl hhl hk0 hh0 hhh h00

Cubic
48* 24 24* 12 8 6
hk.l hh.l h0.l hk.0 hh.0 h0.0 00.l
Hexagonal
24* 12* 12* 12* 6 6 2
hkl hhl h0l hk0 hh0 h00 00l
Tetragonal
16* 8 8 8* 4 4 2
hkl hk0 h0l 0kl h00 0k0 00l
Orthorhombic
8 4 4 4 2 2 2
hkl h0l 0k0
Monoclinic
4 2 2
hkl
Triclinic
2

* Altered in crystals with lower symmetry (of the same crystal class)
 The polarization factor and the Lorentz factor both have ‘ ’ dependence (only) can be combined into the
L-P factor. Note that the LP factor has a dip in middle 2  values (with large values at low and high
angles). [Fig.1].
 The signature of this factor is evident in the powder diffraction pattern from Po (simple cubic)  as shown
in Fig.2.
Lorentz factor
Polarization factor
 1 

I P  1  Cos  2  2
 Lorentz factor    Cos   1 
30
 Sin2   Sin2 

 1  Cos 2  2   25
Lorentz Polarization factor   
 Sin  Cos 
2
Fig.1

Lorentz-Polarization factor
20

Click here for details XRD pattern from Polonium 15

All peaks present

Fig.2 10
Look at general trend line!

0
Example of effect of Polarization factor 0 20 40 60 80
on power pattern Bragg Angle (q, degrees)
Intensity of powder pattern lines (ignoring Temperature & Absorption factors)

 Valid for Debye-Scherrer geometry

 1  Cos 2 
2
2
I  F p   I → Relative Integrated “Intensity”
 Sin  Cos 
2
 F → Structure factor
 p → Multiplicity factor

 POINTS
 As one is interested in relative (integrated) intensities of the lines constant factors are
omitted:
 Volume of specimen  me , e  (1/dectector radius)
 We have assumed random orientation of crystals  in a material with Texture relative
intensities are modified. So if a powder pattern has to be compared (both in intensity and
angle of peaks) with standard JCPDS/ICDD files, then the effect of texture has to be
removed first. Texture can be removed by: (i) making a fine powder and then annealing the
same (if required) or (ii) rotating the sample to all orientations (practically how this can be
done is not explained here!).
 I is really diffracted energy (as Intensity is Energy/area/time).
 Ignoring Temperature & Absorption factors is valid for lines close-by in pattern.