Structural probes for

solid materials

3. Using diffraction to
probe crystal structures
 Contents

1. The reciprocal lattice in X-ray diffraction

2. Bragg’s Law in reciprocal space

3. Intensity of scattered X-ray beams

Lecture material and further reading:

1. “The Basics of Crystallography and Diffraction” (C. Hammond), Chapter 6, 8.4, 9.1, 9.2

2. “Elements of X-ray Diffraction” (B.D. Cullity and S.R. Stock), chapters 2, 3, 4

3. “Fundamentals of Powder Diffraction and Structural Characterization of Materials” (V.K.

Pecharsky and P.Y. Zavalij), chapter 2

4. “Elements of Modern X-ray Physics” (J. Als-Nielsen and D. McMorrow), chapter 4

5. “X-ray Structure Determination” (G.H. Stout and L.H. Jensen) , chapter 2

6. “Fundamentals of Crystallography” (C. Giacovazzo), chapter 3

7. http://www.chembio.uoguelph.ca/educmat/chm729/recip/8ewald.htm
The reciprocal lattice
in X-ray diffraction
Reciprocal lattice

(110)

a
 Reciprocal lattice

d(110)

(110)
 Reciprocal lattice

length = 2π/d(110)
(110)

*
O

(110)
Reciprocal lattice

(210)
 Reciprocal lattice

(210)
(110) length = 2π/d(210)

**
O

(110)
(210)
Reciprocal lattice

(010)

(310)
 Reciprocal lattice

(210) (310)
(010)
(110)

* * *
* (010)

(110)
(210)
(310)
 Reciprocal lattice

•Taking normals of length 2π/dhkl from the origin to every direct-space lattice
plane (hkl) leads to the formation of a set of points in three dimensions that
constitutes the reciprocal lattice.

•Each point on the reciprocal lattice corresponds to a plane in direct space.

 Reciprocal lattice

Direct space Reciprocal space

b b*
(010)
4
040
(Å)
030
(110)
(100)
2
020

010 110 210

(210)

a a*
c 2 4 c* 100 200 300 400
(Å)
2π/4 Å-1
 Properties of reciprocal lattice

Orthorhombic/tetragonal/cubic direct-reciprocal relationships

a* = 2π
a a = 2π α = β = γ = α* = β* = γ* = 90°
a*

b* = 2π b = 2π
b b*

c* = 2π c = 2π
c c*

(2π) 3
V* = = a*b*c*
V
3
V = (2π) = abc
V*
 Properties of reciprocal lattice

(for orthorhombic/tetragonal/cubic cell)

d*hkl = ha* + kb* + lc*

|d*hkl|2 = h2a*2 + k2b*2 + l2c*2

we measure the
O magnitude of this
vector in a diffraction
experiment:
|d*hkl| = 2π/dhkl

(Note: the reciprocal lattice vector is sometimes denoted by G

instead of d*)
 Properties of reciprocal lattice

The relationships between the direct space and reciprocal space unit cell
parameters allow us to obtain the expression for determining the direct space unit
cell parameters from Bragg’s law.

For orthorhombic, tetragonal and cubic symmetry, use the expression

|d*hkl|2 = h2a*2 + k2b*2 + l2c*2

and the relationships a* = 2π/a, b* = 2π/b, c* = 2π/c, |d*hkl| = 2π/dhkl

By substituting for the reciprocal parameters, 1 h2 + k2 l2

= +
dhkl2 a2 b2 c2
 Bragg’s Law in
reciprocal space
 Ewald sphere construction (1)

Paul Peter Ewald 1888 - 1985

•Build the reciprocal lattice and choose a reciprocal lattice point as the origin.
 Ewald sphere construction (2)

•Draw a vector AO in the incident X-ray beam direction of length 2π/λ

terminating at the origin. Let this vector correspond to the wavevector k
(since |k| = k = 2π/λ)
 Ewald sphere construction (3)

•Construct a circle of radius 2π/λ with its centre at A.

 Ewald sphere construction (4)

•Note whether this circle passes through any point of the reciprocal lattice; if
it does, then draw a vector AB to the point of the intersection. This
corresponds to diffracted X-ray wavevector k′.
 Ewald sphere construction (5)

k´

•Draw another vector OB = G to the point of the intersection.

•Because G ends on a point in the reciprocal lattice, it is normal to the set of
lattice planes (hkl) associated with that point and is of length 2π/d.
Therefore, |G| = 2π/d.
 Ewald sphere construction (6)

k´

•Draw a line AE perpendicular to G.

 Ewald sphere construction (7)

k´
k´

•Since k  2
   sin  , thus G  22  sin 
, then OE  2
 Ewald sphere construction (8)

k´
k´

•Since G  2
d
  sin  , we obtain   2d sin 
 2 2

•This implies that Bragg’s Law is satisfied when a reciprocal lattice point lies on the
circumference of the circle.

•The hkl diffraction peak corresponding to this reciprocal lattice point can then be
measured when the X-ray detector is at the correct θ.
 Ewald sphere construction (9)

k´
k´

•If the crystal is rotated (equivalent to rotating the grid of reciprocal lattice
points around O), then all the reciprocal lattice points inside the circle will
cross the circumference and thus be in the Bragg condition at some angle of
rotation.
Ewald sphere- diffraction geometry
 Ewald sphere and limiting sphere

4π / λ

2π / λ

The limiting sphere has twice the radius of the Ewald sphere and contains all of the reciprocal
lattice points that are accessible in a diffraction experiment for a given X-ray wavelength.
Intensity of scattered
X-ray beams
 Scattering from a unit cell

•Bragg’s Law allows us to determine d-spacings for different hkl planes and
hence the unit cell dimensions and angles.

•However, the positions of diffraction peaks give no information on the

contents of the unit cell.

•For this we need to measure the intensities of the diffracted beams when
the Bragg condition is satisfied.

•We need to consider the coherent scattering from all atoms in the crystal.

•We want to obtain an expression for the intensity of the diffracted beam as a
function of atom positions.

•It is enough to consider the arrangement of atoms in one unit cell.

 Scattering from a unit cell

•In an atom, phase differences are found for waves scattered by different
electrons in the same atom. This is accounted for by the atomic form factor
(a function of scattering angle).

•Similarly, phase differences are found for waves scattered by different

atoms in a unit cell.

•We start by considering the phase difference due to scattering from two
atoms when the Bragg condition is satisfied.
 Scattering from a unit cell

(h00) (h00)
2'
Atom A at origin 1' N

Incident beams c
diffracted from θ
(h00) planes θ
A B C A a
d

1 2 M

•Path difference between beams 11′ and 22′ (diffracted from parallel (h00)
planes) is given by distance MCN:

 21  2d h 00 sin    (due to Bragg’s law)

a
where d h 00  ( AC )  by the definition of Miller indices
h
 Scattering from a unit cell

(h00) (h00)
3' 2'

1' N

λ/2 c
R
θ
A θ B C A a

S
λ/2
1 3 2 M

•Now consider path difference between beams 11′ and 33′.

By proportionality   AB  ( AB )
31  ( SBR)    
 AC  a
h

 2  2h( AB )
Thus, phase difference in radians is 31   31  
   a
 Scattering from a unit cell

(h00) (h00)
3' 2'

1' N
c
R
θ
A θ B C A a
(x,0,0)
S

1 3 2 M

•If atom B is at fractional coordinate x = (AB)/a with respect to the origin, then

2h( AB )
31  31  2hx
a
•For an atom at any general point
in any type of unit cell with   2 hx  ky  lz 
fractional coordinates (x,y,z):
 Scattering from a unit cell

(h00) (h00)
3' 2'

1' N
c
R
θ
A θ B C A a
(x,0,0)
S

1 3 2 M

•If atoms A and B are of different types then waves 1′ and 3′ also differ in amplitude.

•The amplitudes are given by the atomic scattering factors fn(θ)

•Scattering from a unit cell can be described by adding the waves scattered from all
the atoms in the unit cell at the particular scattering angle θ where the Bragg
condition is satisfied.
 Scattering from a unit cell

kz

•Two scattered waves E1 and E2 should be added to obtain E3.

E1  A1 sin kz  1 
E2  A2 sin kz  2 

•The waves can be represented by vectors

and added geometrically:
 Scattering from a unit cell

•However, it is much easier to use the complex plane representation:

Im

E
•In general, a wave can be described by

φ
E  E0 cos   E0i sin   E0 ei
Re

kz
E3  A1e i1  A2 e i2
 Scattering from a unit cell

•The scattered wave from any atom in the unit cell can be expressed in complex
form, remembering that   2 hx  ky  lz 

Ae i  fe 2i hx  kylz 

•The amplitude of the resultant wave scattered by all the atoms in the unit cell can
then be obtained as the sum of scattered waves from each atom with coordinates
(xn,yn,zn) and is known as the unit cell structure factor:

N
Fhkl   f n e 2i hxn  kyn lzn 
1

N
or Fhkl   f n cos 2 hxn  kyn  lzn   i sin 2 hxn  kyn  lzn 
1
 Scattering from a unit cell

To summarise:

N
Fhkl   f n e 2i  hxn  kyn  lzn 

Form factor of
atom n for
Structure factor for scattering Atom n in unit cell
peak hkl. angle θ and has coordinates
Sum the wavelength λ (xn, yn, zn)
expression
for all N
atoms in the
unit cell
 Scattering from a unit cell
•Remember that the intensity of the scattered beam (the experimentally
measured quantity) is proportional to the square of the amplitude:
2
 N
2i  hxn  kyn  lz n  
I  Fhkl    f ne
2

 1 
2 2
 N
  N

I    f n cos 2 hxn  kyn  lzn     f n sin 2 hxn  kyn  lzn 
 1   1 
we want to work backwards to get Fhkl

N
Fhkl   f n cos 2 hxn  kyn  lzn   i sin 2 hxn  kyn  lzn 
1

•The measured X-ray intensity only gives us the “amplitude” Fhkl  I hkl
(a real quantity).

•We cannot obtain Fhkl (an imaginary quantity) directly- we do not know the
phases of the scattered waves and cannot directly get the atomic positions from
intensity information. Known as the phase problem.
 Effect of symmetry on the structure factor

•Some useful relations to note in structure factor calculations:

ei  e3i  e5i  1

e 2i  e 4i  e 6i  1

ni
  1
n
In general, e where n is any integer

e ni  e  ni where n is any integer

eix  e  ix  2 cos x

 Effect of symmetry on the structure factor

1. Primitive cell with one atom at origin

N
Fhkl   f n e 2i hxn  kyn lzn 
1

Fhkl  f n e 2i 0   f n

 fn
2 2
Fhkl

Fhkl is the same for all peaks

(independent of h, k, l).

(However, remember that fn and

hence the intensity depends on
diffraction angle)
 Effect of symmetry on the structure factor

2. Body-centred cell with one atom at (0,0,0) and another of same kind at (½,½,½)

N
Fhkl   f n e 2i hxn  kyn lzn 
1
½ 2i 0  
2i h  k  l 
Fhkl  f n e  f ne 2 2 2


Fhkl  f n 1  ei h  k l  
If (h + k + l) is even: Fhkl  2 f n
If (h + k + l) is odd: Fhkl  0

Therefore, there is non-zero diffracted intensity only when (h + k + l) is even.

Peaks such as 012, 111, 113, 102, 410 are systematically absent.
Effect of symmetry on the structure factor

_
Iron: space group Im3m

h + k + l = 2n
 Effect of symmetry on the structure factor

3. Face-centred cell with four atoms of the same kind

½ N
Fhkl   f n e 2i hxn  kyn lzn 
1

½ ½ 2i 0  
2i h  k  
2i k  l  
2i h  l 
Fhkl  f n e  f ne 2 2
 f ne 2 2
 f ne 2 2


Fhkl  f n 1  ei h  k   ei k l   ei h l  
½
If h, k and l are “unmixed”: Fhkl  4 f n
If h, k and l are “mixed”: Fhkl  1  1  1  1  0

Therefore, there is diffracted intensity only when h, k and l are all odd or all even.

Peaks such as 111, 200, 220 are present but 100, 210, 112 are systematically absent.
Effect of symmetry on the structure factor

_
NaCl: space group Fm3m

h, k and l are all odd or all even.

 Effect of symmetry on the structure factor

The so-called reflection conditions for lattice centring are summarised as follows:

Symmetry Reflection conditions

Primitive (P) None
Side-centred (C) hkl, h+k = even
Body-centred (I) hkl, h+k+l = even
Face-centred (F) all indices odd or all even

•In a diffraction experiment one can observe whether there are any reflection
conditions and hence determine the type of centring of the unit cell.
 Effect of symmetry on the structure factor

4. Screw axis (21) parallel to the a-axis at y=½

O N
Fhkl   f n e 2i hxn  kyn lzn 
b
1
(x,y,z)
ℎ −𝑘𝑦−𝑙𝑧
𝐹ℎ𝑘𝑙 = 𝑓𝑛 𝑒 2𝜋𝑖(ℎ𝑥+𝑘𝑦+𝑙𝑧 + 𝑓𝑛 𝑒 2𝜋𝑖(ℎ𝑥+ 2
(x+½,-y,-z)

There will be systematic absences when k = l = 0

a 𝐹ℎ𝑘𝑙 = 𝑓𝑛 𝑒 2𝜋𝑖ℎ𝑥 1 + 𝑒 𝜋𝑖ℎ

The screw axis generates a If h is even: Fhkl  2 f n

second atom at (x+½, -y, -z)
from the first atom at (x, y, z). If h is odd: Fhkl  0

Therefore, h00 diffraction peaks have non-zero intensity only when h is even.
 Effect of symmetry on the structure factor

Infinite symmetry elements also give rise to reflection conditions:

Symmetry Reflection conditions

Primitive (P) None
Side-centred (C) hkl, h+k = even
Body-centred (I) hkl, h+k+l = even
Face-centred (F) all indices odd or all even
21 screw axis parallel to b 0k0, k = even
b-glide plane perpendicular to a 0kl, k = even
c-glide plane perpendicular to b h0l, l = even
n-glide plane perpendicular to c hk0, h+k = even etc.

•The reflection conditions in a diffraction experiment can also tell us about the
presence or absence of infinite symmetry elements (screw axes, glide planes).
•They tell us nothing about finite symmetry elements that might be present:
rotation axes, mirror planes and inversion points do not give reflection conditions.
 Effect of symmetry on the structure factor

5. Inversion centre N
Fhkl   f n e 2i hxn  kyn lzn 
1

(-x,-y,-z) Fhkl  f n e 2i hx  kylz   f n e 2i  hx  kylz 

(x,y,z)
Fhkl  2 f n cos 2 hx  ky  lz 

(because eix  e  ix  2 cos x )

•The imaginary part of Fhkl is zero if the crystal structure has a centre of symmetry.

•The phases of the waves scattered by each atom are therefore 0 or π (scattered
wavevector lies horizontally in the complex plane). However, the phase problem
still applies- from the measured diffraction intensity we do not know if Fhkl is positive
or negative.
 Effect of symmetry on the structure factor

Friedel’s law

Fhkl  f n  A  iB 
N
Fhkl   f n ei 2 hxn  kyn lzn 
1

I hkl  f n2 ( A  iB )( A  iB )  f n2 A2  B 2 

F h  k l  f n  A  iB 
N
Fh k l   f n ei 2 hxn kyn lzn 
1

I h k l  f n2 ( A  iB )( A  iB )  f n2 A2  B 2 
•For an inversion centre, Fhkl  F h  k l However,

I hkl  I  h  k l is always valid, no matter whether or not Fhkl  F h  k l

•In reciprocal space a centre of symmetry (inversion centre) is always present,
whether or not the structure has an inversion centre in real space.
Influence of inversion symmetry on physical properties

•Quartz can be depicted (in a simplified way) as positively charged Si surrounded

by negatively charged O. It has no centre of inversion.
 Influence of inversion symmetry on physical properties

•If a mechanical stress is applied, individual SiO4 tetrahedra deform and become
elecrically polarized. The symmetry of quartz allows a net polarization under stress:
piezoelectricity. Vice versa, an electrical voltage causes structural distortion.
Influence of inversion symmetry on physical properties

Piezoelectric materials
S
+++++ V
-----

Pb(Ti1-xZrx)O3
Mechanical strain is converted
into electric current or voltage.
 Influence of inversion symmetry on physical properties

Multiferroics (combination of piezoelectrics / ferroelectrics with magnetic order)

[newsroom.ucla.edu]

• Data storage: electric writing, magnetic reading (large savings in power)

• Novel device architectures that mix electric and magnetic signals

• In the development of many new and potentially technologically important materials we

would like to know if an inversion centre is present. This cannot be done directly from
diffraction data.
 Effect of thermal vibration on the structure factor

•Atoms vibrate more as the temperature increases. This has a significant effect
on the structure factor and must be modelled using atomic displacement
parameters, often known as “thermal parameters”.

•The more an atom vibrates, the larger its electron cloud appears to the
incoming X-ray beam and the greater the degree of destructive interference.
Effect of thermal vibration on the structure factor

correction term

N
Fhkl   f n e M n
e 2i  hxn  kyn  lzn 

1
 sin  
2

Isotropic approximation: M n  Bn  
  

atomic displacement factor

of nth atom (units Å2)
 Effect of thermal vibration on the structure factor

 sin  
2

M n  B 
  

eM n

•Atomic displacement factor becomes more significant with increasing

diffraction angle as well as increasing temperature.

•Diffraction peaks have much lower intensity at high temperature.

 Effect of thermal vibration on the structure factor

•Thermal vibrations always cause a rapid decrease in the intensities of

diffraction peaks with increasing diffraction angle.

•This effect becomes more obvious as the temperature increases.

X-ray powder diffraction pattern of LaB6

 Effect of thermal vibration on the structure factor

•In a more sophisticated anisotropic approach “thermal ellipsoids” are used to

model the vibrations. This can also give information on electron density between
atoms (chemical bonding). Electron density is usually elongated perpendicular to a
chemical bond and vibrations are larger for atoms at ends of bonds.