X-ray Diffractometry

Basic Concepts

T. P. Radhakrishnan
School of Chemistry
University of
Hyderabad
This powerpoint presentation is available
at the following website

http://202.41.85.161/~ch521/

Click on x-ray_powd.ppt
 Outline
• Crystals
èsymmetry
èclassification of lattices
èMiller planes
• Waves
èphase, amplitude
èsuperposition of waves
• Bragg law
• Powder diffraction
• Systematic absences, Structure factor
• Single crystals - Solution and Refinement
• Diffraction line width
• Applications of Powder diffraction
• Crystals
• Waves
• Bragg Law
• Powder diffraction
• Systematic absences, Structure factor
• Single crystals - Solution and Refinement
• Diffraction line width
• Applications of powder diffraction
Crystal and its structure

Anthony, Raghavaiah,
Radhakrishnan,
Cryst. Growth Des. 2003, 3,
3-
dimensions
STM image of 1,3-diheptadecylisophthalate
on HOPG
(with a model of two molecules)

Plass, Kim, Matzger, J. Am. Chem. Soc.

2-dimensional square
lattice
 Point group symmetries :
Identity (E)
Reflection ()
Rotation (Rn)
Rotation-reflection (Sn)
Inversion (i)
In periodic crystal lattice :
(i) Additional symmetry - Translation
(ii) Rotations – limited values of n
Translation
Translation
Translation
Translation
Rotatio
n
Rotatio
n
Rotatio
n
 Restriction on n-fold rotation
symmetry
in a periodic lattice
a
a 

na
(n-1)a/2

cos (180-) = - cos = (n-1)/2

n 3 2 1 0 -1
o 180 120 90 60 0
Rotation 2 3 4 6
1
 Seven Crystal
Systems

Cubic Tetragonal Orthorhombic

Monoclinic Triclinic Trigonal Hexagonal

 Cubic Bravais
Lattices

Primitive cube (P) Body centred cube (I)

Face centred cube (F)

 Fourteen Bravais
Lattices

Cubic - P, F (fcc), I (bcc)

Tetragonal - P, I
Orthorhombic - P, C, I, F
Monoclinic - P, C
Triclinic - P
Trigonal - R
Hexagonal/Trigonal - P
Point group 7 Crystal systems
operations

Point group
operations + 14 Bravais lattices
translation
symmetries
Lattice
(o)basis
+ = crystal structure
(x)
 C4
Spherical
basis

Non-spherical C4

basis
 Lattice + Lattice +
Spherical Basis Nonspherical Basis
Point group 7 Crystal systems 32 Crystallographic
operations point groups

Point group
operations + 14 Bravais lattices 230 space groups
translation
symmetries
 Miller plane in 2-D
a

Distance
between
lines = a

y
(01)
x
(10)
 Miller plane in 2-D

Distance
between
lines = a/
2
y = 0.7 a

x
(11)
 Miller plane in 2-D

Distance between
lines =  
(2)2+(3)2
= 0.27 a

(23)
x
 Miller plane in 2-D

Distance
between
lines =
2
= 0.5 a
y

x
(20)
Lattice in 3-
dimensions
 Miller plane in 3-D

(100
) Distance
between
z planes =
y 
x

a
 Miller plane in 3-D

(010
)Distance
between
z planes =
y 
x
 Miller plane in 3-D

(110)
Distance
between
z planes = a/
y 2
= 0.7 a
x
 Miller plane in 3-D

(111)
Distance
between
z planes = a/
y 3
= 0.58 a
x
Spacing between Miller
planes

dhkl = a


for cubic crystal

system
• Crystals
• Waves
• Bragg Law
• Powder diffraction
• Systematic absences, Structure factor
• Single crystals - Solution and Refinement
• Diffraction line width
• Applications of powder diffraction
 0   Phase
0 /  Displacemen
t
=
A sin{2(x/ -
wavelength
 = frequency

sin (0) = sin (n) = 0

sin (n/2) = +1 when n is odd
= -1 when n is
 Superposition of Waves

amplitude = A amplitude =
2A
Constructive
interference
 Superposition of Waves
/

amplitude = A amplitude =
1.4A
Total wave = A{sin[2

22

22

22


 222
 2
 Superposition of Waves
/

amplitude = A amplitude =
0
Destructive
interference
 x
1

x+
2
/2
x+
 3

Waves 1 and 2 interfere destructively

Waves 1 and 3 interfere constructively
• Crystals
• Waves
• Bragg Law
• Powder diffraction
• Systematic absences, Structure factor
• Single crystals - Solution and Refinement
• Diffraction line width
• Applications of powder diffraction
Wavelength =

 
dhkl

hkl plane

2dhkl sin = n
• Crystals
• Waves
• Bragg Law
• Powder diffraction
• Systematic absences, Structure factor
• Single crystals - Solution and Refinement
• Diffraction line width
• Applications of powder diffraction
Single crystal Collection of several small
crystals

Cones intersecting a film

Powder diffraction
setup
 Powder x-ray
diffractogram
1296
(sodium chloride) P o w d e r C e ll 2 . 2

Nacl

200

220
Counts
648

420

422
222

400
111

311

511
331
0

10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100

2
NaCl - powder x-ray
data
source Cu-K ( = 1.540598
Indexin
g

a=
d(h2+k2+l2)½
• Crystals
• Waves
• Bragg Law
• Powder diffraction
• Systematic absences, Structure factor
• Single crystals - Solution and Refinement
• Diffraction line width
• Applications of powder diffraction
Primitive
cube

b.c.c. (h+k+l = odd absent )

f.c.c. (h, k, l all even or all odd present )

 (h00)

a/h

a
 2' (h00)
3'
1'
2dh00sin =



dh00 =

 
Path difference 2'1',  = 
1
2 Path difference 3'1',  = 
3 xa xa/(a/h)
a/h
=  hx
a

Phase difference 3'1' = (2/ hx =

In 3-D, the phase difference 3'1' =

2 hx+ky+lz)
The two waves 1 and 3 scattered from different
atomic layers have different phases,  1 and  2.

They will have different amplitudes A1and A2

if the atoms in the two planes are not the same.
 The scattered x-ray intensity is
the sum of the contributions from the
different scattered waves
Two waves having the same frequency, but different amplitude
and phase can be represented as :

E1 = A1sin 1 and E2 = A2sin 2

3

1 2
 Waves can be represented as
vectors in complex space

imaginar
y The wave vector can be written as

A A(cos + i.sin) = Aei


real
 Structure
Factor
Atomic scattering factor,

f= amplitude of wave scattered by an atom

amplitude of wave scattered by one electron

Wave scattered with phase, 2 hx+ky+lz)

from atoms having scattering factor, f contribute to the
Structure Factor for the Miller plane, (hkl) :

Shkl =  fn e2ihx +ky +lz )

n n n

n represent the atoms in the

basis
Shkl =  fn e2ihx +ky +lz )
n n n

Atom position
Relates to
Atom type
Intensity of x-ray scattered from
an
(hkl) plane

Ihkl  Shkl2
1 Reflection from (hk0)A plane
2 Reflection from (hk0)B plane
 Systematic Absences

Shkl = fA + fB e2
For body centred cubic lattice (bcc)
x = 1/2, y = 1/2, z = 1/2

(h+k+l) is even e i(h+k+l) = +1

2 i(hx+ky+lz) =
i(h+k+l) i(h+k+l)
(h+k+l) is odd e = -1
Shkl = fA + fB e i(h+k+l)

If fA = fB = f

Shkl = 2f when h+k+l is even

= 0 when h+k+l is odd

• Crystals
• Waves
• Bragg Law
• Powder diffraction
• Systematic absences, Structure factor
• Single crystals - Solution and Refinement
• Diffraction line width
• Applications of powder diffraction
Single Crystal X-ray Diffractometer
with CCD detector
 X-ray tube
Filament
X-rays

Cathode Water

Anode

Tungsten wire at 1200 – 1800oC

Heating current ~ 35 mA
Voltage ~ 40 kV (Cu), 45 kV (Mo)
 Goniometer

3-circle goniometer with fixed

CCD based detector
 Charge Coupled Device

http://www.sensorsmag.com/articles/0198/cc0198/main.shtm
 Fourier Synthesis

Shkl =  fn e2ihxn +ky +lz

n n

SK= f(r).eiK.r dr

by Fourier
transformation,
(r) f(r) = SK.e-iK.r.dK
 Structure Solution

•The Fourier map provides a structure

solution

•Using the initial solution a structure factor is

calculated for each (hkl)  Shkl(calc)

•For each (hkl) there is also an experimental

structure factor  Shkl(exp)
 Structure Refinement

•Least square method to carry out

regression
of Shkl(calc) against Shkl(exp). Quality of
refinement represented by the r factor

•The final model used for the best Shkl(calc)

is the structure solution
• Crystals
• Waves
• Bragg Law
• Powder diffraction
• Systematic absences, Structure factor
• Single crystals - Solution and Refinement
• Diffraction line width
• Applications of powder diffraction
 Effect of particle size on diffraction
lines
A
max
½Ama
B

 
 B (Bragg 

 

Particle size small Particle size large

Scherrer formula for particle size
estimation

0.9
t=
B
cosB

t = average particle size

 = wavelength of x-ray
B = width (in radians) at half-
height
B = Bragg angle
 Path
difference,
 A'D' =
0
d
 A'M' =
1

3  B'L' =

t = md  C'N' = (m-

m
 A'D' 2d sin B = 
A'M' 2(md)sin B = m
 i.e. 2d sin B = 

B'L' 2(md) sin 1 = (m+1)

C'N' 2(md) sin 2 = (m-1)

sin m When m
sin
= m+1


If m is finite, Bragg reflection is satisfied at    

• Crystals
• Waves
• Bragg Law
• Powder diffraction
• Systematic absences, Structure factor
• Single crystals - Solution and Refinement
• Diffraction line width
• Applications of powder diffraction
1. Finger printing

a) Qualitative/quantitative analysis of mixtures

Excedrin - composition of caffeine, aspirin,
acitaminphen
Fly ash - for cement industry
b) Monitoring asbestos, silica in paints
c) Degradation of drugs due to humidity
d) ‘Builders’ in detergents
Sodium and potassium phosphates
e) Phase analysis of cement
2. Polymorph characterisation

a) Paints and pigments

White pigment, TiO2 - rutile, anatase, brookite
Quinacridone paints
b) Pharmaceuticals
Sulfathiazole (antibacterial) - four polymorphs
Ranitidine (antiulcer) - active/inactive polymorphs
c) Food industry
Chocolate - 5 polymorphs stable at room temperature
3. Determination of degree of crystallinity and stress
- linebroadening

a) ‘Excipients’ in pharmaceutical formulations

cellulose - different derivatives have different
extents of crystallinity
b) Photography
Silver halide in gelatin- stress due to drying of
gelatin
c) Polymers - crystalline/amorphous phases
d) Preliminary characterisation of nanomaterials
Thank you
This powerpoint presentation is available
at the following website

http://202.41.85.161/~ch521/

Click on x-ray_powd.ppt