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You are on page 1of 82

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)

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

n 3 2 1 0 -1

o 180 120 90 60 0

Rotation 2 3 4 6

1

Seven Crystal

Systems

Cubic Bravais

Lattices

Fourteen Bravais

Lattices

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

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 (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

22

22

22

222

2

Superposition of Waves

/

amplitude = A amplitude =

0

Destructive

interference

x

1

x+

2

/2

x+

3

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

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

(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

2 hx+ky+lz)

The two waves 1 and 3 scattered from different

atomic layers have different phases, 1 and 2.

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 :

3

1 2

Waves can be represented as

vectors in complex space

imaginar

y The wave vector can be written as

real

Structure

Factor

Atomic scattering factor,

amplitude of wave scattered by one electron

from atoms having scattering factor, f contribute to the

Structure Factor for the Miller plane, (hkl) :

n n n

basis

Shkl = fn e2ihx +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

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

• 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

Heating current ~ 35 mA

Voltage ~ 40 kV (Cu), 45 kV (Mo)

Goniometer

CCD based detector

Charge Coupled Device

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

Fourier Synthesis

n n

SK= f(r).eiK.r dr

by Fourier

transformation,

(r) f(r) = SK.e-iK.r.dK

Structure Solution

solution

calculated for each (hkl) Shkl(calc)

structure factor Shkl(exp)

Structure Refinement

regression

of Shkl(calc) against Shkl(exp). Quality of

refinement represented by the r factor

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

Scherrer formula for particle size

estimation

0.9

t=

B

cosB

= 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 =

C'N' 2(md) sin 2 = (m-1)

sin m When m

sin

= m+1

• 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

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

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

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

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