Outline

 Matter State
 7 System Crystal
 14 Bravais Lattice
 32 Point Group
 230 Space Group
 Miller Indices
Crystallography

Physics

Crystallo-
Engineering Chemistry
graphy

Biology
Matter State
Matter
Gaseous Liquid
State State
Solid
State
Amorphous Crystalline
(disordered) (ordered)
Energy and Packing
• Non dense, random packing Energy
typical neighbor
bond length

typical neighbor r
bond energy

Energy
• Dense, ordered packing typical neighbor
bond length

typical neighbor r
bond energy

Dense, ordered packed structures tend to have

lower energies & thus are more stable.
 Density of Material Classes
In general Metals/
Graphite/
Composites/
r metals > r ceramics > r polymers Alloys
Ceramics/
Semicond
Polymers
fibers
30
Why? 20 Platinum *GFRE, CFRE, & AFRE are Glass,
Gold, W
Metals have... Tantalum Carbon, & Aramid Fiber-Reinforced
Epoxy composites (values based on
• close-packing 60% volume fraction of aligned fibers
(metallic bonding) 10 Silver, Mo in an epoxy matrix).
Cu,Ni
Steels
• often large atomic masses Tin, Zinc
Zirconia
Ceramics have... 5

r (g/cm3 )
Titanium
4 Al oxide
• less dense packing 3
Diamond
Si nitride
• often lighter elements Aluminum Glass -soda
Concrete
Glass fibers
Silicon PTFE GFRE*
2
Polymers have... Magnesium G raphite
Silicone
Carbon fibers
CFRE*
A ramid fibers
• low packing density PVC
PET AFRE*
1 PC
(often amorphous) H DPE, PS
PP, LDPE
• lighter elements (C,H,O)
0.5
Composites have... 0.4
Wood
• intermediate values 0.3
Data from Table B1, Callister 7e.
What is a crystal？

A crystal is defined as a solid composed of atoms

arranged in a periodic pattern in three dimensions
 How to describe a crystal
Imagine…
 having to describe an infinite crystal with an infinite number of atoms
 or even a finite crystal, with some 1020 atoms
Sounds horrible? Well, there’s symmetry to help you out! Instead of an infinite
number of atoms, you only need to describe the contents of one unit cell, the
structural repeating motif…
 and life could be even easier, if there are symmetry elements present
inside the unit cell!
 you only need to describe the asymmetric unit if this is the case
 Lattice Symmetry

 Lattice symmetry refers to the unit cell size and shape

 Without rules, there would be an infinite number of different unit cells to
describe any given lattice
Unit Cell Choices
 By convention, a unit cell is chosen as
 the smallest possible repeat unit (2 priority)
 which has the highest symmetry (1 priority)
 This can result in primitive unit cells or centered unit cells
 not all crystal systems can be centered by this definition
 the seven crystal systems in combination with the centering
operations give rise to the 14 Bravais lattices
 Lattice Symmetry

 Lattice symmetry refers to the unit cell size and shape

 Without rules, there would be an infinite number of different unit cells to
describe any given lattice
 Without Symmetry

1,1,1
0,1,1
1,0,1
0,0,1
z 1,1,0
1
0,1,0
y
1,0,0
x 1 0,0,0
1 atom or molecule
 With Symmetry

z
1
y

x 1 0,0,0
1
 With Symmetry

0,0,0

y
x
 Symmetry Elements
 When talking about symmetry operations, we must distinguish
- point symmetry elements
- rotation axes
- mirror planes
- rotation-inversion axes
- translational symmetry
- translation
- glide (translation reflection)
- screw (translation rotation)
Rotation axes
 Example: A two-fold rotation axis
 no change in handedness
 referred to as “proper
symmetry operation”
 An n-fold rotation axis will rotate
the object by 360/n°

 Symbol: n (e.g., 2, 3, 4, 6)
 Graphical symbol:
Mirror planes
 A mirror plane changes the
handedness of the object it is
operating on.
 cannot exist in crystals of an
enantiomerically pure substance
 referred to as “improper
symmetry operation”

 Symbol: m
 Graphical symbol:
Inversion Centers
 “Turning an object inside out”
 Equivalent to a “point
reflection” through the inversion
center
 similar to focal point of a lense
 changes handedness
 Symbol: I
 Graphical symbol :
Rotation - Inversion Centers
 Rotation followed by
inversion
 An inversion center can be
regarded as a “one-fold rotation”
followed by an inversion

 Symbol: -n or n
 Graphical Symbol :
7 - Crystal Classes
 14 – Bravais Lattice
Crystal Family Bravais Lattice
c

β α
b
γ
a
Higher Symmetry
32 - Point Group
 Show 3D repeat pattern
 Contain symmetry elements
Triclinic Point Group
Monoclinic Point Group
Orthorhombic Point Group
Tetragonal Point Group
Trigonal Point Group
Hexagonal Point Group
Cubic Point Group
Translation – Glide – Screw axis
a

a/2

1/2 lattice (glide)

a/2

21 ( Screw )
3n Screw axis
32
31
1”
2’

1’ 3’
3
2 1’
2

3
1
1
Graphical symbols of crystallographic symmetry elements

For more details, see International Tables for Crystallography vol. A

Space Group
 When talking about crystal structures, people will usually
report the space group of a crystal
 Space groups are made up from
 point symmetry (not translational)
 lattice symmetry (translational)
 glide and/or screw axes (some translational component)

7 crystal 14 Bravais 32 point 230 space

systems lattices groups groups

For more details, see International Tables for Crystallography vol. A

Defining Crystallographic Planes
 Miller Indices: reciprocals of the (three) axial
intercepts for a plane and common multiples.

 Algorithm (in cubic lattices this is direct)

1. Read off intercepts of plane with axes in
terms of a, b, c
2. Take reciprocals of intercepts
3. Reduce to smallest integer values
4. Enclose in parentheses, no
commas i.e., (hkl) → families {hkl}
Crystallographic Planes (1)
z
example a b c c
1. Intercepts 1 1 ∞
2. Reciprocals 1/1 1/1 1/∞
1 1 0 b
3. Reduction 1 1 0 y
a
4. Miller Indices (110)
x
z
example a b c
1. Intercepts 1/2 -1 ∞ c
2. Reciprocals 1/½ 1/-1 1/∞
2 -1 0
3. Reduction 2 -1 0 b
y
4. Miller Indices (210) a
a
x
 Crystallographic Planes (1)
z
example a b c c
1. Intercepts 1/2 1 3/4 •
2. Reciprocals 1/½ 1/1 1/¾
2 1 4/3 •
• y
3. Reduction 6 3 4 a b
4. Miller Indices (634) x

Family of Planes {hkl}

Ex: {100} = (100), (010), (001), (100), (010), (001)

Crystallographic Planes (2)
In hexagonal unit cells the same idea is used
z

example a1 a2 a3 c
1. Intercepts 1 ∞ -1 1
2. Reciprocals 1 1/∞ -1 1
1 0 -1 1
3. Reduction 1 0 -1 1
a3

4. Miller-Bravais Indices (1011) a1

Adapted from Fig. 3.8(a), Callister 7e.

Plane families
Distance Between Planes
(100) d100
a at 1
a b at ∞
d(100) = =a
1 +0 +0
2 2 2 c at ∞

(100)
d200
(200) a at 1/2
a a b at ∞
d(200) = =
2 +0 +0
2 2 2 2 c at ∞
(200)

(110) a at 1
a a b at 1
d(110) = 2 2 2 =
1 +1 + 0 2 c at ∞
(110)
A Simple Crystal Structure
CsCl - Cesium Chloride

Cs+
z
(100)
(001)
{100}
(010)
a
Cl-
x y

a a
A Simple Crystal Structure
CsCl - Cesium Chloride

Cs+
z
(200)
{200}
a
Cl-
x y

a a
A Simple Crystal Structure

‘Building block’ = 1 Cs ion + 1 Cl ion

‘Grid system’ = primitive cube
one Cs ion at each corner site (0,0,0)
one Cl ion in the center of the cube (1/2,1 /2,1 /2)

Note: 8 corner sites - each corner site shared

by 8 cubes.
∴ One Cs ion + one Cl ion per cube.
A (not quite so) Simple Crystal Structure

NaCl - Sodium Chloride

Na+

Cl-
A (not quite so) Simple Crystal Structure

Lattice = FCC = Face Centred Cubic

Cl Na
FCC - atoms at (0, 0, 0) (1/2,1/2,1/2)
(1/2,1/2,0) (0, 0,1/2)
(1/2,0,1/2) (0,1/2, 0)
(0,1/2,1/2) (1/2, 0, 0)
Quiz 1

http://www.ruppweb.org/Xray/tutorial/centrics.htm
Questions
Outline
 Diffraction by Slit
 Diffraction by atom
 Diffraction by plane (set of atoms)
 Miller Indices and Diffraction (examples)
 Structure Factor
Diffraction
Diffraction is the “interference” phenomenon where the wave
path bent by object

Diffraction need:
 Monochromatic in order to fix wavelength
 Collimated beam in order to fix the angle
 Coherent radiation to have coherent interference between
the waves
Single Slit Diffraction
The ‘slit’ scatters light and become a point source
λ

d
Single Slit Diffraction

d
Double Slit Diffraction
λ
d.sinθ = m.λ

m=2

m=1
θ
d m=0

m= -1

m= -2
Multiple Slits Diffraction
λ
d.sinθ = m.λ

d m=2

m=1
θ
m=0

m= -1

m= -2
Diffraction (constructive interferences)
λ

x = d sinθ = λ
Diffraction (destructive interferences)
λ

x = d sinθ = λ
Single Atom Diffraction

d
Lattice Diffraction

dhkl

2λ = x + x = d sinθ + d sinθ = 2d sinθ (Bragg’s law)

Powder Diffraction Pattern
c
(110) c
c

a b (211)
a b
a b

(200)

2 theta (deg)

Diffraction pattern for polycrystalline a-iron (BCC)

Reflection Position and Intensity
What influences the peak position and intensity of Bragg
reflections?
Example: CsCl

Cs+ a

a a Cl-
Reflection Position and Intensity
Real crystal structure CsCl a = 4.11Å, λ=1.54Å
Calculate: d(hkl) and θhkl for the following (hkl)

hkl d θ 2θ I
(001)
(011)
(111)
{002)
(001) reflection

d(001) = a = 4.11 Å
Re-call Bragg equation: λ = 2𝑑𝑑 sin θ
−1 λ −1 1.54
θ = sin = sin =10.80°
2𝑑𝑑 4.11
(001) reflection

d(001)

Cl-

Cs+
 (001) reflection
The diagram shows the (001) planes scattering in phase
 The reflecting power of atoms (normally called the
atomic scattering factor) is related to the number of
electrons in the atom
Cs+ = 54 electrons
Cl- = 18 electrons
 the reflected beam from Cs+ atoms has an
amplitude 3x larger than the beam from Cl- atoms
 (001) reflection
Look at the wavefront A - A of the reflected beam.
 Beams from Cl- atoms (on planes d100 apart) are in phase.
 Beams from Cs+ atoms (also on planes d100 apart) are in phase.
But, since Cs+ planes are exactly half-way between Cl- planes,
beams from Cs+ and Cl- planes are exactly out of phase.
 Amplitude of diffracted beam ∝ y(54 - 18) = y(36)
(y is some constant)
 Intensity = I001 ∝ y2 (36)2 = 1296y2 (Weak reflection)
 (002) reflection

𝑎𝑎 4.11
d(002) = = = 2. 055 Å θ = 22.07°
2 2
This time all atoms scatter in-phase.
 Amplitude of diffracted beam ∝ y (54 + 18) = y(72)
 Intensity of diffracted beam I(002) ∝ y2 x 722 = 5184y2 (Strong
reflection)
(002) reflection

d(002)

Cl-

Cs+
 (011) reflection

Cs+ and Cl- ions all lie in the (011) planes

Cs+ and Cl- scatter in phase
𝑎𝑎 4.11
d(011) = = = 2. 91 Å θ = 15.34°
2 2
I(011) ∝ 𝑦𝑦 2 (54 + 18)2 = 5184𝑦𝑦 2 (Strong reflection)
 (111) reflection

Cl- ions lie in (111) planes and d(111) apart. Cl- ions scatter in phase
Cs+ ions lie mid-way between Cl- planes. Cl+ ions scatter out of phase
𝑎𝑎 4.11
d(111) = = = 2. 373 Å θ = 18.94°
3 3
I(111) ∝ 𝑦𝑦 2 (54 − 18)2 = 1296𝑦𝑦 2 (Weak reflection)
Reflections
To summarize:
hkl d θ 2θ I remark
100 4.11 10.84 21.60 1296 Weak
110 2.91 15.34 30.69 5184 Strong
111 2.373 18.94 37.88 1296 Weak
200 2.055 22.07 44.01 5184 Strong

from lattice from ‘building block’

Crystal Structure
CsCl Diffraction Pattern

Multiplicity not taking into account

A (not quite so) Simple Crystal Structure

NaCl - Sodium Chloride

Na+

Cl-
Reflections
NaCl (FCC) Top View
Cl-
Na+
d(200)
d(100)

 (100) absent completely

 (200) strong
 (110) absent completely
 (220) strong
(111) reflection

Na+

Cl-
(111) reflection
Cl- atoms lie in (111)planes
Na+ atoms lie in between Scatter out of phase
I ∝ A2(18-8)2 = 100 A2
= (111) is quite weak
Cl- atoms lie in (222)planes
Na+ atoms lie in (222)planes Scatter in phase
I ∝ A2 (18+8)2 = 262 A2
= (222) is quite strong
NaCl Diffraction Pattern

Multiplicity not taking into account

 Summary

The diffraction pattern is like a finger print of the

crystal structure:

 d values reflect the unit cell parameters (grid)

 intensities reflect the atoms/molecules (building blocks)

 Structure Factor
𝑁𝑁

𝐹𝐹ℎ𝑘𝑘𝑘𝑘 = � 𝑓𝑓𝑛𝑛 𝑒𝑒 2𝜋𝜋𝜋𝜋(ℎ𝑥𝑥𝑛𝑛 +𝑘𝑘𝑘𝑘𝑛𝑛 +𝑙𝑙𝑙𝑙𝑛𝑛 )

1

 The structure factor quantifies the amplitude of X-rays scattered by a crystal

 Fhkl sums the result of scattering from all of the atoms in the unit cell to form
a diffraction peak from the (hkl) planes of atoms
 The amplitude of scattered light is determined by:
 where the atoms are on the (hkl) planes
 this is expressed by the fractional coordinates xj yj zj
 what atoms are on the atomic planes
 the scattering factor fj quantifies the relative efficiency of scattering at
any angle by the group of electrons in each atom
 Atomic Scattering Factor
2
2 −𝐵𝐵 𝑠𝑠𝑠𝑠𝑠𝑠2 𝜃𝜃 ⁄𝜆𝜆2
𝑓𝑓 = 𝑓𝑓0 𝑒𝑒 + (Δ𝑓𝑓𝑓)2 + (Δ𝑓𝑓")2

 X-rays are electromagnetic radiation that interact with an electron,

which reradiates the X-ray as a spherical wave
 The number of electrons around an atom defines how strongly it will
scatter the incident X-ray beam
 the initial strength of the atomic scattering factor is equal to the
number of electrons around the atom
 The scattering factor, f, is a product of several terms describing the
interaction of the X-ray with the electrons around an atom
Atomic Scattering Factor effect
 Atomic Scattering Factor
 f0 at 0° is equal to the number of 40
Y
electrons around the atom 35 Y(3+)
Zr
 Y and Zr are similar, but slightly different, Zr(4+)
30
at 0° O(2-)
25
 Zr and Zr4+ are slightly different at 0°
 Y3+ and Zr4+ are identical at 0° 20

fo
 the variation with (sin θ)/λ depends 15

on size of atom 10

 smaller atoms drop off quicker 5

 at higher angles, the difference between 0

Y3+ and Zr4+ is
more readily discerned 0 0.5 1 1.5
(sin θ)/ λ
 at higher angles, the difference between
different oxidation states (eg Zr and Zr4+)
is less prominent
 Temperature Factor
 the efficiency of scattering by an atom  B sin 2 θ 
f = f 0 exp − 
is reduced because the atom and its  λ2

electrons are not stationary
 the atom is vibrating about its 40
B=0
equilibrium lattice site 35 B=1
 the amount of vibration is quantified by B=10
30
the Debye-Waller temperature factor:
B=8π2U2 25
○ U2 is the mean-square amplitude of the
20
vibration

f
 this is for isotropic vibration: sometimes 15

B is broken down into six Bij anistropic 10

terms if the amplitude of vibration is
not the same in all directions. 5

 aka temperature factor, displacement 0

factor, thermal displacement parameter 0 0.5 1 1.5 2
(sin θ)/ λ
Temperature Factor effect
Real Space
a
100

200

300
400

c
004

003

001
002

202

101
Reciprocal Space
𝜆𝜆 = 2𝑑𝑑ℎ𝑘𝑘𝑘𝑘 𝑠𝑠𝑠𝑠𝑠𝑠𝑠𝑠
a*
∗
𝑑𝑑ℎ𝑘𝑘𝑘𝑘 = 1/𝑑𝑑ℎ𝑘𝑘𝑘𝑘
200 201 202 203 204

h0l = 2n
h+l = 2n
Systematic presence
100 101 102 103 104
Weak reflection

Systematic absence
001 002 003 004
0
c*
 Real and Reciprocal Space
Crystal Space Diffraction Space
(𝑑𝑑ℎ𝑘𝑘𝑘𝑘 ) ∗
(𝑑𝑑ℎ𝑘𝑘𝑘𝑘 = 1/𝑑𝑑ℎ𝑘𝑘𝑘𝑘 )
Crystal lattice Reciprocal lattice

𝝀𝝀
s𝑖𝑖𝑖𝑖𝑖𝑖 =
2𝑑𝑑ℎ𝑘𝑘𝑘𝑘
Diffraction
Crystal
pattern

Unit cell contents Structure factor

(x,y,z) (𝐹𝐹ℎ𝑘𝑘𝑘𝑘 )
Crystal System Reciprocal Space
 Quiz 2

Peak 𝟐𝟐
𝒔𝒔𝒔𝒔𝒔𝒔𝟐𝟐 𝜽𝜽 𝒔𝒔𝒔𝒔𝒔𝒔𝟐𝟐 𝜽𝜽 𝒔𝒔𝒔𝒔𝒔𝒔𝟐𝟐 𝜽𝜽
2𝜃𝜃 𝒔𝒔𝒔𝒔𝒔𝒔 𝜽𝜽 𝟐𝟐 × 𝟑𝟑 × 𝒉𝒉𝟐𝟐 + 𝒌𝒌𝟐𝟐 + 𝒍𝒍𝟐𝟐 𝒉𝒉𝒉𝒉𝒉𝒉 a (Å)
No. 𝒔𝒔𝒔𝒔𝒔𝒔𝟐𝟐𝒎𝒎𝒎𝒎𝒎𝒎 𝒔𝒔𝒔𝒔𝒔𝒔𝟐𝟐𝒎𝒎𝒎𝒎𝒎𝒎 𝒔𝒔𝒔𝒔𝒔𝒔𝟐𝟐𝒎𝒎𝒎𝒎𝒎𝒎

1 38.43
2 44.67
3 65.02
4 78.13
5 82.33
6 96.93
7 111.83
8 116.36
Questions