Structures and

X-Ray Diffraction
Lectures 4-6

Last revised 4/13/10 5:13 am

 Learning Objectives
• Know the definition of a crystal
• Recognize lattice and motif in 2D and 3D
crystals
• Classify structures by Bravais Lattice
• Be able to draw, describe, and do
calculations with the cubic crystal
structures.
 Learning Objectives
• Calculate likely CNs of cations and anions,
using r/R
• Calculate whether a compound is likely to
form a glass, using Zachariasen’s rules
• Determine the likely unit cell of a material,
given its x-ray powder diffraction pattern
• Determine stoichiometry, density, APFs,
CNs of all ions, given a unit cell
 Crystal = Lattice + Motif
• Lattice = mathematical framework of
identical points, defined by the lattice
parameters

• Motif (or Basis) = the pattern that is

associated with each lattice point.
– Will be one or more atoms, or ions, in a
crystal
b

a
Will these same lattice vectors
work?

a
All lattice points are equivalent

a
All lattice points are equivalent

b a
All lattice points are equivalent

b a
All M.C. Escher works (c) 2006 The M.C. Escher Company - the Netherlands.
All rights reserved.
All M.C. Escher works (c) 2006 The M.C. Escher Company - the Netherlands.
All rights reserved.
 Hard sphere model:
• Atoms touch, don’t overlap
• Atoms have a size, defined by their radius
• Bonds are non-directional
– bonding: what does it mean to form a bond?
• What types of materials can we easily
think about with this model?
• 1) metals
• 2) ionic solids
 Close Packed Planes
• Maximizes the number of NN

• More bonding = lower energy

• Two patterns for Layering

– ABAB
– ABCABC
 Metal Structures
What determines the number of nearest
neighbors in metals?
 Metallic Bonding
• Atoms can bond at any angle because
electrons are delocalized.
• CN is not limited by orbitals, so metals will
maximize CN to minimize energy.
– Close packed structures are common
• FCC and HCP
– BCC is another common structure
f13_03_pg62 Callister
Hexagonal Close Packed crystal structure (HCP), Callister
FCC crystal structure, Callister
f01_03_pg40 Callister
Body Centered Cubic (BCC) unit cell

Callister
7 Crystal Systems, Callister
 3 Cubic Bravais Lattices
within the Cubic crystal system

• Simple Cubic
• Body Centered Cubic (BCC)
• Face Centered Cubic (FCC)

• a=b=c, alpha=beta=gamma=90 degrees

Simple Cubic unit cell

Callister
 Covalent Bonding
• What determines the number of nearest
neighbors?
 Covalent Bonding
• Maximize number of bonds to minimize
energy
• Number of bonding orbitals limits
coordination number
 Ionic Bonding
• What determines the number of nearest
neighbors?
 Ionic Bonding
Maximize the number of bonds
Ions have different sizes
Overall charge neutrality must be
maintained

Together, these place restrictions on the

types of structures that can form.
 Stability of ions in solids
• For stability, the central ion must be in contact with the
surrounding ions, otherwise their mutual charge
repulsion will be too great.
• To reduce energy, the central ion will bond with the
greatest number of surrounding ions possible.

Callister
Radius Ratio Rules

Callister Chapter 12
Shackelford Ch. 2

Purely geometrical

Applies to
Non-Directional Bonding

Radius Ratio Rules Callister

Example: Predict the structure of NaCl
Atomic radius Ionic radius
Na 0.186 nm 0.098 nm
Cl 0.107 nm 0.181 nm

Radius Ratio Coordination Number

< 0.155 2
0.155 – 0.225 3
0.225 – 0.414 4
0.414 – 0.732 6
0.732 – 1.0 8
1 12
The NaCl Crystal Structure

Callister
 Close Packed Planes
Interstices: The spaces between the atoms

– Octahedral

– Tetrahedral

In some ionic structures, the cations fit in

interstices formed in close-packed anion
planes
Callister
NaCl has an FCC structure with 1
Na+ and 1 Cl- ion per lattice site.

Calculate the theoretical density of

NaCl
r(Na+) = 0.102 nm
r(Cl-) = 0.181 nm

Callister
 Draw Axes &

Write down positions

Of the ions

Callister
Example: Predict the structure of GaAs
Atomic radius Ionic radius
Ga 0.135 nm 0.062 nm
As 0.125 nm 0.040 nm

Radius Ratio Coordination Number

< 0.155 2
0.155 – 0.225 3
0.225 – 0.414 4
0.414 – 0.732 6
0.732 – 1.0 8
1 12
 Example: SiO2
• Assuming that this is an ionic structure,
what is the coordination number of Si 4+ in
SiO2?
Example: Predict the structure of SiO2
Atomic radius Ionic radius
Si 0.117 nm 0.040 nm
O 0.060 nm 0.140 nm

Radius Ratio Coordination Number

< 0.155 2
0.155 – 0.225 3
0.225 – 0.414 4
0.414 – 0.732 6
0.732 – 1.0 8
1 12
 Example: SiO2
What is the coordination number of Si 4+ in SiO2?

What is the CN of O 2-?

First, check to see whether SiO2 is ionic or not

• O has an electronegativity of 3.5
• Si has an electronegativity of 1.8
• What is the difference in electronegativity? 1.7
• This means that Si-O bonds are about 50%
ionic, and 50% covalent.
 Are we justified in using r/R?
• O has an electronegativity of 3.5
• Si has an electronegativity of 1.8

The difference in electronegativity is 1.7

This means that Si-O bonds are 55% ionic,
and 45% covalent.
What if SiO2 had covalent bonding?
• If the bonds were completely covalent,
what type of bond would they be? (what
would be their shape and configuration?)

• What orbitals would be used to bond?

f12_09_pg426
 CN of the larger species
• Charge Neutrality: number of positive
charges = number of negative charges

• CN of Si4+ = 4
• This means that there are 4 O2- around
each Si4+
• How many Si4+ are there around each O2-?
• (What is the CN of O2-?)
iClicker: How many Si4+ are there around each O2-?

A. 1
B. 2
C. 3
D. 4
E. 6
 Problem-Solving approach
• How did you approach this problem?

Draw a picture
Write down an equation
Guess and check
 Guess and Check Method
• What if the CN(O2-) were 4?

• There would be 4 Si4+ around each O2-.

• Check charge neutrality:
4(4+) =? 2(2-)
This will not work!
• Should the next guess be higher or lower?
• CN(O2-) = 2
• How can the SiO44- tetrahedra be
attached?
t12_04_pg422
 Silicate Ceramics
Most common elements on earth are Si & O

Si4+

O2-

Adapted from Figs.

12.9-10, Callister 7e.
crystobalite

SiO2 (silica) crystal structures are quartz,

crystobalite, & tridymite
The strong Si-O bond leads to a high melting
material (1710ºC)
Callister
Callister
 Silica Glass
• The angle between tetrahedra is variable

• Rings and chains can organize

themselves in 3 dimensions in many non-
regular ways

• This ability is what makes SiO2 so good at

forming a glass network.
 Amorphous Structures
SiO2 can crystallize into an ordered structure if
given enough time

SiO2 can also form a glass if cooled quickly

Glass = amorphous
 SRO and LRO

Glasses have Short Range Order (SRO)

Can predict the number of NN

Glasses do not have Long Range Order (LRO)

No lattice vectors
No long range predictability of positions of individual
ions or atoms
Zachariasen’s Rules for Glass Formation
1. Cation coordination number is 3 or 4 (small)
(triangles and tetrahedra)

2. Oxygen coordination number is 1 or 2

BRIDGING or NON-BRIDGING oxygen

3. Oxygen polyhedra share corners, not edges or

faces
(Some faces can be shared as long as other corners are
shared.)

4. For 3D networks, at least 3 corners must be

shared–
There will be some non-bridging oxygen as well.
 Structure Determination
How can we experimentally determine
whether a material is crystalline or
amorphous?

What is the fundamental difference between

crystalline and amorphous structures?
X-Ray Diffraction
 Crystal Structure
• Crystal structure = Lattice + Motif
Crystal Planes
 (010)
Crystal Planes
y d010

x
 Crystal Planes
(100)
y
d100

x
 Crystal Planes
(110)
y
d110

x
 Crystal Planes
(120)
d120
y

x
d-spacing of (hkl) planes in a cubic
system

a
d hkl =
h +k +l
2 2 2
 X-Ray Diffraction
Reflection Rules for (hkl) planes
Example XRD Pattern
(200)

(220)

(222)
(111) (331)
 Indices for points, directions and
planes

• Points = 3 fractional coordinates within a

unit cell

• Directions = [u v w] square brackets!

– No fractions

• Planes = (h k l) Parentheses
– No fractions
Callister
Callister
Callister
 Density
Mass per volume

m
ρ=
V
The unit cell can be repeated to form the
entire structure, so the density of the unit
cell is the same as the density of the entire
solid.
 Atomic Density
• Number of atoms per volume
– Calculate atomic density for the three cubic
structures
 Atomic Packing Factor

• Volume of atoms per total volume

– Calculate APF for the three cubic structures
 Calculate the Density of Cr
• r(Cr) = 0.125 nm
• Cr = 52.00 amu

• What else do we need to know?

• Actual density is 7.19 g/cm3

 Density of Ni
Ni has an FCC structure. Calculate the
theoretical density of Ni.

What additional information do we need?

 Density of Ni
r(Ni)=0.125 nm
Ni = 58.67 amu

8.90 g/cc
 More Unit Cell Practice
• Identify the Bravais Lattice
• How many of each atom per unit cell
• What is the chemical formula
(stoichiometry)
• How many nearest neighbors does each
have?
• What is the volume of the unit cell?
Callister
Callister
Callister
Callister
NOTE: This was an animation showing how the motif is made
Of 2 carbon atoms related by a ¼ ¼ ¼ translation. All of the atoms
Are carbon, the blue color was just to distinguish the two positions.

Callister
Callister
Graphite from Callister