Week 2 Crystallography

Video 5 Broad description of crystals

“An ideal crystal is constructed by the infinite repetition of identical structural

units in space” – Charles Kittel
 The Stacking of Atoms in Solids
The stacking order of atoms to form single crystals is dependent on the shape of the
electron clouds and a general trend is observed across the Periodic Table. The
outmost orbitals (plural) take part in the bonding process as this is where we find the
valence electrons

l=0 s shells – 2 electrons to fill completely

l=1 p shells – 6 electrons to fill completely

d shells – 10 electrons to fill completely

The location of the electrons in atoms can be predicted if we know the wave function (r),
is a point in space.
However, the valence electrons in a crystal have overlapping wave functions with a
superposition
𝑎𝑙𝑙 𝑎𝑡𝑜𝑚𝑠
The probability of finding an electron
𝜓 ( 𝑟 )= ∑ 𝜓 𝑛 ( 𝑟 𝑛 ) in a crystal is still but complicated by
𝑛=1 the number of atoms
Periodic Table – Outer atomic shells & bonding trend

Insulators

Semi-conductors

Metals

s BLOCK d BLOCK p BLOCK

2 groups 10 groups 6 groups

Delocalised localised

Metallic Metallic & Covalent Covalent

Bonding Bonding Bonding
Simple metals Transition metals Nonmetals (or insulators)
 The crystal – A periodic array of atoms

Lattice + basis = crystal structure

The lattice is a three dimensional construction of points in space. These points do

not necessarily coincide with the position of an atom (however it is helpful if they
do) but rather defines an origin for the location of a unit cell or primitive cell.

The unit cell contains the primitive cell and also atoms from adjacent lattice
positions.

The basis refers to the primitive cell.

The unit cell is helpful to visualise the symmetry of the lattice.

Crystal Structure – A simple concept…

• Crystal structure can be obtained by attaching atoms, groups of atoms or

molecules which are called basis or motif to the crystal lattice points.

Crystal Structure = Crystal Lattice + Basis

Simplistically where to hang the atoms!

 A two-dimensional Bravais (c.1850) lattice
with different choices for the basis

Bravais showed there are 7 lattice systems (matrix of points in space) which expand
into a total of 14 sub-divisions in three-dimensional space.

The basis can be anything ranging from single atoms to complex protein molecules
 Crystallography is complex science in 3D

Here we have three common Unit Cells as they appear in 3D. The unit cell is useful
for the visualization of how the atoms are arranged (as we see whole atoms).

But unit cell is not the motif or basis – for this we define the Primitive Cell albeit less
intuitive for visualization purposes.
 Examples of primitive cells and lattice points
4 atoms/primitive cell
2 atoms/primitive cell
1 atom/primitive cell

Lattice point
Atom in the primitive cell
 Calculating the Atomic Packing Fraction (APF)
Single crystals form (condense) in a particular way to become thermodynamically
more stable.
If you think of many glass marbles dropped into a box, they will arrange in an orderly
way to maximize the number of marbles in a unit volume – similar to the formation
of a single crystal. If the marbles are of the same size the arrangement would be
hexagonal. Each marble will have six nearest neighbours.

Atomic Packing Fraction (APF) is a property of the type of crystal & defined as the
volume of atoms within the unit cell divided by the volume of the unit cell.

𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑎𝑡𝑜𝑚𝑠 𝑖𝑛 𝑡h𝑒 𝑈𝑛𝑖𝑡 𝐶𝑒𝑙𝑙

𝐴𝑃𝐹=
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡h𝑒 𝑈𝑛𝑖𝑡 𝐶𝑒𝑙𝑙

• Assume the atoms occupy a spherical space defined by the atomic radius r
• Note the number of atoms in a unit cell.
• Find the length where the atoms are touching.
• Calculate the lattice parameter a0.
• Note some unit cells will have more than one lattice parameter (e.g. HCP).
 Determining the Relationship between Atomic Radius and
Lattice Parameters
Question

Determine the relationship between the atomic radius

and the lattice parameter in SC, BCC, and FCC
structures when one atom is located at each lattice
point.

(c) 2003 Brooks/Cole Publishing / Thomson

Learning™

The relationships between the atomic radius and the Lattice

parameter in cubic systems
Solution
We find that atoms touch along the edge of the cube in SC structures.

a0  2r
In BCC structures, atoms touch along the body diagonal. There are two atomic
radii from the center atom and one atomic radius from each of the corner atoms
on the body diagonal, so

4r
a0 
3

In FCC structures, atoms touch along the face diagonal of the cube. There are
four atomic radii along this length—two radii from the face-centered atom
and one radius from each corner, so:
4r
a0 
2
 Calculating the Atomic Packing Factor

Question Calculate the packing factor for the Face Centered Cubic (FCC) crystal
Solution The primitive cell of a FCC crystal has four atoms. Or the unit cell
sitting over 8 lattice points defining a “cube” of space will have 8 atoms at each
corner with a volume of 1/8 inside the cube – the volume of one atom. There
are six atoms on each face with a volume of 1/2 inside the cube – the volume
of 3 atoms. Total volume is therefore four atoms.
The volume of the cube of space is .
4 3
(4 atoms/cell )( r )
Packing Factor  3
a03
Since, for FCC unit cells, a 0  4r/ 2
4 3
(4)( r )
3 
Packing Factor  3
  0.74
( 4r / 2 ) 18
 Theoretical Density, r
Modelling the atom as a sphere occupying space can be tested by using the model to
predict the density of a solid. If the predicted density and the measured density are
in agreement, then we have confidence the APF methodology is validated.

Mass of Atoms in Unit Cell

Density =  =
Total Volume of Unit Cell

nA
 = [grams]
VC NA

where n = number of atoms/unit cell

A = atomic weight
VC = Volume of unit cell = a03 for a cube
NA = Avogadro’s number = 6.023 x 1023 atoms/mol
 Theoretical Density, r
• Example: Chromium Cr (BCC)
A = 52.00 g/mol
R = 0.125 nm atomic radius
n=2
 a0 = 4R/3 = 0.2887 nm
R
a
atoms theoretical = 7.18 g/cm3
g
unit cell 2 52.00
mol ractual = 7.19 g/cm3
=
a3 6.023 x 1023
volume atoms
unit cell mol