The Solid State

Crystals and symmetry

Unit cells and packing
Types of solid
Phase diagrams
 Solids tend to be regular
At equilibrium an atom will tend to occupy the
position of lowest energy (highest stability)
One position will be more stable than any others
If one atom occupies this position then all the
other atoms will occupy the same position
All atoms occupy the same position and a
regular lattice evolves
Amorphous solids have no regular structure and
tend to be metastable or unstable
 Four solids
Ionic Ionic bonds Brittle, hard, NaCl, K2O
high m.p.
Molecular Van der Soft, low m.p. CO2, Br2
Waals
Covalent Covalent Hard, high Diamond,
lattice bonds m.p. SiO2
Metallic Metallic Variable Cu, Hg
bonds hardness and
m.p.
conductors
 Probing crystal structures
Light is scattered by objects that are larger than
the wavelength
Crystal lattices are too small for visible light
X-rays have wavelengths on the order of the
interatomic distance in crystals
X-rays suffer diffraction by crystals like visible
light diffracted by blinds
X-ray diffraction is the most powerful structural
tool developed
 Diffraction and interference
Diffraction arises by interference of
electromagnetic radiation
•Constructive interference – the waves are in
phase – increase in intensity
•Destructive interference – the waves are out of
phase – loss of intensity
X-ray beams diffract from a crystal to give a
pattern of spots where constructive interference
has occurred on a sea of destructive interference
 The crystal lattice and Bragg
scattering
X-rays are scattered by the electrons in
the atoms
The array of atoms in the crystal is like a
diffraction grating for X-rays as a set of slits
is for visible light
Diffraction only occurs under conditions of
constructive interference
The Bragg equation gives the conditions
 The Bragg condition
Waves reflected from adjacent layers must be in
phase
The path length difference must then be a whole
number of wavelengths

n  2d sin 
 X-ray diffraction and data
collection
A crystal or powder is swept through the
range of angles of θ and the positions where
there are reflections are tabulated
Analysis of the d spacings gives information
about the type of crystal lattice
Deeper analysis of the reflection intensities
gives a complete description of the structure
and positions of all of the atoms
 Symmetry and crystal
structure
Symmetry underlies chemistry
•Arrangements of atoms in crystals
•Determination of spectra
•Mixtures of orbitals in bonds
Symmetry operators relate the positions of
the atoms in the unit cell
Common symmetry elements
Translation
Rotation
Reflection

After application of a symmetry operation

to a set of atoms related by symmetry, the
system appears unchanged
 Symmetry operations
Translation

Reflection

Rotation
 Packing of spheres and simple
structures
Atoms and simple molecules can be
treated like spheres
The crystal lattice can be derived from
packing together spheres
There are limited possibilities
 Cubic packing
In simple cubic the atoms stack directly on top of each
other
•Not close packed (very uncommon)
Body-centered cubic: denser packing achieved by putting
a layer in the depression of the first
•Not close packed (quite common)
 Close packing
Two arrangements achieve a higher
density
•Hexagonal close-packed- abab
•Face-centered cubic – abcabc
Both are common for metallic elements
Summary of packing
arrangements
 Building patterns with unit
cells
A floor is made from a mosaic of tiles
A wall is made from stacking of bricks
A crystal is made from stacking unit cells
In each case one unit contains all of the
information required to describe the
structure completely without any gaps or
deficiencies
 Building lattices with unit cells
Consider a cube

Component Number

Center 1

Face 6

Edge 12

Corner 8
 Counting atoms in a unit cell
The ratio of the atoms in a unit cell must
equal the composition of the compound
Count atoms as follows:
Component Shared Fraction of atom
between in cell
Center 0 1

Face 2 0.5

Edge 4 0.25

Corner 8 0.125
 Primitive and body-centered
cells
Alternate views of the primitive and body-centered cell
Primitive:
•8 atoms on the corners each contribute 1/8th to the contents –
overall cell contents = 1
BCC:
•8 atoms on the corners contribute 1
•1 atom in center contributes 1
•Overall contents = 2; composition AB
 Face-centered cube
Two views of the FCC lattice
Also viewed along 3-fold axis which is
perpendicular to the close-packed layers
Contents:
•8 at corners = 1
•6 on faces = 3
•Total contents = 4
 Calculations with unit cells
Calculating unit-cell size from atom size
In FCC cell, the atoms touch along the
diagonal
•Length of diagonal = 4r
•Length of edge = d  8r
 Estimate density
If we know the unit cell size we can
calculate the unit cell volume
If we know the unit cell contents we know
the total mass of the cell
Density = mass/volume
 Simple ionic compounds
In general, anions are larger than cations
Lattices can be described by close
packing of anions with cations occupy
regular “holes” in the anion lattice
 Sodium chloride
Chloride ions form FCC lattice
Sodium ions occupy octahedral holes
Composition check:
•Cl:
8 on corners = 1 +
6 on faces = 3
Total = 4
•Na:
 12 on edges = 3
1 in center = 1
Total = 4
 Covalent networks
Ionic lattices are characterized by high
coordination numbers and non-directional
bonding
Covalent lattices have low coordination
numbers and highly directional bonding
The bonds are formed from hybridized
atomic orbitals to use the valence bond
model
 Diamonds are forever
The diamond lattice is a very common covalent
lattice
It is a three dimensional tetrahedral net
Bonds are made from sp3 hybrid orbitals
Very strong covalent bonds make the lattice
extremely stable
 Compounds also have diamond
lattice
In GaAs, the Ga and As atoms alternate in
the diamond lattice
GaAs is an important semiconductor and
laser material
Many other similar materials
 Diamond and graphite
Infinite covalent lattices in different dimensions
•Diamond 3D
•Graphite 2D
Graphite is more stable than diamond, but can
be transformed into diamond by application of high
pressure
Summing it up: phase diagrams
Phase diagrams summarize the states of a
substance as a function of the pressure and
temperature
They reveal:
•The areas where one phase is stable
•The lines where two phases are in
equilibrium
•The points where three phases are in
equilibrium
 Phase diagram for water
A piece of ice at 1 atm pressure will convert to liquid at 0ºC and into
gas at 100ºC
Below at pressure of 6 x 10-3 atm the ice converts directly into a gas
(sublimation)
At the triple point the three phases are in equilibrium – a single
temperature and pressure
Beyond the critical point is the region of supercritical fluid:
•Cannot be condensed no matter what the pressure (critical
temperature)
•Cannot be vaporized no matter what the temperature (critical
pressure)
 Phase diagrams explain well
known phenomena
The slope of the solid-liquid phase boundary for
water is negative, while for CO2 it is positive
•A sample of ice under pressure melts
•A sample of liquid CO2 under pressure
solidifies
At 1 atm pressure:
•Ice melts on heating
•Solid CO2 sublimes (dry ice)