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,

high m.p.

NaCl, K2O

Molecular Van der

Waals

Soft, low m.p.

CO2, Br2

Covalent Covalent
lattice
bonds

Hard, high
m.p.

Diamond,
SiO2

Metallic

Variable
hardness and
m.p.
conductors

Cu, Hg

Metallic
bonds

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 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

Face

Edge

12

Corner

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 between Fraction of atom

in cell

Center

Face

0.5

Edge

0.25

Corner

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
d 8r
Length of edge =

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 0C and into
gas at 100C
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)