The Crystalline Solid State

Crystalline Solid State

Many more molecules in the solid state.
We will focus on crystalline solids composed of
atoms or ions.
Unit cell structural component that, when
repeated in all directions, results in a
macroscopic (observable) crystal.
14 possible crystal structures (Bravais lattices)
Discuss positions of atoms in the unit cell.
The Cubic Unit Cell (or
Primitive)
1 atom per unit cell (how?).
What is the coordination number? Volume
occupied?
Lets calculate the length of the edge. What
size of sphere would fit into the hole?
The Body-Centered Cubic
How many atoms per unit cell?
What is the length of the edge? This is a
more complicated systems than the simple
cubic.
Close-Packed Structures
How many atoms is each atom surrounded by in
the same plane?
What is the coordination number?
Hexagonal close packing (hcp) discuss the third
layer (ABA).
Cubic close packing (ccp) or face-centered cubic
(fcc) discuss the third layer (ABC).
Two tetrahedral holes and one octahedral hole per
atom. Can you see them?
Close-Packed Structures
The hcp has hexagonal prisms sharing vertical
faces (Figure).
How many atoms per unit cell in the hcp structure?
What is the length of the cell edge?
The unit cell for the ccp or fcc is harder to see.
Need four close-packed layers to complete the cube.
What is the length of the cell edge?
In both close-packed structures, 74.1% of the total
volume is occupied.
Ionic Crystals
The tetrahedral and octahedral holes can
have varying occupancies.
Holes are generally filled by smaller ions.
Tetrahedral holes
Octahedral holes
NaCl structure
Metallic Crystals
Most crystalize in bcc, ccp, and hcp structures.
Hard sphere model does not work well.
Depends on electronic structure.
Properties
Conductivity
Dislocations
Diamond
Each carbon atom is bonded tetrahedrally to
four nearest neighbors (Figure).
Essentially the same strength in all directions.
Structures of Binary Compounds
Close-packed structures are generally defined by
the larger ions (usually anions). The oppositely-
charged ions occupy the holes.
Two important factors in considering the
structure
Radius ratio (r
+
/r
-
)
Relative number of combining cations and anions.
NaCl Crystal Structure
Face-centered cubes of
both ions offset by a
half a unit cell in one
direction.
Many alkali metals have
this same geometry.
What is the coordination
number (nearest
neighbor)?
CsCl Crystal Structure
Chloride ions form
simple cubes with cesium
ions in the center (Figure
7-7).
The cesium ion is able to
fit in to center hole.
How?
Other crystal structures.
TiO
2
(the rutile structure)
Distorted TiO
6

octahedra.
Ti has a C.N. of 6,
octahedral coordination
O has a C.N. of 3
Rationalization of Structure of
Crystalline Solids
Predicting coordination number from radius
ratio (r
+
/r
-
).
A hard sphere treatment of the ions.
Treats bonding as purely ionic.
Simply, as as the M
+
ratio increases, more
anions can pack around it.
Table 7-1.
Lets look at a few (NaCl, CaF
2
, and CaCl
2
).
Thermodynamics of Ionic Crystal
Formation
A compound tends to adopt the crystal structure
corresponding to lowest Gibbs energy.
M
+
(g) + X
-
(g) MX(s)
AG = AH - TAS (standard state), 2
nd
term can be
ignored
Lattice enthalpy
MX(s) M
+
(g) + X
-
(g) AH
L
(standard molar
enthalpy change)
Currently, we are interested in lattice formation.

The Born-Haber Cycle
A special
thermodynamic cycle
that includes lattice
formation as one step.
The cycle has to sum up
to zero if written
appropriately.
Write down values for
KCl.
The Born-Haber Cycle
Calculate the lattice enthalpy for MgBr
2
.
A discrepancy between this value and the
real value may indicate the degree of
covalent character.
We have assumed Coulombic interactions
between ions.
The actual values for KCl and MgBr
2
are 701
and 2406 kJ/mol (versus 720 and 2451).
Lattice Enthalpy Calculations
Considering only Coulombic contributions
The electrostatic potential energy between each pair.


z
A
, z
B
= ionic charges in electron units
r
0
= distance between ion centers
e = electronic charge
4tc
o
= permittivity of a vacuum
e
2
/ 4tc
o
= 2.307 10
-28
J m
Calculation would be performed on each cation/anion pair
(nearest neighbor).

|
|
.
|

\
|
= A
o
2
0
B A
4
e
r
z z
U
tc
Lattice Enthalpy Calculations
A more accurate equation depicts the Coulombic
interactions over the entire crystal.


N
A
= Avogadros constant
A = Madelungs constant, value specific to a crystal type (in
table). This is a sum of all the geometric factors carried
out until the interaction become infinitesimal.
A
|
|
.
|

\
|
= A
0
B A
o
2
A
r
z z
4
e N
U
tc
Lattice Enthalpy Calculations
Repulsions between ions in close proximity term.


C = constant (will cancel out when finding the minimum)
= compressibility constant, ~ 30 pm
Combining terms

0
r
'
A
e C N U

= A

tc
0
r
A
0
B A
o
2
A
e ' C N A
r
z z
4
e N
U

+
|
|
.
|

\
|
= A
Lattice Enthalpy Calculations
Finding the minimum
energy
dU/dr
0
= O




A negative of this value
may be defined as the
lattice enthalpy.
A
r
1
r 4
e z z N
U
0 0 o
2
B A A
|
|
.
|

\
|
= A

tc
Lattice Enthalpy Calculations
As the polarizability of the resultant ions
increase the agreement with this ionic
model worsens.
Polarizibility generally indicates more covalent
character.
Calculations
NaCl and CaBr
2
Molecular Orbitals in Solids
A very large number of atoms
are used to generate molecular
orbitals.
One-dimensional model.
Creation of bands that are closely
spaced.
Factors affecting the width of the
band.
This would be called an s band. A
similar model can be constructed
for the p-orbitals and d-orbitals.
The Bonding Picture in Solids
Molecular Orbitals in Solids
Band gap separation
between bands in which no
MOs exist (Figure 7-13).
Valence band highest
energy band containing
electrons.
Conduction band the band
immediately above the
valence band in energy.
Metals and Insulators
Metals
Partially filled valence band (e.g. s band)
Electrons move to slightly higher energy levels by
applying a small voltage. Electrons and holes are
both free to move in the metal.
Overlapping bands (e.g. s and p bands)
If the bands are close enough in energy (or
overlapping) an applied voltage can cause the
electrons to jump into the next band (conduction
band).
Density of States
Concentration of
energy levels within a
band.


Helps to describe
bonding/reactivity in
solids.
dE
)) E ( N ( d
Conductivity of Solids Versus
Temperature
Metals decrease with
temperature.
Semiconductors increase
with temperature.
Insulators increase with
temperature (if
measurable).
Semiconductor Types
Intrinsic semiconductors
pure material having
semiconductive properties.
Doped semiconductors
semiconductors that are
fabricated by adding a small
amount of another element
with energy levels close to
the pure state material.
n-type semiconductors
p-type semiconductors (look at
figure)
Semiconductors
Fermi-level (semiconductor) the energy at
which an electron is equally likely to be in
each of two levels (Figure).
Effects of dopants on the Fermi level.
n-type and p-type.
Diodes (creating p-n junctions)
Migration of electrons from the n-type
material to the p-type material.
Equilibrium is established due to charge transfer.
Application of a negative potential to the n-
type material and a positive potential to the p-
type material.
Discuss (Figure 7-16).
Superconductivity
No resistance to flow of electrons.
Currents started in a loop will continue to flow
indefinitely.
Type I superconductors expel all magnetic fields
below a critical temperature, T
c
(Meisner effect).
Type II superconductors below a critical
temperature exclude all magnetic fields
completely. Between this temperature and a
second critical temperature, they allow partial
penetration by the magnetic field.
Levitation experiment works well.
Theory of Superconducting
Cooper pair theory
Bardeen, Cooper, and
Schrieffer
Electrons travel through the
material in pairs.
The formation and
propagation of these pairs is
assisted by small vibrations
in the lattice.
discuss
YBa
2
Cu
3
O
7
High-Temperature
Superconductors
Discovered in 1987
and has a T
c
of 93 K.
N
2
(l) can be used
Type II
superconductor.
Difficult to work
with.
Possesses copper
oxide planes and
chains.
Bonding in Solid State Structures
The hard-sphere model is too simplistic.
Deviations are observed in ion sizes.
Sharing of electrons (or transfer back to the
cation) can vary depending upon the
polarizability.
LiI versus NaCl (which structure would exhibit
more covalent character?)
Bonding in TiO
2
The crystal has a rutile
structure.
Each titanium has ___ nearest
neighbors and each oxygen
atom has ___ nearest
neighbors.
There is no effective O O
or Ti Ti interactions (only
Ti O interactions). Why?
The structure consists of
TiO
6
fragments (discuss).
Bonding in TiO
2
For a TiO
6
monomer (no
significant t-bonding).
An approximation of the
bands in the solid structure.
Bonding in TiO
2
The calculated DOS curve
in 3-d space is slightly
more complicated.
The O 2s, O2p, Ti t
2g
, and
e
g
bands are well separate.
The separation predicts
that this material has
insulator-like properties.
Bonding in TiO
Several of the 3d monoxides
illustrate high conductivity
that decreases with
temperature.
TiO and VO (positioning in the
table).
TiO adopts the rocksalt
structure (NaCl).
Discuss geometry and
consequences on bonding.
Bonding in TiO
The titanium atoms are
close enough to form a
conduction band.
Overlap of t
2g
orbitals of
the metal ions in
neighboring octahedral
sites.
Illustrated for d
xy
orbitals.
Bonding in TiO
The calculated DOS
curve for TiO reveals
that the bonds arent
well separated.
Diffuse bands indicate
more conductive
behavior.
Why is TiO
2
different
than TiO?
Bonding in TiO
MnO, FeO, CoO, and NiO do not conduct,
but they have the same basic structure.
Why?
Imperfections in Solids
All crystalline solids possess imperfections.
Crystal growth occurring at many sites causes
boundaries to form.
Vacancies and self-interstitials
Substitutions
Dislocations
Silicates
The earths crustal rocks (clays, soils, and sands)
are composed almost entirely (~95%) of silicate
minerals and silica (O, Si, and Al).
There exist many structural types with widely
varying stoichiometries (replacement of Si by Al is
common). Consequences?
Common to all:
SiO
4
tetrahedra units
Si is coordinated tetrahedrally to 4 oxygens
http://www.soils.wisc.edu/virtual_museum/displays.html
http://mineral.galleries.com/minerals/silicate/class.htm
The Tetrahedral SiO
4
Unit
Cheetham and Day
Structures with the SiO
4
Unit
Discrete structural units which commonly
contain cations for charge balance.
Corner sharing of O atoms into larger units.
O lattice is usually close-packed (near)
Charge balance is obtained by presence of
cations.
Individual units, chains, multiple chains
(ribbons), rings, sheets and 3-d networks.
Structure Containing Discrete
Units
Nesosilicates no O atoms are shared.
Contain individual SiO
4
4-
units.
ZrSiO
4
(zircon) illustrate with softwares
Stoichiometry dictates 8-fold coordination of the
cation.
(Mg
3
or Fe
3
)Al
2
Si
3
O
12
(garnet) illustrate with
softwares
8-fold coordination for Mg or Fe and 6-fold
coordination for the Al.
Structure Containing Discrete
Units
The sorosilicates (disilicates) 1 O atom is
shared.
Contain Si
2
O
7
6-
units
Show Epidote (Ca
2
FeAl
2
(SiO
4
)(Si
2
O
7
)O(OH))
with softwares.
Epidote contains SiO
4
4-
and Si
2
O
7
6-
units
Near linear Si-O-Si bond angle between
tetrahedra.
Cyclosilicates (discrete cyclic
units)
Each SiO
4
units shares two O atoms with
neighboring SiO
4
tetrahedra.
Formula SiO
3
2-
or [(SiO
3
)
n
]
2n-
(n=3-6 are the most
common.
Beryl six-linked SiO
4
tetrahedra (show with
softwares).
Be
3
Al
2
(SiO
3
)
6
contains Si
6
O
18
12-
cyclic units
The impurities produce its colors.
Wadeite three-linked SiO
4
tetrahedra (dont have an
actual picture)
K
2
ZrSi
3
O
9

Silicates with Chain or Ribbon
Structures
Corner sharing of SiO
4

tetrahedra (SiO
3
2-
)

Very common (usually to
build up more complicated
silicate structures).
Differing conformations can
be adopted by linked
tetrahedra.
Changes the repeat distance.
The 2T structure is the most
common (long).
Silicates with Chain or Ribbon
Structures
The chains are usually packed parallel to
provide sites of 6 and 8 coordination for the
cations.
Jadeite [NaAlSi
2
O
6
]
Illustrate the different repeat units.
What is the repeat unit?
Silicate Chains Linking Together
Can form double or triple
chains/ribbons linked
together (or more).
Depends on the repeat unit in
the chain.
Tremolite
[Ca
2
Mg
5
(Si
4
O
11
)
2
(OH)
2
(illustrate with softwares)
Asbestos mineral (fibrous)
Triple chain
Phyllosilicates (Silicates with
Layer Structures)
Clay minerals, micas, talc, soapstone.
Individual layers are formed by sharing 3 of
the 4 atoms of each tetrahedron.
Simplest structure is made up of a 2T
network of silicate chains to give a network
composition of Si
2
O
5
2-
.
This is exhibited with kaolinite (illustrate the
silicon tetrahedral layer).
Creation of Layers in the
Phyllosilicates
Can be formed by
sharing the fourth O
atom between pairs of
tetrahedra.
Produces an SiO
2

stoichiometry (neutral)
Replacing Si with Al
Al
2
Si
2
O
8
2-
; requires charge
balance. The cations
connect the double layers.
Creation of Layers in the
Phyllosilicates
Double layers can be produced by interleaving
layers of the gibbsite Al(OH)
3
or brucite
Mg(OH)
2
structure.
Incorporation of gibbsite produces kaolinite,
[Al
2
(OH)
4
Si
2
O
5
] (China clay); illustrate with
software the different layers present.
Placing a SiO layer on the other side of the AlO layer
produces pyrophyllite, [Al
2
(OH)
2
Si
4
O
10
].
Illustrate both with software.
More Layered Structures
The Al can be replaced by Mg (2:3) ratio.
Kaolinite serpentine asbestos
Pyrophyllite talc
Charged layers can also result by replacing the
framework Si with Al or other cations. For charge
balance these layers can be interleaved with
M(+1) or M(+2) to give micas (illite) or by layers
of hydrated cations to give montmorillonite.
Illustrate both.
The Tectosilicates
Each oxygen atom is shared by 2 tetrahedra
(SiO
2
formula).
Silica (o-quartz; one crystalline form)
Si-O-Si bond angles are ~144 degrees.
Contains helical chains of SiO
4
.
Six combine to form hexagonal shape (illustrate).
The Tectosilicates (Zeolites -
aluminosilicates)
A large fraction of the Si atoms are replaced
with Al (other metals can also be used).
Charge balance will be required (Si,Al)
n
O
2n
.
Contain cavities that allow molecules to enter.
Able to tailor electronic and physical properties.
Pore structure and cation exchange.
Illustrate with software.