1 Crystal Solids

Introduction to Condensed
Matter Physics
Crystalline Solids - Introduction
M.P. Vaughan
Overview
Overview of course
Crystal solids
Crystal structure
Crystal symmetry
The reciprocal lattice
Band theory
X-ray diffraction
Phonons
Specific heat
Elasticity
Coliste na hOllscoile Corcaigh, ire
University College Cork, Ireland
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Department of Physics
PY3105 Introduction to
Condensed Matter Physics
Overview of crystal solids

Ordered and disordered materials
Atomic orbitals
The hydrogen atom
The Aufbau Principle
Molecular bonds
Hybridised orbitals
Covalent bond
Ionic bond
Polar covalent bond
Metallic bond
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Ordered and disordered

materials
Classifying solids structural
Ordered
(crystalline)
Disordered
(glasses)
Semidisordered

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N.B. glass is used as

a generic term here
(not just the glass you
drink from!)
Disordered (amorphous) solids
Disordered
materials
Usually electrically
insulating
Physics similar to
liquids (difficult!)
E.G. amorphous SiO2 (silicon

dioxide or silica primary
component of every day glass)
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Ordered (crystalline) solids
Crystalline
materials
Physics far more

tractable
Regularly
repeating structure
E.G. crystalline SiO2 (quartz),

rock salt, diamond, most
metals, silicon, germanium...
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Electronic classification of crystals
insulators
(dielectrics)
conductors
(metals)
semiconductors
For crystalline materials, the explanation of the electronic

properties is quite tractable
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Atomic orbitals
The hydrogen atom
The hydrogen atom is one of the few real

systems for which analytical solutions of the
Schrodinger equation exist [1]
The solutions are characterised by 3

quantum numbers, n, l and ml
A fourth quantum number, ms, must also be

added describing the intrinsic angular
momentum or spin
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Atomic quantum numbers

Quantum
number
Name
Meaning
Values
principle
(radial) energy level
1,2,3,...
azimuthal
orbital angular momentum
0,1,2, ..., n-1
ml
magnetic
projection of orbital
angular momentum along
an axis
0, 1, 2, ..., l,
ms
spin
projection*
projection of spin along an

axis
-s, -(s-1), ..., s-1, s
*Note that the spin quantum number (giving intrinsic angular momentum), s,
of an electron is 1/2
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The Pauli Exclusion Principle
Each set the four quantum numbers, n, l, ml

and ms, characterises a quantum state of
the system. In an atom, these are often
called atomic orbitals.
Since electrons are fermions, they are
subject to Paulis Exclusion Principle,

which states that:
No two fermions may occupy the
same quantum state.

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Electron shells
l=0
m=0
l=1
l=2
m=0
m = -1
m=1
m=0
m = -2
m = -1
m=1
m=2
n=1
1s
n=2
2s
2p
2p
2p
n=3
3s
3p
3p
3p
3d
3d
3d
3d
3d
...
4s
4p
4p
4p
4d
4d
4d
4d
4d
...
Note that the number of states in each shell is twice that shown due to spin.
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Subshells - notation
The notation used is a legacy of the categorisation of
spectral lines:
s
p
d
f
sharp
principle
diffuse
fundamental
These correspond to l = 0, 1, 2 and 3. There after, we

use g, h, i,... . Each of these denotes a subshell.
(Unfortunately!) the following mnemonic is highly
effective: sexy people dont fart. (Sorry!)
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The Aufbau Principle

The Aufbau Principle describes how electronic shells are
built up (aufbau comes from the german aufbauen,
meaning building up).
Shells build up in the order
1s
1s 2s 2p 3s 3p 4s 3d ...
2s
2p
3s
3p
3d
4s
4p
4d
5s
5p
5d
6s
...

4f
N.B. only works well for first 18

atoms
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Hunds Rule
When we consider how states fill with

electrons, we must take account of spin and
apply Hunds Rule:
States of the same energy are each filled

with one electron of the same spin before
electrons of the opposite spin are added

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Hunds Rule - example

Example: 2p orbitals
(1)
(4)
(2)
(5)
(3)
(6)

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Rule of stability
A subshell has the highest stability if it is half full or full
Stable configurations
Unstable configurations
readily loses the

electron
readily accepts
an electron
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Occupation notation
To denote the occupation of a subshell, we

use a superscript notation.
E.g.
2p3
means there are 3 electrons

in the 2p subshell
We may now see how the electronic

configurations of the elements of the
periodic table are built up
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Electronic configurations
atomic number
element
configuration
abbreviated
notation
1s
1s
He
1s2
1s2
Li
1s22s1
[He]2s1
Be
1s22s2
[He]2s2
1s22s22p1
[He]2s22p1
1s22s22p2
[He]2s22p2
1s22s22p3
[He]2s22p3
1s22s22p4
[He]2s22p4
1s22s22p5
[He]2s22p5
10
Ne
1s22s22p6
[He]2s22p6
11
Na
1s22s22p63s1
[Ne]3s1
12
Mg
1s22s22p63s2
[Ne]3s2
...
...
...
...

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Core and valence electrons
Note that each of the noble gases, He, Ne, etc., has
a full shell
Also, each element with a higher atomic number
than a given noble gas has the electronic
configuration of that gas in common (hence the
abbreviated notion)
These filled inner shells may be referred to as core
electrons
The outer most electrons on top of the filled shells
are called valence electrons and are responsible
for an atoms chemical interactions

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Valence configurations
I
II
III
IV
VI
VII
H
1s1
VIII
He
-
Li
2s1
Be
2s2
2s22p1
2s22p2
2s22p3
2s22p4
2s22p5
Ne
-
Na
3s1
Mg
3s2
Al
3s23p1
Si
3s23p2
P
3s23p3
S
3s23p4
Cl
3s23p5
Ar
-
K
4s1
Ca
4s2
Sc
4s23d1
...
Zn
4s23d10
Ga
Ge
As
Se
Br
4s23d104p1
4s23d104p2
4s23d104p3
4s23d104p4
4s23d104p5
Kr
-
...
...
...
...
...
...
...
...
...
...
...

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Atomic orbitals: n = 1
Images are isosurfaces of constant amplitude
1s orbital

1s orbital (section)
red and blue regions indicate
a change of sign.
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s orbital
p orbitals
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s orbital
p orbitals
d orbitals

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Molecular bonds
Hybridised orbitals
The atomic orbitals may hybridise with one

another to produce molecular bonds
between atoms
Typically, these hybridised orbitals may be

formed from s and p orbitals. Two hybrid
orbitals of particular interest are
sp3 hybrid
formed from 1 s and 3 p orbitals
sp2 hybrid
formed from 1 s and 2 p orbitals

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sp3 hybrid
An s and 3 p orbitals may hybridise to produce

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sp3 hybrid
Note that the sp3 hybrid has a tetrahedral form

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s bond (covalent bond)

If other atoms are close enough together, the lobes of
the sp3 hybrids may overlap to produce the s bond, in
which 2 electrons are shared. This is the covalent
bond.
The red shading is electron density.

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s* bond
As well as the bonding s bond, there is also the antibonding s* bond, which has a nodal plane between
the atomic nuclei (region of zero electron density)

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Diamond structure
For s bonded atoms of the sp3 type, the atoms form the
tetrahedral diamond structure lattice.
This will be discussed in more detail later in the section

on crystal structure.
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Diamond structure
Examples of materials with the diamond

structure include
Diamond (carbon)
Crystalline silicon
Crystalline germanium
Note that these elements all come from

group IV of the periodic table

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Diamond structure elements

III
IV
Group IV
(group 14 in chemistry)
...
...

2s22p1
2s22p2
2s22p3
Al
3s23p1
Si
3s23p2
P
3s23p3
...
...
Ga
Ge
As
4s23d104p1
4s23d104p2
4s23d104p3
...
...
...
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...
...
The ionic bond

Recall the rule of stability
Stable configurations
Unstable configurations
readily loses the

electron
readily accepts
an electron
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The ionic bond

For s and p orbitals, this means
ns
np
N.B. configuration of
outer subshell of noble
gases (Ne, Ar, etc.)
stable
ns
np
unstable
In other words, the orbitals like to fill a complete subshell

of 8 atoms (an octet). This is Lewis octet rule of
stability.
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The ionic bond

I
Consider elements from

groups I and VII
alkali metals
halogens

VII
VIII
H
1s1
He
-
Li
2s1
...
F
2s22p5
Ne
-
Na
3s1
...
Cl
3s23p5
Ar
-
K
4s1
...
Br
4s23d104p5
Kr
-
...
...
...
...
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The ionic bond

These have the valence electrons in the configurations
ns
np
alkali metals
ns
np
halogens

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The ionic bond

Thus, if the alkali metal loses its s state electron, the
remaining outer subshell will be filled
ns
np
alkali metals
ns
np
halogens
By accepting this electron, the halogen then fills its outer

shell
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The ionic bond

The alkali metal (e.g. Na) then becomes positively
charged and the halogen ion (e.g. Cl) becomes
negatively charged, resulting in an electrostatic force
between them.
Na+
Cl-
This is the basis of the ionic bond.

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The ionic bond packing rules
For the ionic bond, the resulting crystal

structure depends on packing rules of the
atoms.
For simplicity, we shall model the atoms as

rigid spheres.
We will consider two general categories:
Atoms of the same size

Two types of atoms of different size

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Close packing of equal spheres

hexagonal close
packing (HCP)
face-centred cubic
packing (FCC)*
*The FCC structure will be discussed later in the

section on crystal structure
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Close packing of equal spheres

Comparison of the HCP and FCC structures
HCP

FCC
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Packing of two different types of sphere

Example: NaCl (salt)

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Ionicity
In practice, all ionic bonds have some
covalent character due to the unequal

distribution of electron density between them
The ionicity of a bond will depend on the
difference in electronegativity of the two
atoms
Electronegativity is a measure of the power
of an ion to attract electrons to it
Bonds with mixed ionic and covalent
character are often termed polar covalent
bonds

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Polar covalent bonds

III
IV
B
2s22p1
C
2s22p2
N
2s22p3
...
Al
3s23p1
Si
3s23p2
P
3s23p3
...
...
Consider elements from

groups III and V
group III
...
group V
...

Ga
Ge
As
4s23d104p1
4s23d104p2
4s23d104p3
...
...
...
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...
Polar covalent bonds
Pairs of atoms from these groups have 8
valence bands between them as do the

group IV elements. They may therefore form
sp3 hybridised orbitals with some ionic
character.
Two types of polar structure are typically
formed:
zinc blende like the diamond structure but with

two types of atom
wurtzite typically, the nitrides (GaN, AlN etc.)
These structures will be discussed in more detail
later

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The metallic bond
In the metallic bond, the localised ions are

bonded together via their interaction with a
sea of delocalised conduction electrons
The nature of metals will be discussed in

more detail later

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Summary
Summary of atomic orbitals
Quantum mechanics yields electronic
solutions for an atom characterised by 4

atomic numbers
These solutions are known as atomic orbitals
Using the Exclusion Principle and Hunds
rule, the systematic occupation of these
atomic orbitals explains the periodic table
The atomic orbitals can hybridise to produce
bonding states
The resulting bonds give rise to crystal
structure

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References
[1]
See, for example, L.I. Schiff, Quantum Mechanics,

McGraw-Hill

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Additional material
The periodic table

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Electronegativity
Paulings measure of
electronegativity

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Introduction to Condensed

Overview of crystal solids

Ordered and disordered

Classifying solids structural

Coliste na hOllscoile Corcaigh, ire

N.B. glass is used as

Disordered (amorphous) solids

E.G. amorphous SiO2 (silicon

Ordered (crystalline) solids

Physics far more

E.G. crystalline SiO2 (quartz),

Electronic classification of crystals

For crystalline materials, the explanation of the electronic

The hydrogen atom

The hydrogen atom is one of the few real

The solutions are characterised by 3

A fourth quantum number, ms, must also be

Atomic quantum numbers

(radial) energy level

orbital angular momentum

0,1,2, ..., n-1

projection of spin along an

-s, -(s-1), ..., s-1, s

The Pauli Exclusion Principle

Each set the four quantum numbers, n, l, ml

Since electrons are fermions, they are

subject to Paulis Exclusion Principle,

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These correspond to l = 0, 1, 2 and 3. There after, we

The Aufbau Principle

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N.B. only works well for first 18

When we consider how states fill with

States of the same energy are each filled

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Hunds Rule - example

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readily loses the

To denote the occupation of a subshell, we

means there are 3 electrons

We may now see how the electronic

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Core and valence electrons

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The atomic orbitals may hybridise with one

Typically, these hybridised orbitals may be

formed from 1 s and 3 p orbitals

formed from 1 s and 2 p orbitals

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An s and 3 p orbitals may hybridise to produce

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s bond (covalent bond)

The red shading is electron density.

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This will be discussed in more detail later in the section

Examples of materials with the diamond

Note that these elements all come from

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Diamond structure elements

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