Week 1 Introduction to Solid State physics

Video 1 Historical Context

“Solid state physics is largely concerned with crystals

and electrons in crystals” - Charles Kittel
 19th Century Classical physics and the Solid State

Many physicists by the end of the 19th Century were openly confident all the big
questions in science were answered.

Lord Kelvin stated scientific discovery was nearing completion with only “small clouds
on the horizon [left to investigate]”

Newtonian mechanics, Thermodynamics, Electricity & Magnetism, Kinetic theory of

Gases, Statistical Physics…and so on, were firmly established.

All this changed with the discovery of the electron and its role is key in the
development of Solid-State physics.

Predating this activity, chemists have developed an atomic theory of the

elements and how they combine to form new compounds (by chemical
reactions).
John Dalton – An early Periodic Table (1808)

The main points of Dalton's atomic theory

were:
- Elements are made of extremely small
particles called atoms.
- Atoms of a given element are identical in size,
mass, and other properties; atoms of different
elements differ in size, mass, and other
properties.
- Atoms cannot be subdivided, created, or
destroyed.
- Atoms of different elements combine in
simple whole-number ratios to form chemical
compounds.
-In chemical reactions, atoms are combined,
separated, or rearranged.
 Discovery of the electron (1897)

19th Century natural philosophy enjoyed much

success. However a number of unexplained
experimental results started to erode
confidence in classical physics. Relativity and
quantum theory was only a few years away
when Thomson studied electrical discharges in
evacuated glass flasks.

So called “cathode rays” were observed

suggesting some ethereal substance with a
negative charge was responsible for generating a
glowing discharge in the flask. Charge carriers
had been assumed to be positively charged.

The properties of cathode rays rather than the plasma they generated was possible
once most of the air was removed from the vacuum flask.

Thomson had discovered a negatively charged particle with a mass of approximately

1/1840 of a hydrogen atom – he was awarded the Nobel Prize for his work.
 Thomson’s Plum Pudding model

Thomson proposed the electrons were

contained within a sphere of positive charge.

The “atom” therefore contained particles (Thomson

called them corpuscles) significantly smaller than
the hard shell of the atom.

Dalton’s “atom” now contained a sub atomic particle

of little mass which helped to develop ideas
regarding ionic and covalent bonding in chemistry.

The development of Quantum Mechanics from this point onwards until the early 1920’s
was primarily concerned with atoms and spectroscopic measurements of absorbed and
emitted radiation.
 Nagaoka’s Planetary Model of the Atom (1904)

Hantaro Nagaoka (1865-1950)

A discredited model where the electrons follow orbits around a tiny positively
charged nucleus.

The model did not make sense as classical physics predicts the electrons would
emit electromagnetic radiation and quickly merge with the nucleus.

However a simple calculation using classical physics predicted the diameter of the
atom to be  10-10m assuming the electrons hold their position in orbit!
 Rutherford’s Model of the Atom (1911)

e
e
e
 10-15m
++++
++ e
e

e
e
Ernest Rutherford, (1871 –1937)
 10-10m

Rutherford finally replaced Thomson's model in 1911 with his gold foil experiment in
which he demonstrated the atoms have a tiny and heavy nucleus.

Rutherford’s experiment seemed to agree with Nagaoka’s Planetary Model of a

positively charged nucleus.

However the experimental result did not confirm the electrons followed a circular
path round a dynamically stable orbit.
 Bohr’s Model of the Hydrogen Atom (1913)

Ref. Hyperphysics

Niels Bohr (1885 –1962)

Bohr postulated the electrons have certain specific orbits with discrete energy levels.

The fixed radius of these stationary orbits also implies the angular momentum must be
discrete.

The postulates are valid if it assumed each energy level (kinetic energy of the electron) is
modelled as a stationary wave. The quantum number n defines the energy level.
 Atoms – Electron filling and quantum numbers
Bohr’s model applied to one electron atoms and could be extended to atoms
with an atomic number Z > 1.
2 4

( )
𝑚𝑒 𝑍 𝑒 1 1
h 𝑖𝑗 =𝐸 𝑖 − 𝐸 𝑗= 2 2 2 2
− 2
8 𝜀 𝑜 𝑛𝑖 h 𝑛 𝑗 𝑛𝑖

However in this case the potential energy of the electron is only a function of the
radius from the nucleus. In most atoms with Z > 1 it is generally the case there are
Z electrons surrounding the nucleus.

Solutions of Schrodinger’s equation generates wave functions describing the shape

and orientation of the electronic orbitals for each energy state given by the
principal quantum number n.

[ ]
2
−ħ 2
𝛻 + 𝑈 ( 𝒓 )  𝑛 ( 𝒓 )=𝐸  𝑛 ( 𝒓 )
2𝑚 𝑒

As the electrons in the atom have strong Coulomb repulsion and becomes
complicated in the many-bodied problem the orbitals take on shape in order to
reduce the free energy of the atom. Orbitals or “electron clouds” are usually
drawn to illustrate location with 95% confidence (arbitrarily chosen).
 Atoms – Quantum numbers
There are 4 quantum numbers describing the orbital electrons

1. Principle quantum number, n = 1,2,3,4,….. (determines the energy of

the electron as well as defining the radial position of the probability
distribution function – the “cloud”)
2. Angular momentum quantum number, l = 0,1,2,3,…..n-1, (specifies
the orbital shape and essentially divides the shells into sub-shells or
sub-levels)
3. Magnetic quantum number, ml = -l,……,0,…….+l, (specifies the
orientation of the shells for a given n and l quantum numbers)
4. Spin quantum number ms = +1/2 or -1/2, (specifies the orientation of
the electron spin axis, the Pauli exclusion principle allows these two
spin states to occupy each n, l, ml quantum state)
Spectroscopy has given the orbital shapes names as follows:

Sharp s l=0
Principal p l=1
Diffuse d l=2
Fundamental f l=3 and so on
Atoms – Stacking order and orbital shapes
Both spin states

l=0

l=1

l=2

assume
Red sub shell +1/2 spin
Blue sub-shell -1/2 spin
When full
s shell has 2 electrons
p shell has 6 electrons
d shell has 10 electrons