CHAPTER 9 Statistical Physics

 underpins thermodynamics, ideal gas (a classical physics model),

ensembles of molecules, solids, liquids … the universe
 9.1 Justification for its need !
 9.2 Classical distribution functions as examples of distributions of
velocity, speed, and velocity2 = KE when multiplied by ½ m in ideal gas
9.3 Equipartition Theorem and speed distribution as proof
9.5 Classical and Quantum Statistics – when do we need to use
them, can’t get away with the classical distribution?
 9.6 Bose-Einstein statistics: Black body radiation, Liquid Helium, Bose-
Einstein condensates, quantum oscillators, heat capacity of crystalline solids
 9.7 Fermi-Dirac Statistics, quantum theory of electric conductivity in
metals, small contribution of the free electron gas to the heat capacity of metals
 archetypical Fermi problem, Drake equation

Ludwig Boltzmann, who spent much of his life studying statistical mechanics,
died in 1906 by his own hand. Paul Ehrenfest, carrying on his work, died
similarly in 1933. Now it is our turn to study statistical mechanics.
Perhaps it will be wise to approach the subject cautiously.

- David L. Goldstein (States of Matter, Mineola, New York: Dover, 1985) 1

First there was classical physics with a cause
(or causes)
Newton’s three force laws, first unification in physics
Lagrange around 1790 and Hamilton around 1840 added significantly to the
computational power of Newtonian mechanics.

Pierre-Simon de Laplace (1749-1827) made major contributions to the theory of

probability and the well-known clockwork universe statement:

It should be possible in principle to have perfect knowledge of the universe. Such

knowledge would come from measuring at one time the position and velocities of
every particle of matter and then applying Newton’s law. As they are cause and
effect relations that work forwards and backwards in time, perfect knowledge can
be extended all the way back to the beginning of the universe and all the way
forward to its end.

So no uncertainty principle allowed … no free will, no reason to do anything

2
 then there was the realization that one does not
always need to know the cause (all causes), can
do statistical analyses instead
Typical problem, flipping of 100 coins,

One can try to identify all physical condition before the toss, model the
toss itself, and then predict how the coin will fall down

if all done correctly, one will be able to make a prediction on how many
heads or tails one will obtain in a series of experiments

Statistics and probabilities would just predict 50 % heads 50% tails (for
a fair coin) by ignoring all of that physics,

The more experimental trials, 100,000 coin tosses, the better this
prediction will be borne out (provided the coin is fair)
The field of statistical (macroscopic) physics that is concerned with
3
the effects of many particle at once
 Path to statistical physics from classical to quantum for
bosons and fermions
Benjamin Thompson (Count Rumford) 1753 – 1814
 Put forward the idea of heat as merely the kinetic energy of individual
particles in a gas or condensed matter. Ignored by vast majority for a
very long time! One really need experiments to convince people!!
James Prescott Joule 1818 – 1889
 Demonstrated the mechanical equivalent of heat, so central concept of
thermodynamics becomes internal energy of systems (many many particles at
once)

4
 Speed distribution of
particles in an ideal gas
in equilibrium at one
temperature, instead of
analyzing what each
individual particle is going to
do, we determine the
density of states
(degeneracy) and a
distribution function of the
property, and then calculate
the expectation value of the
physical properties of the
system (always by the same
procedures !!)
We can then predict
<KE>= <p2>/2m
what we will measure
<KE> = 3/2 kT
There is one characteristic kinetic energy (and speed) distribution as a function of T, so
we would like to have a function that gives these distribution for all temperatures !! 5
 Beyond first and second year college physics
James Clark Maxwell 1831 – 1879, Josiah Willard Gibbs 1839 – 1903, Ludwig
Boltzmann 1844 – 1906 (all believed in reality of atoms, tiny minority at that time)

Brought the mathematical theories of probability and observational statistics to bear

on the physical thermodynamics problems of their time.

Showed that statistical distributions of physical

properties of an ideal gas (in equilibrium – a
stationary state) can be used to explain the observed
classical macroscopic phenomena (i.e. well-known
gas laws)

Gibbs invents notation for vector calculus, the form in which we use Maxwell’s
equations today
Maxwell’s electromagnetic theory succeeded his work on statistical foundation of
thermodynamics – so he was a genius twice over.
6
 and then there came modern physics …
Einstein 1905
 PhD thesis, the correct theory of Brownian motion, a theory that

required atoms to be real, because there are measurable

consequences to their motion, (also start of quantitative
nanoscience as size of a common sugar molecule (≈ 1 nm) was
determined correctly)
Bose (with Einstein’s generalization) 1924
 Statistics of indistinguishable particles that are bosons (photons:

Bose, all other bosons: Einstein’s generalization)

Fermi and Dirac independently 1926
 Statistics of indistinguishable particles that are fermions

Procedure is always: we have a part of the distribution function that is

property specific (deriving this is the ingenious physics bit) and one of three
characteristic statistical expressions for each of the three different types of
particles. The product-function of these two factor-functions is the distribution
function for the problem at hand. From the distribution function we calculate
expectation values, i.e. make predictions. (The relationships between the
7
various physical entities are just the same as in classical/quantum physics)
 9.2: Maxwell Velocity Distribution
= 3 Maxwell-Boltzmann factors times 3 C’(T) normalization factors

 internal energy in an ideal gas depends only on the movements

of the entities that make up that gas.

 Define a velocity distribution function .

= the probability of finding a particle with velocity
between,
(it will also have a certain kinetic energy, proportional to v 2)
. factor by itself: probability that a certain energy state is
Boltzmann
occupied, to be multiplied by degeneracy to get density of states

It’s similar to the product of a wavefunction with its complex conjugate (in
3D), from that we can calculate expectation values (what is measured
on average) by an analogous integration procedure as in previous chapters
on quantum mechanics !!

8
Maxwell Velocity Distribution
 Maxwell proved that the velocity distribution function is
proportional to exp(−½ mv2 / kT), special form of exp(-E/kT) –
the Maxwell-Boltzmann statistics distribution function of classical
distinguishable particles, probability that a certain state of energy
E is occupied

where C is a temperature depended proportionality factor-

function and β ≡ (kT)−1. k: Boltzmann constant, which we find
everywhere in this field, often kB
 Because v2 = vx2 + vy2 + vz2 then C’ a function of T, equal in x, y, z

 Rewrite this as the product β = β(T)

of three factors.

is the product of C’3 and three functions) 9

g(T) are the statistical weights of states for velocity components vx ,vy , vz
 Maxwell Velocity Distribution: Normalization and expectation
values
 g(vx) dvx is the probability that the x component of a gas
molecule’s velocity lies between vx and vx + dvx.
if we integrate g(vx) dvx over all of vx and set it equal to 1,
we get the normalization factor

problem specific factor, proportional T

Maxwell Boltzmann factor
= probability that
 The mean value (expectation value) of vx a certain energy
state is occupied
Full Widths at
Half Maximum
e-0.5 = 0.607 g(0)
At any temperature T
That is similar to the expectation value of momentum in the square wells, but
10
functions are real, so different form
Symmetry of velocity distribution in each space coordinate around the expectation
value was one of the guiding principles in deriving the velocity distribution !

Some important symmetries in physics and the corresponding conservation laws:

Isotropy of 3D pace and translation symmetry, conservation of linear momentum

Isotropy of 3D space and rotation symmetry, conservation of angular momentum

Isotropy of time: conservation of energy

“… it is only slightly overstating the case to say that physics is the study of
symmetry.” Philip Anderson, Nobel Prize 1977, 1/3 for “for their fundamental theoretical
investigations of the electronic structure of magnetic and disordered systems”

Pierre Curie’s principle; physics effect due to internal symmetry breaking in crystals, 1903 Nobel
prize ½ with his wife and ½ Becquerel (radioactivity)

Anisotropy and periodic translation symmetry in crystals, conservation of structural and physical
information in the translations periodic unit cell

Anisotropy and space group symmetry in crystals, conservation of structural and physical
information in the asymmetric part of the translation periodic unit cell (also called asymmetric unit)
https://www.youtube.com/watch?v=04ERSb06dOg&list=PLsPUh22kYmNAnurqRx9JlDGukZCsYcLhF,
9:40 min, symmetry group of the sphere is incorrect 11
Expectation value for Velocity2 = 0
 The mean value of vx2, also an expectation value that is a simple
function of x

Analogous for vy and vz

Note how expectation values are

usually written in this field

This is not zero because it

is related to kinetic energy,
remember the expectation
value of p2 was also not
zero in the square wells

It relates the human invented energy

1.3806488(13)×10 −23
JK −1
scale (at the individual particle level)
8.6173324(78)×10−5 eV K−1 to the absolute temperature scale (a
physical thing)

gas constant R divided by Avogadro’s number NA 12

Average kinetic energy in classical limit
 The results for the x, y, and z velocity2 components are identical.

 The mean translational kinetic energy of a molecule:

 Equipartion of the kinetic energy in each of 3 dimension a particle may

travel, in each degree of freedom of its linear movement

 this result can be generalized to the equipartition theorem

13
9.3: Equipartition Theorem
For a system of classical particles (e.g. atoms or molecules in a dilute
state so that they are distinguishable) in equilibrium, a mean energy
of ½ kT per system member is associated with each independent
quadratic term in the energy of the system member.

 That can be movement in a direction, rotation about an axis, vibration

about an equilibrium position, …, 3D vibrations in a harmonic
oscillator of atoms about their equilibrium position (in a crystal at very
high quantum numbers only)

 Each independent phase space coordinate = a degree of freedom

phase space is a mathematical construct, to be used to calculate

“density of states” analogues

14
Equipartition Theorem
 In a monatomic ideal gas, each molecule has

 There are three degrees of freedom.

 Mean kinetic energy is 3(½ kT) = 3/2 kT (expectation value)
 In a gas of N helium atoms, the total internal energy is

NAvogadro kB = R
We will need often
 CV = 3/2 N k - for any number of particles N the number of
 For the heat capacity for 1 mole particles, often also
with energy in
interval E and E +
dE as a distribution
 The ideal gas constant R = 8.31 J/K function, density of
energy states

15
 As predicted, only 3
translational
degrees of freedom

2 more (rotational)
Causes degrees of freedom
global
warming
2 more (vibrational)
degrees of freedom,
which also adds two
times 1/2 kBT
Geo- discrepancies due to quantized vibrations, not due to high particle
engineering density as this is all about gasses, i.e. distinguishable particles

We get excellent agreement for the noble gasses, they are just single atom-particles
16
and far away from other particles, no overlap in wavefunctions, classical physics
 “… basic difference between the care
economists bring to statistics and the
seeming carelessness of the physicists. For
example, when the Boyle law was found to
differ from the facts, the physicists simply
invented the concept of a “perfect gas,” that
is, a body that follows Boyle's law perfectly.
Naturally, perfect gas approximations are
absurd in some problems but are adequate in
many others, and they are so simple that one
must consider them first".
Benoȋt Madelbrot, New methods in statistical economics, The Journal of
Political Economy 71 (1963) 421–440.

https://www.youtube.com/watch?v=B-eh2SD54fM, Feynman’s comment 17

 A graph of Robert
Boyle's original data,
helped establishing
equation of state of
ideal gases

https://en.wikipedia.org/wiki/Boyle%27s_law, pV = constant (= N kB T),

ideal gas, 1662 Johannes Diderik van der Waals "for his work on the
equation of state for gases and liquids."

Nobel Prize Physics, 1910 18

Molar Heat Capacity
 The heat capacities of diatomic gases are temperature dependent,
indicating that the different degrees of freedom are “turned on” at
different temperatures.
Example of H2

From table on one of the previous slides

kT

19
The Rigid Rotator Model
 For diatomic gases, consider the rigid rotator model.

 The molecule rotates about the x and y axes easily.

 The corresponding rotational energies are ½ Ixωx2 and ½ Iyωy2, with I as
rotational moment of inertia
 There are five degrees of freedom in total, three translational and two
rotational.

20
Justification for two rotational degrees of freedom for
dumbbell shaped molecules
 In the quantum theory of the rigid rotator the allowed energy levels
are

 From previous chapters, the mass of an atom is largely confined to

its nucleus
 Iz is much smaller than Ix and Iy. Only rotations about x and y are
allowed at reasonable temperatures, low energies.

 Model of diatomic molecule, two atoms connected to each other by

a massless spring.
 The vibrational kinetic energy is ½ m(dr/dt)2, there is both kinetic
and potential energy ½ κ r2 in a harmonic vibration, so two extra
degrees of freedom
 There are seven degrees of freedom in total (three translational,
two rotational, and two vibrational for a two-atom molecule in a gas).
21
Two more degrees of freedom, so 7 in total

Two more degrees of

freedom, because
there are kinetic and
potential energy, both
are “quadratic”, i.e.
both have variables
that appear squared in
a formula of energy,
are both a degree of
freedom, ½ m (dr/dt)2
and ½ κ r2

22
 six degrees of freedom
not that simple at high temperatures
Condensed matter rather than dilute gas

Very high quantum numbers

6
/2 kT ?

according to classical physics, Cv should

be 3 R = 6/2 kBT NA for all crystals and
independent of the temperature

We will revisit this problem when we have learned about quantum distributions, concept of
phonons, which are quasi-particles that are not restricted by the Pauli exclusion principle 23
Maxwell Speed Distribution ΙvΙ derived from Velocity
Distribution as illustration of the procedure
 Maxwell velocity distribution:

Where is a function of T due to β = (kT)-1

 let’s turn this into a speed distribution.

 F(v) dv = the probability of finding a particle with speed
between v and v + dv.

One cannot derive F(v) dv (i.e. a distribution of a scalar entity) simply

from f(v) d3v (the velocity distribution function, i.e. a distribution of
vectors and their components), we need idea of phase space for
this derivation

A tool to count the available states of the system 24

 Maxwell Speed Distribution
 phase space, to count how many states there are
 Suppose some distribution of particles f(x, y, z) exists in normal three-
dimensional (x, y, z) coordinate space.

speed distribution function is

different to velocity distribution
function, but both have the same
Maxwell-Boltzmann statistical factor
as they refer to classically
distinguishable particles

 The distance of the particles at the point (x, y, z) to the origin is

 the probability of finding a particle between .

25
Maxwell Speed Distribution
 Radial distribution function F(v) of finding a particle with speed
between v and v + dv is what we are interested in {surely analogous to
f(x,y,z) a “density of states” (number of “vector magnitudes” within a dr
segment in 3D space), we want to go from coordinates to length of the vector,
a scalar} Phase space for |v |
 The volume of any spherical shell is 4πr2 dr.

replace the 3D “space coordinates x, y, and z”

with the “speed-space” components vx, vy, and vz
change from maths to physics

 Maxwell speed distribution: Velocity distribution

It is only going to be valid in the classical limit, as a few particles would have speeds in
excess of the speed of light. But there are very very few of those particles
26
 Maxwell Speed Distribution
What we were looking at on slide 5

g(T,v) = 4πCv2 is “speed states

factor”, depends on T and v2 , a
statistical weight concerning the
v*
physical property gets multiplied with
probability that the corresponding
a bit off energy state is occupied

Note that function is normalized so

1
that 100% of all the particles are
under this curve
 The most probable speed v*, the mean speed , and the root-
mean-square speed vrms are all different.

F(v) goes to zero at infinity, very very few particles have speeds higher than c 27
Maxwell Speed Distribution
 Most probable speed (at the peak of the speed distribution), take the first
derivative of the speed distribution function and set it zero, derive the
consequences:

 Average (mean) speed, will be an expectation value that we calculate from an

integral on the basis of the speed distribution function

28
 average (mean) of the square of the speed, will be an expectation value that we
calculate from another integral on the basis of the speed distribution function

<KE> = 3/2 kT
Slide 32
We define root mean square speed on its basis

which is of course associated with the

mean kinetic energy
We can also calculate the spread (standard deviation) of the speed
distribution function in analogy to quantum mechanical spreads

Note that σv in proportional to

So now we have the whole function, can make calculations for all T !!! 29
 Maxwell’s speed distribution experiments

Slits have small

widths, size of it
defines Δv (a small
speed segment of the
speed distribution)

Spread ~ square root of T 30

Straightforward: turn speed distribution into kinetic energy (internal energy of ideal
gas) distribution

Two total energy specific

factors (a function)

31
 Number of So we recover the equipartition theorem
particles with for a mono-atomic gas, it’s what we
energy in wanted to know on side 5 so that we
interval E and could make prediction on other physical
E + dE entities about what is going to be
measure on average in equilibrium (a
stationary state)

Is temperature
dependent as it should
according to Count
Rumford, slide 4

n(E) is a continuous function of E in classical physics,

32
but will be a series of discrete values in quantum physics, i.e. 6 quantum states in 2p
9.5: Needs for Quantum Statistics
When molecules, atoms, or subatomic particles are fermions, i.e. most of
condensed matter, in the liquid or solid state, the Pauli exclusion principle
prevents two particles with identical wave functions from sharing the same
quantum state. The 3D spatial part of the wavefunction can be identical for
two particles in the same state, but the spin part of the wavefunction has to
be different to fulfill the Pauli exclusion principle.
 If the particles under consideration are indistinguishable and bosons, they

are not subject to the Pauli exclusion principle, i.e. behave differently

 There are only certain energy values allowed for bound systems in quantum
mechanics, so energy states will be a series of discrete values, rather
than a continuous function

 There was no restriction on particle energies in classical physics, relativistic

correction when necessary.

33
Classical physics Distributions
 Boltzmann showed that the statistical factor exp(−βE) is a characteristic of any
classical system in equilibrium (in agreement with Maxwell’s speed
distribution) quantities other than molecular speeds may affect the energy of a given state
(as we have already seen for rotations, vibrations)
 Maxwell-Boltzmann statistics for classical system: β ≡ (kBT)−1

 The energy distribution for classical system:


A is
n(E) dEa=normalization
the number offactor, problem
particles with specific
energies between E and E + dE.

 g(E) = problem specific continuous function of classical energy

distribution function for ideal gas. In case of quantum particles often
discrete
 FMB gives the relative probability that an energy state is occupied at a
given temperature.
34
Classical / quantum distributions
 Characteristic of indistinguishability makes quantum statistics different
from classical statistics.

 The possible configurations for two distinguishable particles in either

of two energy (or anything else) states:

State 1 State 2
AB 1/4
A B
B A
AB
 There are four possible states the system can be in, each of them is
equally likely.

35
Quantum Distributions
 If the two particles are indistinguishable:

State 1 State 2
A and B in XX
previous X X
1/3
slide
XX
 There are only three possible states of the system.

 Because there are two types of quantum mechanical particles, two

kinds of quantum distributions are needed.
 Fermions:
 Particles with half-integer spins, obey the Pauli principle.
 Bosons:
 Particles with zero or integer spins, do not obey the Pauli principle.

36
6 particles distributed over 9 energy states

Multiply each state with its number of

microstates for distinguishable particles –
sum it all up and you get the distribution of
classical physics particles

Ignore all microstates for indistinguishable

particles – sum it all up, that would be the
distribution for bosons over 20 macrostates

Ignore all microstates and states that have

more than two particle at the same energy
level, - sum it all up, that would be the
distribution of fermions
Serway et al, chapter 10 for details

Realize, there must be three different

distribution functions !!

37
Quantum Distributions
 Fermi-Dirac distribution: different energy states have different degeneracies

Are no longer continuous

where functions in quantum
mechanical statistics
 Bose-Einstein distribution:

We call them in general discrete density of

Where energy states and typically drop the discrete
as this is understood due to being quantum

 In each case Bi (i = 1 or 2) is a normalized factor which depends on the

physics of the problem.
 Both distributions reduce to the classical Maxwell-Boltzmann distribution
when Bi exp(βE) is much greater than 1, this happens at low densities (i.e. in a
dilute gas at moderately high temperatures, i.e. room temperature

Different version 38
Classical and Quantum Distributions
For
photons in
cavity,
Planck’s
black
body
radiation,
B2 = 1

E is quantized in units of hf
if part of a bound system

e0 = 1
39
 Quantum Distributions If all three
normalization
has to do with factors = 1,
specific just for
normalization comparison
factor

differences large for

small quantum numbers

 The exact forms of normalization factors for the distributions depend on the
physical problem being considered.
 Because bosons do not obey the Pauli exclusion principle, more bosons can
fill lower energy states (are actually attracted to do so per minimization of total E)
 All three graphs coincide at high energies – the classical limit.
Maxwell-Boltzmann statistics may be used in the classical limit when
particles are so far apart that they are distinguishable, can be tracked by their
paths, even when densely packed, at high T we recover classical physics 40
 When there are so many
states that there is a very low
probability of occupation, high
temperatures

From the equipartition theorem for kinetic energy, Ek

also if the particles are

heavy (macroscopic),
i.e. a bunch of classical
physics particle
41
at very high temperatures, discrete energy levels appear continuous
 One US gallon = 3.785 liter = dm3
5.9 gallons ≈ 22.4 liter

Anything to do with solids, when high probability of occupancy of energy

states, e.g. electrons in a metal, which are fermions
Only the form of Ohm’s law survives, but the classical Drude theory
42
predicts the wrong temperature dependence of electrical resistance
 anything to do with
liquids, when high
probability of
occupancy of energy
states
Bose-Einstein
4
condensate for 2 He
at 2.17 K superfluidity
(explained later on)

https://www.youtube.com/watch?v=2Z6UJbwxBZI, 2 min 43
 degeneracy of
the first exited
state in H atom
n l ml ms up ms down

2 0 0 +1/2 -1/2
2 1 1 +1/2 -1/2
2 1 0 +1/2 -1/2
g(E) is the statistical weight of the state with energy E 2 1 -1 +1/2 -1/2

g functions here: how many states there are per unit energy value, in other words:
the degeneracy if we talk about many hydrogen atoms

g functions are always problem specific ! 44

 Revisited from slide 21

Einstein’s assumptions in 1907, atoms vibrate independently

of each other
(not starting from zero point energy,
due to uncertainty principle not known
yet)
he used Maxwell-Boltzmann statistics (because the other
distribution functions were not known at the time) and aimed
for a large quantum number expression, which should be 6/2
kT, Dulong-Petit law

A. Einstein, "Die Plancksche Theorie der Strahlung und die

Theorie der spezifischen Wärme", Annalen der Physik 22
(1907) 180–190

(moderate to high T)

i.e. at high temperatures it approaches the classical value of 2 degrees of freedom

45
with ½ kT each times 3 vibration directions (Bohr’s correspondence principle once more)
To account for different bond strength, something crystal structure specific, a constant
that need to be measured

n: integer quantum number

hetero-polar bond in diamond much stronger than metallic bond in lead and
aluminum, so much larger Einstein Temperature for diamond (1,320 K) >> 50 to
100 K for typical metals 46
Peter Debye lifted in 1912
the assumption that atoms
vibrate independently,
similar statistics, Debye
temperature TD

even better modeling with

phonons, which are
pseudo-particles of the
boson type

47
 https://
www.youtube.com/
watch?v=le_ORQZzkmE
quasiparticles in
semiconductors,
phonons, Cooper pairs,
14 min
collective motions called phonons (Public Domain; Sean Kelley via NIST)

48
Blackbody Radiation
Blackbody Radiation
 Power density of the emitted radiation

W/m2 also called spectral density

Use Bose-Einstein distribution because photons are bosons with

spin 1 (they have two polarization states)
 For a particle in terms of momentum in a 3D infinitely deep cubic

well: now our particles are massless,

so we need alternative
formulation

 E = pc = hf so we need the equivalent of this formulae in terms of

momentum (KE = p2 / 2m)

49
 Phase space again, this time is how many “momentum states” are
there in the whole volume

Density of states in cavity, we can assume the cavity is a

sphere, we could alternatively assume it is any kind of shape
that can be filled with tiny cubes …

E is again a scalar just as speed was, just as integer numbers are, no

negative numbers allowed
50
 Bose-Einstein Statistics
 The number of allowed energy states within “radius” r of a sphere is

1/8 comes from the restriction to positive values of ni and 2 comes from the
fact that there are two possible photon polarizations.
 Rewrite Energy equation in terms of r,

and substitute into the above equation for Nr

 Then differentiate to get statistical weight g(E)

a.k.a. density of energy states

 Multiply in Bose-Einstein distribution factor

For photons, the normalization factor is 1, they are created and destroyed as needed
51
 Bose-Einstein Statistics
 Convert from an energy “number” distribution to an energy
“density” distribution u(E).
3
L3 cancels, so
the shape of
 For all photons in the range E to E + dE the cavity does
not matter

 Using E = hf and |dE| = (hc/λ2) dλ, –sign dropped as meaningless

Correct in 4th
c = λf edition available
as *.pdf in library
 multiplying by c/4 is required to convert from energy density
Ws/m3 to power density W/m2
(factor ¼ due to surface area of a sphere 4πr2)

and worldwide fame for Satyendra Nath Bose 1894 – 1974 but he didn’t get a Nobel
52
Liquid Helium
 Has the lowest boiling point of any element (4.2 K at 1 atmosphere
pressure) and has no solid phase at normal pressure.
 The density of liquid helium as a function of temperature.

Part II: https://www.youtube.com/watch?v=1RJKnbIvbMg 53

Liquid Helium
 The specific heat of liquid helium as a function of temperature

Thermal conductivity goes to infinity

at lambda point, so no hot bubbles
can form while the liquid is boiling,

 The temperature at about 2.17 K is referred to as the critical

temperature (Tc), transition temperature, or lambda point.
 As the temperature is reduced from 4.2 K toward the lambda point,
the liquid boils vigorously. At 2.17 K the boiling suddenly stops.
 What happens at 2.17 K is a transition from the normal phase to
the superfluid phase.

54
Liquid Helium

 The rate of flow increases dramatically as the temperature is

reduced because the superfluid has an extremely low viscosity.
 Creeping film – formed when the viscosity is very low and some
helium condenses from the gas phase to the glass of some beaker.
55
https://www.youtube.com/watch?v=2Z6UJbwxBZI 56
Liquid Helium
 Liquid helium below the lambda point is part superfluid and part
normal.
 As the temperature approaches absolute zero, the superfluid
approaches 100% superfluid and zero viscosity.

 The fraction of helium atoms in the superfluid state:

 Superfluid liquid helium is referred to as a Bose-Einstein

condensation.
not subject to the Pauli exclusion principle because (the
most common helium isotopes are bosons, spin 0
all particles are in one and the same quantum state

Final part: https://www.youtube.com/watch?v=7U4hQ_Y9_Jk 57

Unlike most dimensionless numbers used in the study of fluid mechanics, the Kapitza number
represents a material property, as it is formed by combining powers of the surface tension,
density, gravitational acceleration and kinematic viscosity. [4]

where σ is the surface tension (SI units: N/m), g is gravitational acceleration (m/s 2), ρ is
density (kg/m3), β is inclination angle (rad), and ν is kinematic viscosity (m 2/s).

"Complete list of L D Landau's works". doi:10.1070/PU1998v041n06ABEH000413

http://bukovsky-archives.net/pdfs/sovter74/land-17.pdf about “red fascism” in

58
Russian, from the year I was born
9.7: Fermi-Dirac Statistics

 EF is called the Fermi energy

 When E = EF, the exponential term is e0 = 1
FFD = ½
 In the limit as T → 0,

 At T = 0, fermions occupy all of the lowest energy levels.

 Near T very low, there is very very little chance that thermal
agitation will kick a fermion to an energy greater than EF.

59
Fermi-Dirac Statistics
T=0 T>0 ½

 As the temperature increases from T = 0, the Fermi-Dirac factor “smears out”.

 Fermi temperature, defined as TF ≡ EF / k. .

T = TF T >> TF

 When T >> TF, FFD approaches a decaying exponential of the Maxwell Boltzmann
statistics. At room temperature, only tiny
= Fermi energy / kB
amount of fermions are in the region
around EF,i.e. can contribute to
electric current, heat capacity, …60
In metals, we have
a free quantum
electron gas of
fermions
(electrons)

A mono-atomic classical
gas has a molar heat
capacity of 3/2 kT NA
and very low density

Electron densities are pretty high, but due to their property

of being fermions, they do not contribute much to molar
heat capacity, ≈ 1 % in Cu, electrical conductivity, …

61
Classical Theory of Electrical Conduction
 Paul Drude (1900) showed on the basis of the idea of a free
electron gas inside a metal that the current in a conductor should
be linearly proportional to the applied electric field, that would be
consistent with Ohm’s law, an empirical observation
 His prediction for electrical conductivity:

 Mean free path

and mean free particle speed
(expectation values) .
 Drude electrical conductivity:

62
Classical Theory of Electrical Conduction
Based on Maxwell’s speed distribution, as derived on
slide 26

 According to the Drude model, the conductivity should be

proportional to T−1/2.

 But for most metals is very nearly proportional to T−1 !!

 This is not consistent with experimental results.

 l and τ make only sense for a realistic microscopic model, so

whole approach abandoned, but free electron gas idea kept, just a
different kind of gas that obeys Fermi-Dirac statistics

63
Quantum Theory of Electrical Conduction

 The allowed energies for electrons in an infinitely deep 3D well

(cubic box) are

 The parameter r is the “radius” of

a sphere in phase space
 The volume is (4/3)πr 3
 The number of energy states up
to radius r is . I think there are inconsistencies in the
derivation of g(E) in Thornton-Rex book,
but their result is correct
due to spin
Density of discrete energy states
64
Quantum Theory of Electrical Conduction
 At T = 0, All states up to EF are filled,
all higher states are empty
 The mean electronic energy per particle:

 Internal energy of the free electron gas of N electrons:

At T = 0

 Only those electrons within about kT of EF will be able to absorb thermal

energy and jump to a higher state. Therefore the fraction of electrons
capable of participating in this thermal process is on the order of kT / EF.

65
 Quantum Theory of Electrical Conduction
 In general,
At T > 0
Where α is a constant π2/4.
Product of near
step function for FFD
with density of state
function g(E)

 The exact number of electrons depends on temperature.

 Heat capacity is EF = kB TF

 Molar heat capacity is Earlier estimates ≈

35,000 K for Na

66
Quantum Theory of Electrical Conduction
 With the value TF ≈ 80,000 K for copper, we obtain cV ≈ 0.02 R,
which is consistent with the experimental value! Quantum theory
has proved to be a success. For cV of crystalline metals, we
can ignore contribution of the free electron gas to the molar
heat capacity, Dulong-Petit law cV_crystal ≈ 3 R at moderate to
higher temperature
 Replace mean electron speed on slide 61 by Fermi speed uF
defined from EF = ½ m uF2.
 Conducting electrons are loosely bound to their atoms.
these electrons must be at the highest energy levels
at room temperature the highest energy level is close to
the Fermi energy.
 Fermi speed to be used instead of

One order of magnitude higher than of Drude’s classical physics model 67

speed

68
 Quantum Theory of Electrical Conduction
 Drude thought that the mean free path could be no more than a
few tenths of a nanometer, but it is much longer than his simple
estimation, because electrons have wave-particle duality

 Einstein calculated the value of ℓ to be on the order of 40 nm in

copper at room temperature.
As measured in
 The conductivity is experiments at room
temperature
at moderate to high temperature, classical
 Sequence of proportions. oscillator limit

Scattering cross section Is due to vibrations of harmonic oscillators, U  πr2

Exact quantum calculations will get it exactly right, the T-1 dependency of σ is approx.
69
 ) Like an atom
) 70
 Fermi Problems
The classic Fermi problem, generally attributed to Enrico Fermi, is "How many
piano tuners are there in Chicago?"

A typical solution to this problem would involve multiplying together a series of

estimates that would yield the correct answer if the estimates were correct. For
example, we might make the following assumptions:

1. There are approximately 5,000,000 people living in Chicago.

2. On average, there are two persons in each household in Chicago.

3. Roughly one household in twenty has a piano that is tuned regularly.

4. Pianos that are tuned regularly are tuned on average about once per year.

5. It takes a piano tuner about two hours to tune a piano, including travel time.

6. Each piano tuner works eight hours in a day, five days in a week, and 50 weeks
in a year.
71
From these assumptions we can compute that the number of piano
tunings in a single year in Chicago is: (5,000,000 persons in Chicago) / (2
persons/household) × (1 piano/20 households) × (1 piano tuning per
piano per year) = 125,000 piano tunings per year in Chicago.

And we can similarly calculate that the average piano tuner performs: (50
weeks/year)×(5 days/week)×(8 hours/day)×(1 piano tuning per 2 hours
per piano tuner) = 1,000 piano tunings per year per piano tuner.

Dividing gives: (125,000 piano tuning per year in Chicago) / (1,000 piano
tunings per year per piano tuner) = 125 piano tuners in Chicago.

A famous example of a Fermi-problem-like estimate is the Drake

equation, 1961, which seeks to estimate the number of intelligent
civilizations in the galaxy. The basic question of why, if there are a
significant number of such civilizations, ours has never encountered any
others is called the Fermi paradox.
72
1961 “As I planned the meeting, I realized a few day[s] ahead of time we needed an
agenda. And so I wrote down all the things you needed to know to predict how hard
it's going to be to detect extraterrestrial life. And looking at them it became pretty
evident that if you multiplied all these together, you got a number, N, which is the
number of detectable civilizations in our galaxy. This was aimed at the radio search,
and not to search for primordial or primitive life forms.”
Frank Drake, https://en.wikipedia.org/wiki/Drake_equation

73
 N = 1.5 × 10−5 × 10−9 × 0.2 × 304 = 9.1 × 10−13
If communication capable civilizations are short
lived, a few hundred years, or don’t make an effort
announcing their presence
N = 3 × 1 × 0.2 × 0.13 × 1 × 0.2 × 109 =
15,600,000
If communication capable civilizations live for a
very long time and are actually broadcasting all the
time, wasting an enormous amount of energy
Take your pick ½ Physics Nobel prize 2019 jointly to Michel
Mayor and Didier Queloz "for the discovery
of an exoplanet orbiting a solar-type star”

Such planets are some 50 or 100 light years away from us.
74
An “earth-like” planet around Proxima Centauri in 2016, only about half as hot as sun,
Stefan-Bolzmann law predicts 6.25 % of the total radiant energy, red dwarf, about 1 m
peak of radiation (from Wien’s displacement law), so not a good place for us to live 75on
76
 https://physicsworld.com/a/spin-3-2-superconductor-is-a-first-say-physicists/

Spin
3/2

“The first known superconductor in which spin-3/2 quasiparticles form Cooper

pairs has been created by physicists in the US and New Zealand. The
unconventional superconductor is an alloy of yttrium, platinum and bismuth,
which is normally a topological semimetal …”
77
 B for Boltzmann, also MB

Ideal gas

78
 eα problem specific

>>
Typically at high T

e.g. laser

Two 3He pair up to form a composite boson

79
 Change from Maxwell speed distribution to kinetic energy distribution

 Rewrite Maxwell speed distribution in terms of energy.

 For a monatomic gas the energy is all translational kinetic

energy.

where

80
 statistical

All condensed matter (liquids and solids) problems are statistical quantum
mechanics problems !!

Quantum condensed matter physics problems are typically low temperature

problems

Ideal gasses can be modeled classically, because they have very low matter
densities

81
 After a true story

https://www.youtube.com/watch?v=TaSz18osf5w

Just for the fun of it: https://www.youtube.com/watch?v=9mXJK86GCsI

“How and why” with respect to physics:

https://www.youtube.com/watch?v=mWe5m2Yj9T0

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