Applications of statistical physics to

selected solid-state physics phenomena

for metals
similar models for thermal and electrical
conductivity for metals, on basis of free electron
gas, treated with Maxwell-Boltzmann statistics
i.e. as if it were an ideal gas
Lorenz numbers, a fortuitous result, dont be
fooled, the physics (Maxwell-Boltzmann statistics)
behind it is not applicable as we estimated earlier
But Fermi-Dirac statistics gets us the right physics
1

Metals have high conductivities for both electricity and heat. To explain both
the high conductivities and the trend in this table we need to have a model for
both thermal and electrical conductivity, that model should be able to explain
empirical observations, i.e. Ohms law, thermal conductivity, WiedemannFranz law,

300K
2.3
2.55
2.2

2
B
2

Wiedemann and Franz

Law, 1853, ratio K/s T =
Lorenz number = constant
2.4 10-8 W O K -2
independent of the metal
considered !! So both
phenomena should be
based on similar physical
idea !!!
Classical from Drude (early 1900s)
theory of free electron gas

K 3k
8
2
=
1.12 10 WK
T 2e

Too small by factor 2,

seems not too bad ???

To explain the high conductivities and the trend we need to have a model for
both thermal and electrical conductivity, that model should be able to explain

Ohms law, empirical for many metals and insulators, ohmic

solids Conductivity , resistivity is its reciprocal value

J = s E current density is proportional to

applied electric field
R = U / I for a wire R = ? l / A
J: current density A/m2
s : electrical conductivity O-1 m-1, reciprocal value of electrical
resistivity
E: electric field V/m
Also definition of s : a single constant that does depend on the
material and temperature but not on applied electric field
4
represents connection between I and U

Gas of classical charged particles, electrons, moves through

immobile heavy ions arranged in a lattice, vrms from equipartition
theorem (which is of course derived from Boltzmann statistics)
_2

1
3
me v = k BT
2
2
_

vrms

3kBT
= v =
me

Between collisions, there is a

mean free path length: L = v rms t
and a mean free time t (tau)
Figure 12.11 (a) Random successive displacements of an electron in a metal without
5
an applied electric field.

If there is an electric field

E, there is also a drift
speed vd (108 times
smaller than vrms) but
proportional to E, equal
for all electrons

eE
vd =
me
Figure 12.11 (b) A combination of random displacements and displacements produced
by an external electric field. The net effect of the electric field is to add together multiple
displacements of length vd opposite the field direction. For purposes of illustration, this
6
figure greatly exaggerates the size of vd compared with vrms.

neAvd dt
J=
= nevd
Adt
Substituting for vd

ne
J=
E
me
2

Figure 12.12 The connection between current

density, J, and drift velocity, vd. The charge that
passes through A in time dt is the charge
contained in the small parallelepiped, neAvd dt.

So the correct
form of Ohms law
is predicted by the
Drude model !!
7

ne
=
me

With vrms according to

Maxwell-Boltzmann
statistics

With mean free time t =

L/vrms

ne L
=
3k BTme

ne L
=
mevrms

Proof of the pudding: L should be on the order of magnitude of the inter-atomic

distances, e.g. for Cu 0.26 nm

8.49 1022 cm 3 (6.02 1019 C )2 0.26nm

3 1.381 1023 JK 1 300K 9.109 10 31 kg

s Cu, 300 K = 5.3 106 (Om)-1 compare with experimental value 59 106
(Om) -1, something must we wrong with the classical L and vrms 8

Result of Drude theory one order of magnitude too small, so L

must be much larger, this is because the electrons are not
classical particles, but wavicals, dont scatter like particles, in
addition, the vrms from Boltzmann-Maxwell is one order of
magnitude smaller than the vfermi following from Fermi-Dirac
statistics

3k BTme
=
=

2
ne L
So ? ~T0.5 theory
for all temperatures,
but ? ~T for
reasonably high T ,
so Drudes theory
must be wrong !

Figure 12.13 The resistivity of pure copper as a function of temperature.

10

Phenomenological similarity conduction of electricity and

conduction of heat, so free electron gas should also be the key
to understanding thermal conductivity

V
J =
x
Q
T
= K
At
x

1
K = CV vrms L
3
k B nvrms L
K=
2

Ohms law with Voltage gradient,

thermal energy conducted through area

A in time interval ? t is proportional to
temperature gradient

Using Maxwell-Boltzmann statistics,

equipartion theorem, formulae of Cv for
ideal gas = 3/2 kB n
Classical expression for K
11

vrms

3k BT
= v =
me

Lets
continue

For 300 K and Cu

23

vrms

3 1.381 10 JK 300K
=
9.109 1031 kg

kB nvrms L
K=
2

1.381 1023 JK 1 8.48 1022 cm 3 1.1681 105 ms 1 0.26nm

K=
2
1.381 1023 JK 1 8.48 1028 m 3 1.1681 105 ms 1 0.26 109 m
K=
2

Ws
K = 17.78
Kms

Experimental value for Cu at (300 K) = 390 Wm-1K-1,

again one order of magnitude too small, actually
12
roughly 20 times too small

ne 2 L
=
mevrms

With
MaxwellBoltzmann

This was also one order of magnitude too

small,
2
e mrs
2

k B nvrms Lme vmrs k B m v

=
=
2

2ne L
2e
_

vrms

3kBT
= v =
me

Lorenz number classical K/s

K 3k B2
8
2
= 2 1.12 10 WK
T 2e

2
3
k
K = BT
2e2

Wrong only by a
factor of about 2,
Such an
agreement is called
fortuitous
13

14

replace Lfor_a_particle with Lfor_a_wavial and vrms with vfermi,

2

classical

ne L for _ a _ particle
=
me vrms

L for _ a _ wavical =
_

vrms

3k BT
= v =
me

quantum =

ne2 L for _ a _ wavical

me v fermi

me v fermi quantum
ne

v fermi ==

2EF
me

For Cu (at 300 K), EF = 7.05 eV , Fermi energies have only

small temperature dependency, frequently neglected
15

v fermi

2EF
==
me

v fermi ,copper ,300 K =

2 7.05 1.602 109 J

6
1
=

1
.
57
10
ms
9.109 1031 kg

one order of magnitude larger than classical vrms

for ideal gas

L for _ a _ wavical =

me v fermi quantum
ne

L for _ a _ wavical _ cooper =

9.109 10 31 kg 1.57 106 ms 1 5.9 107 1m 1
8.49 1028 m 3 (1.602 10 19 C )2
L for _ a _ wavical _ cooper = 39nm

two orders of magnitude larger

than classical result for particle16

classical =

ne L for _ a _ particle
me vrms

So here something two orders of two magnitude too small (L)

gets divided by something one order of magnitude too small
(vrms),
i.e. the result for electrical conductivity must be one order of
magnitude too small, which is observed !!
But L for particle is quite reasonable, so replace Vrms with Vfermi
and the conductivity gets one order of magnitude larger, which
is close to the experimental observation, so that one keeps the
Drude theory of electrical conductivity as a classical
approximation for room temperature
17

effect, neither the high vrms of 105 m/s of the electrons

derived from the equipartion theorem or the 10 times higher
Fermi speed do not contribute directly to conducting a current
since each electrons goes in any directions with an equal
likelihood and this speeds averages out to zero charge
transport in the absence of E

.in

Figure 12.11 (a) Random successive displacements of an electron in a metal without an

applied electric field. (b) A combination of random displacements and displacements produced
by an external electric field. The net effect of the electric field is to add together multiple
displacements of length vd opposite the field direction. For purposes of illustration, this figure
18
greatly exaggerates the size of vd compared with vrms.

K classical

k B nvrms Lclassical
=
2

Vrms was too small by one order of magnitude, Lclassical was

too small by two orders of magnitude, the classical
calculations should give a result 3 orders of magnitude
smaller than the observation (which is of course well
described by a quantum statistical treatment)
so there must be something fundamentally wrong with our
ideas on how to calculate K, any idea ???

19

Wait a minute, K has something to do with the heat capacity

that we derived from the equipartion theorem

K classical

1
= CV _ for _ ideal _ gasvrms L for _ particle
3

We had the result earlier that the contribution of the electron

gas is only about one hundredth of what one would expect
from an ideal gas, Cv for ideal gas is actually two orders or
magnitude larger than for a real electron gas, so that are two
orders of magnitude in excess, with the product of vrms and
Lfor particle three orders of magnitude too small, we should
calculate classically thermal conductivities that are one order
of magnitude too small, which is observed !!!
20

2
e mrs
2

k
nv
Lm
v
k
m
v
B
rms
e
mrs
B
K =
=
2

2ne L
2e
K 3k B2
8
2
= 2 1.12 10 WK
T 2e

fortunately L cancelled, but vrms gets squared, we are indeed

very very very fortuitous to get the right order of magnitude
for the Lorenz number from a classical treatment
(one order of magnitude too small squared is about two orders of
magnitude too small, but this is compensated by assuming that the
heat capacity of the free electron gas can be treated classically which in
turn results in a value that is by itself two order of magnitude too largetwo missing orders of magnitude times two excessive orders of
21
magnitudes levels about out


k T
=
(
)nL for _ a _ wavical
3 me v fermi
2

K fermi

2
B

quantum =

ne L for _ a _ wavical
me v fermi

That gives for the Lorenz number in a quantum treatment

K k
8
2
=
= 2.45 10 WK
T
3e
2 2
B
2

22

23

Back to the problem of the temperature dependency of

resistivity

Drudes theory predicted a dependency on square root

of T, but at reasonably high temperatures, the
dependency seems to be linear

This is due to Debyes

phonons (lattice vibrations),
which are bosons and need to
be treated by Bose-Einstein
statistics, electrons scatter on
phonons, so the more
phonons, the more scattering
Number of phonons proportional to Bose-Einstein distribution function

n phonons

1
e

h / k BT

Which becomes
for reasonably
large T

k BT
n phonons
h24

At low temperatures, there are hardly any phonons,

scattering of electrons is due to impurity atoms and
lattice defects, if it were not for them, there would
not be any resistance to the flow of electricity at
zero temperature

Matthiessens rule, the resistivity of a metal can be

written as
s = s lattice defects + s lattice vibrations

25