1.

Conduction electrons in a metal: the free-electron gas 1

1. Conduction electrons in a
metal: the free-electron gas
1 From free atoms to solid state
2 From an electron gas to a free electron gas
3 The Drude model - a classical model for a free
electron gas
4 The Sommerfeld theory - a quantum mechanical
model of a free electron gas
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1.1 From free atoms to solid state 2
From free atoms to solid state.
Consider a collection of free atoms. With the exception of the nucleus, these
atoms consist of 1) inner, relatively tightly bound electrons, so called inner-
shell electrons or core-electrons 2) outer, losely bound electrons, so called
valence electrons. In this description, we can dene the valence electrons
as the electrons which orbit outisde those inner electrons which possess the
electronic structure of a rare gas atom. For examples:
Sodium : 1s
2
2s
2
2p
6
3s
1
[Ne]3s
1
Aluminium : 1s
2
2s
2
2p
6
3s
2
3p
1
[Ne]3s
2
3p
1
Copper : 1s
2
2s
2
2p
6
3s
2
3p
6
4s
1
3d
10
[Ar]3d
10
4s
1
In aluminium, the 1s, 2s and 2p orbitals are completely lled, and so have
the same electronic conguration as the rare gas atom Ne. This means that
the attractive Coulomb-eld from the nucleus is eectively screened, and
why the three outer electrons (in the 3s and 3p orbitals) are more weakly
bound than the inner-shell electrons. The same is true for the single valence
electron in sodium and the eleven electrons in copper.
What happens if we take the same neutral free atoms, e.g. aluminium,
and give them the same separation they would have in the solid state, i.e.,
metallic aluminium?
The inner-shell electrons are hardly aected. Conversely, the outer electrons
- the valence electrons - can be said to move away from their respective atoms
and move about like a more-or-less homogeneous electron gas. The atomic
nuclei and the inner electrons, which remain in approximately unchanged
atomic levels, form positive ions, i.e., ion cores.
This description describes an important dierence between free atoms and
the solid state. An exception to this model are the nobel gases. By denition,
these atoms do not have valence electrons, and in a rare-gas crystal, for
example frozen Argon, the atomic electronic conguration is more-or-less
unchanged.
Valence electrons in the solid state or, to be more precise, their quantum
mechanical wavefunction are only weakly or moderately localised around
atoms; more importantly, they are not localised to any specic atom. In a
single solid state crystal, the wavefunction of a valence electron is spread
out over the entire crystal or, in a polycrystaline material, over the whole
microcrystal. Strictly speaking, this is also true for those electrons in the
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1.1 From free atoms to solid state 1
inner shells, although their wavefunctions are vanishingly small in the areas
between the ion cores, and so it is reasonable to consider these electrons
as localised (bound) to specic ions. Another way of expressing this is to
consider that the probability that these electrons can change location via
tunneling from one atom to another is vanishingly small.
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2. Conduction electrons in a metal: the free-electron gas 2
2. Conduction electrons in a
metal: the free-electron gas
1 From free atoms to solid state
2 From an electron gas to a free electron gas
3 The Drude model - a classical model for a free
electron gas
4 The Sommerfeld theory - a quantum mechanical
model of a free electron gas
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2.2 From an electron gas to a free electron gas 1
From an electron gas to a free electron gas.
With the help of band-gap theory, it can be seen that the electrons in a metal
contribute to its electrical conductivity, and these are called the conduc-
tion electrons, though not every valence electron contributes. For example,
metallic copper has 11 valance electrons but only one of them contributes
to the coppers conductivity.
Consider a metal with n conduction electons per unit volume. These con-
duction electrons also represent a electrical charge density = ne, where
e is the elementary charge. The remaining valence electrons together with
the inner shell electrons consitiute an average electrical charge denisty =
+ne. Therefore, it is a reasonable approximation to assume that a single
conduction electron sees its environment as being electrically neutral. With
this assumption, the electron moves about without the inuence of external
forces, i.e., as a free particle.
This model is called the free elctron gas model. It is noted that the model
assumes that the positive charge density , +ne, is considered as a homoge-
neous continuum in which the conduction electrons move. It follows that
the free electron gas, in equilibrium, is therefore also homogeneous.
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3. Conduction electrons in a metal: the free-electron gas 2
3. Conduction electrons in a
metal: the free-electron gas
1 From free atoms to solid state
2 From an electron gas to a free electron gas
3 The Drude model - a classical model for a free
electron gas
4 The Sommerfeld theory - a quantum mechanical
model of a free electron gas
RDT / FK5015 /
3.3 The Drude model - a classical model for a free electron gas 3
The Drude model - a classical model for a free
electron gas.
When Drude presented the rst classical theory to describe a free electron
gas in 1900, he assumed that the free moving electrons would follow Maxwell-
Boltzmann statistics, similarly to atoms in a classical ideal gas. Their av-
erage translational energy would then be
3
2
k
B
T where k
B
is Boltzmanns
constant, and T the absolute temperature.
Electric current in a metal means that the gas of conduction electrons is
set in coordinated motion, e.g, via an external electric eld. Electric re-
sistance is dependent on the conduction electrons now and then colliding
with something that changes their direction of motion. Drude supposed
that the electrons scattered from the ion cores, but we now know that this
is incorrect: the conduction electrons generally travel over distances that
are considerably larger than the separation between ion cores without scat-
tering, and this is described by band-gap theory. It has been found that
the resistance in crystaline media is mostly due to the conduction electrons
scattering o either vibrations in the crystal structure, i.e., thermal motion,
or defects in the structure. The lattice vibrations are quantised, and these
quanta are called phonons, and so the conduction electrons scatter by ab-
sorption and emission of phonons, i.e., via exchanging momentum (and a
little energy) with the quantised lattice-vibration eld.
As a starting point, we can use the Drude model without specing exactly
what the conduction electrons are scattering o. Here, the Drude model is
then an example of a phenomenological model. It should be noted that the
free electron gas is an approximative model for conduction electrons, and
that it does not work as a model for the other valence electrons in the metal
or for the valence electrons in a crystaline isolator - these electrons do not
contribute to the electrical conductivity.
Electrical conductivity - Ohms law.
Ohms law for the relationship between the current density, j, and the electric
eld strength, E can be expressed by:
j = E (1)
where is the conductivity. We can prove this equation from Drudes model
and a formula for .
If we assume that every conduction electron occasionally scatters (against
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3.3 The Drude model - a classical model for a free electron gas 4
vibrations or defects) in such a way that after every collsion the electron
moves in a random direction. The average time between two collisions (of
the same electron) is called the relaxation time, . Furthermore, if we as-
sume that we have n conduction electrons per unit volume in the metal,
and that we set them in a uniform electic eld, E. We assume that the
electrons accelerate in this eld according to Newtons second law. Even
in the presence of the electric eld, the electrons have a denite terminal
velocity, v
th
, but that their direction of travel is random and changes over
time due to the scattering collisions. If E = 0, the average velocity vector
of the electrons, i.e. their drift velocity, v
d
also zero.
Assume that a collision can occur at any time with equal probability, which
is reasonable if we assume that the metal is a homogeneous medium. In this
case, the probability that the electron will not scatter under a time period, t,
is given by exp(t/). This can be understood in the following way. Assume
that the probability of not undergoing a collision during a period of time
t
1
is P(t
1
), where P is some unspecied function. The probability of not
underging a collision during two consecutive periods of time t
1
and t
2
must,
from the law of the product of two independent probabilities, be given by
P(t
1
+t
2
) = P(t
1
)P(t
2
). The mathematical expression which satises this
requirement is the exponential function, P(t) = exp(t/). This function
gives the correct average time = 1 with t = 0 and decreases with increasing
t, as it should.
The simplest method to prove Ohms law is to start from a statistical equa-
tion of motion with the following form:
dv
d
dt
=
v
d

eE
m
(2)
We can motivate this equation in the following way. The right-hand side
consists of two terms. The rst of these represents the eect of relaxation,
and the second the eect of the electric eld. Next, assume that there are
no scattering collisions with the media, i.e., no relaxation or resistance. We
can achieve this by allowing to go to innity, . Eqn 2 then reduces
to:
dv
d
dt
=
eE
m
(3)
which means that all the electrons accelerate together under the inuence
of the electric eld, E. If we assume instead that at a given time, t = 0, the
electric eld is turned o, i.e., we set the eld E = 0, then eqn 2 reduces to:
dv
d
dt
=
v
d

(4)
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3.3 The Drude model - a classical model for a free electron gas 5
The solution to this equation is:
v
d
(t) = v
d
(0)e
t/
(5)
i.e., the drift velocity decreases exponentially with a relaxation time, . The
current doesnt stop instantaneously. Eqn. 5 is also in agreement with the
probability P(t) = exp(t/) that an electron has not scattered after a time
t.
The explanation as to why the current decreases is not that the electrons
go successively slower. In reality, the drift velocity v
d
is small compared to
the individual electrons thermal average veleocity, v
th
. The current, i.e., the
drift velocity vector v
d
decreases to zero because the conduction electrons
through their collisions with the media lose memory of their direction of
motion. Nevertheless, it is common though slightly incorrect, to occasionally
refer to the second term on the right-hand side of eqn. 2 as a friction term.
We can now prove Ohms law from eqn. 2. If we assume that we have static
equilibrium, i.e. dv
d
/dt = 0, we obtain:
v
d
=
eE
m
(6)
If we combine this expression with the known expression for electric current
density:
j = nev
d
(7)
we obtain the desired result:
j = E (8)
Ohms law, where the conductivity, , is given by:
=
ne
2

m
(9)
Because the eect on the abolute value of the velocity of the applied electric
eld is small, we can say that, on average, the electrons move with the ther-
mal velocity, v
th
, regardless of the electron eld strength, E. The average
distance the electrons travel betwen two scattering collisions is then:
= v
th
(10)
which is usually called the conduction electrons free average wavelength or
mean-free path. We should note that up until now have we assumed that
in every collision the electron scatters in a completely random direction.
In reality, the electron only scatters slighty in every collision (a glancing
collision). However, a succession of such collisions has the same total eect
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3.3 The Drude model - a classical model for a free electron gas 6
as our assumed model single collision. The correct term for is the average
electron transport length, as it describes the characteristic wavelength over
which an electron, due to repeated collisions, loses the memory of its initial
direction of motion.
From eqn 10, the relaxation time, and, therefore, the conductivity, is given
by /. Drude assumed that should be of the same order of magnitude as
the separation between the atoms in the media, while v
th
should approxi-
mate the average velocity of a classical particle with a given temeprature. In
reality, akthough the answer actually agrees quite well with empirical mea-
surements of conductivity, these assumption are wrong: is considerably
larger than the inter-atomic distance, typically 100 larger. Furthermore,
as we will see, the velocity v
th
should be replaced with the so called Fermi
velocity, v
F
, which is also typically 100 larger. However, this also claries
why Drudes classical model works so well: these two errors, each with a
factor of 100, cancel each other out.
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4. Conduction electrons in a metal: the free-electron gas 1
4. Conduction electrons in a
metal: the free-electron gas
1 From free atoms to solid state
2 From an electron gas to a free electron gas
3 The Drude model - a classical model for a free
electron gas
4 The Sommerfeld theory - a quantum model of a
free electron gas
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4.4 The Sommerfeld theory - a quantum model of a free electron gas 2
The Sommerfeld theory - a quantum mechanical
model of a free electron gas.
The Sommerfeld model is the simplest quantum mechanical theory for a
free electron gas. What dierentiates it from the Drude model can be sum-
marised quite briey: using the Schr odinger equation, a quantum mechani-
cal deascription of the electrons in the free electron gas is obtained, taking
into consideration the fact that an electron is a fermion, and must obey the
Pauli exclusion principle, i.e., two or more electrons cannot occupy the same
identical quantum state.
Assume that there are N electrons contained in a cube of length L and
volume V = L
3
. The number of electrons per unit volume is then n = N/V .
It is mathemtically convient to assume that the metal piece has the form
of a cube, but it does not invalidate or limit the validity of the result we
obtain.
As before, assume that by free electron we mean that every electron moves
unaected by external forces, i.e., in a constant potential V . For simplicity,
we can set V = 0. Furthertmore, we also ignore the electrostatic replusion
between the electrons, as well as the electrostatic interactions between the
conduction electrons and the non-conduction electrons and the atom nuclei.
Relaxtion will be introduced later, and will have the same meaning as earlier,
i.e., that occasionally every electron in the gas scatters into a new and
random direction.
In the assumptions we have made, because every electron in the gas moves
around as if the other electrons do not exist, we can calculate the possible
states using the Schr odinger equation for a single free electron, i.e.:

2
2m
(r) = E(r) (11)
The next step is to include the boundary conditions, i.e., the electrons are
conned in a cube of length L. This is usually achieved by considering the
solutions in the form of standing waves in the cube. However, instead we
will use the so-called periodic boundary conditions.
Motivation for the Periodic boundary conditions.
One well known solution to eqn 11 is the plane wave:

k
(r) =
1

V
e
ikr
(12)
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4.4 The Sommerfeld theory - a quantum model of a free electron gas 3
which is already correctly normalised, such the the volume intergral of |

k
| over the whole cube =1. Meanwhile, the plane wava also represents a
free particle with an exactly dened momentum, k, but with a completely
undened position. The last point means that unless we know more we
cannot accept eqn 12 as a solution because it means the electrons cannot be
conned in the cube of volume V .
Nevertheless, if we want to work with solutions of the form given in eqn 12
- as they do represent free particles - we must introduce an approximation.
We assume that the electron has an completely dened momentum, despite
being conned in the cube V , and due to Heisenbergs uncertainty principle
must have some uncertainty in its momentum.
When is this approximation valid? If we consider the electron as a wavepacket,
i.e. as a superposition of plane waves which have the form given by eqn 12,
with a spatial distribution d
v
. The uncertaintly principle tells us that:
( | k|) d
v
, (13)
where ( | k |) is the uncertainty in the electrons momentum. If d
v
L
we can ignore the eect on the electron from the surface of the cube. At
the same time, (k) k so the electron has a well-dened momentum and
can in a good approximation be described by a plane wave according to eqn
12. Another clear requirement that must be satised is L, where is
the electrons de Broglie wavelength, = 2/| k |. If this condition is not
fullled, e.g. if L, the cubes surfaces will have a measureable eect on
the electrons state, and in this case the solutions should be considered as
standing waves between these surfaces.
Providing we do not forget that we have ignored the inuence of the walls
on the wavefunction, we can work with solutions having the form given by
eqn. 12. The following now hold: the functions
k
(r) =
1

V
e
ikr
where:
k
x
= n
x
2
L
k
y
= n
y
2
L
(14)
k
z
= n
z
2
L
,
where n
x
, n
y
, n
z
= 0, 1, 2, 3 . . . dene an orthogonal, normalised, com-
plete basis set for other functions (x, y, z) dened in the cube, V . Any
other function (x, y, z) dened from x, y, z within the cube, V , can always
be written as a superposition of functions from 14. The superposition is, in
itself, a Fourier transform of with a period L in both x, y and z di-
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4.4 The Sommerfeld theory - a quantum model of a free electron gas 4
rections. The states given in 14 are orthogonal means that they are dierent
states with respect to the Pauli principle.
It is usual to state that the functions or (k
x
, k
y
, k
z
)-values in 14 are calculated
with periodic boundary conditions. This means that, for example, k
x
shall
be chosen so that the function exp(ik
x
x) is periodic with a period L so that:
exp(ik
x
(x + L)) = exp(ik
x
x) (15)
It is easy to show that this leads to 14. What this demonstrates is the
key idea to the periodic boundary conditions: they happen to generate a
complete set of plane-wave solutions to the Schr odinger equation which are
othogonal within the cube V .
The ground state of the free electron gas.
In kspace, a cartesian coordinate system with the axes (k
x
, k
y
, k
z
), we can
form k-vectors given in eqn. 14, i.e., those allowed according to the periodic
boundary conditions, forming a lattice of points. This is shown in Fig. 1.
Figure 1: The Fermi sphere
The number of points per unit volume in k-space is (L/2)
3
, i.e., if we
consider that every point in the lattice lies in the centre of its own little
cube of volume (2/L)
3
. Every point represents two electrons according
to the Pauli exclusion principle: one with spin up (/2) and one with spin
down (/2). The energy of this state is given by:
E =

2
2m
k
2
=

2
2m

k
2
x
+ k
2
y
+ k
2
z

(16)
In the ground state, i.e., where the total energy of the gas is as low as
possible, all of the N electrons will be found in the state with the lowest
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4.4 The Sommerfeld theory - a quantum model of a free electron gas 5
possible energy, i.e., as close to the origin (k = 0) as possible, taking into
consideration the exclusion principle which allows two electrons in each and
every point in the lattice. If N is extremely large (1), then the lled states
will form a spherical volume in kspace with its centre at the origin. This
is the Fermi sphere (Fig. 1). If the volume was not spherical, an electron at
the surface could move to a aite closer to the centre and, thus, be in a lower
energy state. The radius of this sphere is called the Fermi wave-vector, k
F
,
and the associated energy of an electron in a state which lies on the surface
of the Fermi sphere (the Fermi surface) is the Fermi energy, E
F
, and is
given by:
E
F
=

2
k
2
F
2m
(17)
A free electron gas is an example of a Fermi gas, i.e. a gas of fermions.
The Fermi wave-vector can be obtained by noting that the volume of the
Fermi sphere mupltipled by the the number of states per unit volume (in
k-space) must equal the number of electrons, N:
N =

4
3
k
3
F

L
2

(18)
and rearranging:
k
F
= (3n)
1/3
(19)
where n = N/V which, as earlier, is the number of electrons per unit volume
(in normal space). Thus:
E
F
=

2
2m

3
2
n

2/3
which states that the Fermi energy is larger of the electron gas is denser.
The so-calledd Fermi temperature is a ctional temperature dened as E
F
=
k
B
T
F
. Finally, we obtain the Fermi velocity of an electron on the surface of
the Fermi sphere:
v
F
=
k
F
m
=

m

2
2
n

1/3
In practice, the Fermi energy in metals is on the order 1-10 eV. This means
that the average kinetic energy of a conduction electron in a metal is con-
siderably larger than would be expected from classical theory.
Electrical conductivity.
How are free electrons inuenced by an electric eld, E?
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4.4 The Sommerfeld theory - a quantum model of a free electron gas 6
For an electron in an allowed state 12 the momentum is p = k. Assume
that we can use Newtons Second Law. Here, dp/dt = eE, so:

d
dt
k = eE (20)
In other words, an electron in a plane-wave state
k
(r) at a time t should
at a time t + dt nd itself in a plane-wave state

k
(r), where:
k

= k + dk = k

eE
h
dt

(21)
This is quantum mechanically exact even if we used a classical argument.
The eect of the electric eld, E, can be therefore seen as that all electrons
in the Fermi sphere at the same time move to a new state in accordance with
eqn. 20: naturally this is not against the exclusion principle. Furthermore,
the result is that the Fermi sphere translates in kspace with a velocity
dk/dt = eE/. The process is illustrated in Fig. 2.
Figure 2: The oset Fermi sphere
If we denote the wavenumber vector at the centre of the Fermi sphere as k
m
(Fig. 2), we can clearly describe the eect of the eld E with the equation:

d
dt
k
m
= eE (22)
As in the Drude model, the resistance depends on the fact that electrons
scatter against the vibrations and defects in the crystal structure. With
these scattering processes, the changes in the energy E of the electrons is
generally signicantly smaller than the Fermi energy, E
F
. Consequently,
these scattering processes can only take place for those electrons which are
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4.4 The Sommerfeld theory - a quantum model of a free electron gas 7
located on or close to the Fermi surface. It is noted that an electron which is
located deeper in the Fermi sphere must therefore absorb considerably more
energy to move to a free state, i.e., a state wich is either on or outside the
Fermi surface.
As earlier, is the mean free wavelength (more exactly, average electron
transport wavelength) between the scattering collisions. Becasue the scat-
tering processes only involve electrons in states close to the Fermi surface,
we take the relaxation time to be:
=

v
F
(23)
Compare this with eqn.10. An important point is that the Fermi velocity
v
F
is signicantly larger than the classical average thermal velocity v
th
.
In the so-called relaxation approximation, the eect of the scattering process
is descibed such that the Fermi sphere returns to its relaxed state (k
m
= 0)
according to the equation:
d
dt
k
m
=
1

k
b
(24)
(compare with eqn. 4). The combination of the eect of the electric eld
and the relaxation time is given by (compare eqn. 2):
d
dt
k
m
=
e

E
1

k
b
(25)
For a stationary state, i.e., constant current, the time derivative is zero and:
k
m
=
e

E (26)
We can now calculate the electric current density, j, from eqn. 26. As the
average value of the electrons wave vector is just k
m
, we determine that the
aveage value of the group velocity, i.e. the drift velocity
d
is:
v
d
=
k
m
m
(27)
Using eqns 27 and 26 we can see that the electrical current density is:
j = nev
d
=
ne
2

m
E = E (28)
And we obtain the following formula for the conductivity:
=
ne
2

m
E =
ne
2

mv
F
E (29)
which is very similar to that given by the Drude model eqn 9.
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4.4 The Sommerfeld theory - a quantum model of a free electron gas 8
Matthiessens Rule.
As we noted earlier, the relaxation is mostly dependent on two processes:
scattering against the vibrations in the crystal structure and scattering
against dierent kinds of defects in the crystal structure. These two pro-
cesses can be seen as approximately independent.
Denote the average electron transport wavelength for the rst of these pro-
cesses is
g
and that for the second is
d
. As the vibrations arise from
the crystal structures thermal motion, it is reasonable to assume that the
scattering increases with increasing temperature, i.e.,
g
decreases. In the
second process,
d
, must depend to a large extent on the density of defects
in the crystal and to a rst approximation is independent of the temperature
(true for the most part). These approximations form Matthiessens Rule.
Figure 3: Resitivity vs temperature
We can then associate a relaxation time,
g
=
g
/v
F
, for scattering against
vibrations and second relaxation time,
d
=
d
/v
F
, for scattering o defects.
If the processes are independent, the total resistivity should be the sum of
the resistivities (the inverse of the conductivities) related to these processes,
i.e.:
=
g
+
d
=
m
ne
2

g
+
m
ne
2

d
=
m
ne
2

g
+
1

(30)
If we compare this with the formula for conductivity eqn 29, we see that the
total relaxation time is given by:
1

=
1

g
+
1

d
(31)
A schematic picture of a typical temperature dependence of the resistivity
of a metal is given in Fig. 3. At low temperatures, the contribution from
scattering from the defects dominates. At higher temperatures, the contri-
bution from scattering o the vibrations in the structure dominates - the
resistivity tends to be proportional to the temperature.
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