Free Electron Fermi Gas

(Kittel Ch. 6)
 Role of Electrons in Solids
• Electrons are responsible for binding of crystals --
they are the “glue” that hold the nuclei together
Types of binding (see next slide)
Van der Waals - electronic polarizability
Ionic - electron transfer
Covalent - electron bonds

• Electrons are responsible for important properties:

Electrical conductivity in metals
(But why are some solids insulators?)
Magnetism
Optical properties
....
Characteristic types of binding

Closed-Shell Binding Ionic Binding

Van der Waals

Covalent Binding Metallic Binding

 Starting Point for Understanding
Electrons in Solids
• Nature of a metal:
Electrons can become
“free of the nuclei” and
move between nuclei
since we observe
electrical conductivity
• Electron Gas
Simplest possible model
for a metal - electrons are
completely “free of the
nuclei” - nuclei are replaced
by a smooth background --
“Electrons in a box”
 Electron Gas - History
• Electron Gas model predates quantum mechanics

• Electrons Discovered in 1897

• Drude-Lorentz Model (1905)-

Electrons - classical particles
free to move in a box
• Model: All electrons
contribute to conductivity.
Works! Still used!

• But same model predicted

that all electrons contribute
to heat capacity. Disaster.
Heat capacity is MUCH less
than predicted.
 Quantum Mechanics
• 1911: Bohr Model for H
• 1923: Wave Nature of Particles Proposed
Prince Louis de Broglie
• 1924-26: Development of Quantum
Mechanics - Schrodinger equation
• 1924: Bose-Einstein Statistics for
Identical Particles (phonons, ...)
• 1925-26: Pauli Exclusion Principle,
Fermi-Dirac Statistics (electrons, ...)
• 1925: Spin of the Electron (spin = 1/2) Schrodinger
G. E. Uhlenbeck and S. Goudsmit
 Schrodinger Equation
• Basic equation of Quantum Mechanics

[ - ( h/2m ) ∆2 + V( r ) ] Ψ ( r ) = E Ψ ( r )

where
m = mass of particle
V( r ) = potential energy at point r
∆2 = (d2/dx2 + d2/dy2 + d2/dz2)
E = eigenvalue = energy of quantum state
Ψ ( r ) = wavefunction
n ( r ) = | Ψ ( r ) |2 = probability density
 Schrodinger Equation – 1D line
• Suppose particles can move freely on a line with
position x, 0 < x < L
0 L
• Schrodinger Eq. In 1D with V = 0
- ( h2/2m ) d2/dx2 Ψ (x) = E Ψ (x)
Boundary Condition
• Solution with Ψ (x) = 0 at x = 0,L
Ψ (x) = 21/2 L-1/2 sin(kx) , k = n π/L, n = 1,2, ...
(Note similarity to vibration waves)

Factor chosen so ∫0L dx | Ψ (x) |2 =1

• E (k) = ( h2/2m ) k 2
 Electrons on a line
• Solution with Ψ (x) = 0 at x = 0,L

Examples of waves - same picture as for lattice

vibrations except that here Ψ (x) is a continuous wave
instead of representing atom displacements

0 L
 Electrons on a line
• For electrons in a box, the energy is just the kinetic
energy which is quantized because the waves must fit
into the box

E (k) = ( h2/2m ) k 2 , k = n π/L, n = 1,2, ...

Approaches
continuum
as L becomes large
k
 Schrodinger Equation – 1D line
• E (k) = ( h2/2m ) k 2 , k = n π/L, n = 1,2, ...

• Lowest energy solutions with Ψ (x) = 0 at x = 0,L

Ψ (x)

x
 Electrons in 3 dimensions
-(h2/2m ) [d2/dx2 + d2/dy2 + d2/dz2 ] Ψ (x,y,z) = E Ψ (x,y,z)

Ψ (x) = 0 at x = 0,L; Ψ (y) = 0 at y = 0,L ; Ψ (z) = 0 at z

= 0,L
Ψ = 23/2 L-3/2 sin(kxx) sin(kyy) sin(kzz) ,
kx = n π/L, n = 1,2, …, same for y,z

E (k) = ( h2/2m ) (kx2 + ky2 + kz2 ) = ( h2/2m ) k2

E
Approaches
continuum
as L becomes large
k
Electrons in 3 dimensions - continued
• Just as for phonons it is convenient to define Ψ with
periodic boundary conditions
• Ψ is a traveling plane wave:
Ψ = L-3/2 exp( i(kxx + kyy + kzz) ,
kx = ± n (2π/L), etc., n = 0,1,2,..

E (k) = ( h2/2m ) (kx2 + ky2 + kz2 ) = ( h2/2m ) k2

Approaches
continuum
as L becomes large
k
 Density of states
• Key point - exactly the same as for vibration waves
• We need the number of states per unit energy to find
the total energy and the thermal properties of the
electron gas.
• Difference: density of states is defined in terms of
energy E, not angular frequency.
• D(E)dE - number of states in energy range E to E+dE
• States in interval (k, E) to (k+ ∆k, E+ ∆E)
∆N= N(k) ∆k=N(E) ∆E
dN/dE=(dN/dk)/(dE/dk)
 Density of States in 3D
• The values of kx ky kz are equally spaced: ∆kx = 2π/L ,.
Thus the volume in k space per state is (2π/L)3
and the number of states N with |k| < k0 is
N = (4π/3) k03 / (2π/L)3 = V/6π2 k03 L3=V
• The density of states per unit energy is
D(E) = dN/dE = (dN/dk) (dk/dE)

E = ( h2/2m ) k2 , dE/dk = ( h2/m ) k

⇒ D(E) = (V/2π2) k2 / (h2/m ) k = (V/2π2) k / (h2/m )
= (V/4π2) E1/2 (2m / h2)3/2
Kittel adds a factor of 2 for multiplicity of electrons in the
same state (spin): D(E) = (V/2π2) E1/2 (2m / h2)3/2
 Electron orbitals
• In 1D E (k) = ( h2/2m ) k 2 , k = n π/L, n = 1,2, …
• In 3D E (k) = ( h2/2m ) (kx2 + ky2 + kz2 ) = ( h2/2m ) k2
kx, ky kz = ± n (2π/L), etc., n = 0,1,2,..
• Thus E1D (k) = n2 ( h2/2m ) (π /L)2
• E3D (k) = (nx+ny+nz)2 ( h2/2m ) (2π /L)2
• To describe a system of Nelec electrons, we assign
the electrons to orbitals of increasing energy, until all
orbitals are filled.
• Order of filling: n=1, 2, .. nF
• nF - topmost filled energy level (Fermi level)
 Electron orbitals
• D(E)= (V/2π2) E1/2 (2m / h2)3/2

D(E) EF
Empty
Filled

• Now we need to figure out how many electrons are on

a given orbital (electron occupancy)
 What is special about electrons?
• Fermions - obey exclusion principle
• Fermions have spin s = 1/2 - two electrons (spin up and
spin down) can occupy each state
• Kinetic energy = ( p2/2m ) = ( h2/2m ) k2
• Thus if we know the number of electrons per unit
volume Nelec/V,
the lowest energy allowed state is for the lowest Nelec/2
states to be filled with 2 electrons each,
and all the (infinite) number of other states to be empty.
• The number of states with |k| < k0 is N = (V/6π2) k03
(from before)
 Fermi momentum and energy
Thus all states are filled up to the Fermi momentum
kF and Fermi energy EF = ( h2/2m ) kF2, given by
Nelec/2 = (V/6π2) kF3
⇒
kF = (3π2 Nelec/V )1/3 and EF = (h2/2m) (3π2 Nelec/V )2/3

Reciprocal space

Filled states Possible k values

Fermi surface in 2D
 Fermi Distribution
• At finite temperature, electrons are not all in the lowest energy
states
• Applying the fundamental law of statistics to this case (occupation
of any state and spin only can be 0 or 1) leads to the Fermi
Distribution giving the probability that an orbital of energy E is
occupied (Kittel appendix)
f(E) = 1/[exp((E-µ)/kBT) + 1]
µ Chemical potential
for electrons =
f(E) Fermi energy at T=0
1
D(E)
1/2 µ is temperature
kBT dependent

E
Ex. How does the Fermi distribution
f(E) = 1/[exp((E-µ)/kBT) + 1]

compare with the Planck distribution for phonons?

n(E) = 1 / [ exp ( E / kB T) - 1 ]

Sketch them as a function of energy for different

temperatures.
 Typical values for electrons?
• Here we count only valence electrons (see Kittel table)

• Element Nelec/atom EF TF = EF/kB

Li 1 4.7 eV 5.5 x104 K

Na 1 3.23eV 3.75 x104 K

Al 3 11.6 eV 13.5 x104 K

• For typical metals the Fermi energy temperature is

much greater than ordinary temperatures – transition
from f(E)=1 to f(E)=0 is sharp at room temperature
 Heat Capacity for Electrons
Just as for phonons the definition of heat capacity is C = dU/dT
where U = total internal energy

• When heated from T=0 only electrons within an energy range

kBT of the Fermi energy can be excited thermally
• For T << TF = EF /kB roughly U ~ U0 + Nelec (T/ TF) kB T so that

C = dU/dT ~ Nelec kB (T/ TF)

Chemical
µ potential
f(E) for electrons
1 D(E)
kBT
1/2

E
 Heat Capacity for Electrons
• More precisely, the change in energy when heated
from 0 to T is
∆U = ∫ dE E D(E) f(E) - ∫
∞ EF
0 0 dE E D(E)

• Using the fact that T << TF:

C = dU/dT = ∫0 dE (E - EF) D(E) (df(E)/dT)
∞

≈ D(EF) ∫0 dE (E - EF) (df(E)/dT)

∞

• The integral can be done almost exactly (exact in the

low T limit) to give
C = (π2/3) D(EF) kB2 T (valid for any metal)
→ (π2/2) (Nelec/EF) kB2 T (for the electron gas)
(using D(EF) = 3 Nelec/2EF )
• Key result: C ~ T - agrees with experiment!
 Heat capacity
• Comparison of electrons in a metal with phonons
Phonons approach
Heat Capacity C classical limit
C ~ 3 Natom kB

T3 T
Electrons have
C ~ Nelec kB (T/TF)

T
Phonons dominate
Electrons dominate at high T because of
at low T in a metal reduction factor (T/TF)
 Heat capacity
• Experimental results for metals
C/T = γ + A T2 + ….
• Find the ratio γ / γfree, γfree = (π2/2) (Nelec/EF) kB2 is the
free electron gas result. Equivalently since EF ∝1/m,
we can consider the ratio γ / γfree = mfree/mth*, where
mth* is an thermal effective mass for electrons in the
metal
Metal mth*/ mfree
Li 2.18
Na 1.26
K 1.25
Al 1.48
Cu 1.38
• mth* close to m(free) is the “good”, “simple metals” !
Electrical Conductivity & Ohm’s Law
• Consider electrons in an external field E. They
experience a force F = -eE
• Now F = dp/dt = h dk/dt , since p = h k
• Thus in the presence of an electric field all the
electrons accelerate and the k points shift, i.e., the
entire Fermi surface shifts E

Equilibrium - no field With applied field

Electrical Conductivity & Ohm’s Law
• What limits the acceleration of the electrons?
• Scattering increases as the electrons deviate more
from equilibrium
• After field is applied a new equilibrium results as a
balance of acceleration by field and scattering
E

Equilibrium - no field With applied field

 Electrical Conductivity and Resistivity
• The conductivity σ is defined by j = σ E,
where j = current density
• How to find σ?
• From before F = dp/dt = m dv/dt = h dk/dt
• Equilibrium is established when the rate that k
increases due to E equals the rate of decrease due to
scattering, then dk/dt = 0
• If we define a scattering time τ and scattering rate1/τ
h ( dk/dt + k /τ ) = F= q E (q = charge)
• Now j = n q v (where n = density) so that
j = n q (h k/m) = (n q2/m) τ E
⇒ σ = (n q2/m) τ Note: sign of charge
does not matter
• Resistance: ρ = 1/ σ ∝ m/(n q2 τ)
 Scattering mechanisms
• Impurities - wrong atoms, missing atoms, extra atoms,
….

Proportional to concentration

• Lattice vibrations - atoms out of their ideal places

Proportional to mean square displacement

• (Really these conclusions depend upon ideas from the

next section that there is no scattering in a perfect
crystal.)
 Electrical Resistivity
• Resistivity ρ is due to scattering: Scattering rate
inversely proportional to scattering time τ

ρ ∝ scattering rate ∝ 1/τ

• Matthiesson’s rule - scattering rates add

ρ = ρvibration + ρimpurity ∝ 1/τvibration + 1/τimpurity

Temperature dependent Temperature independent

∝ <u2> - sample dependent
 Electrical Resistivity
• Consider relative resistance R(T)/R(T=300K)
• Typical behavior (here for samples of potassium)
Relative resistance

Phonons dominate at
0.05 high T because mean square
displacements <u2> ∝ T
Leads to R ∝ T
(Sample independent)
Increase as T2
0.01
T
Inpurity scattering dominates
at low T in a metal
(Sample dependent)
 Interpretation of Ohm’s law
Electrons act like a gas
• A electron is a particle - like a molecule.
• Electrons come to equilibrium by scattering like
molecules (electron scattering is due to defects,
phonons, and electron-electron scattering).
• Electrical conductivity occurs because the electrons
are charged, and it shows the electrons move and
equilibrate
• What is different from usual molecules?
Electrons obey the exclusion principle. This limits the
allowed scattering which means that electrons act like
a weakly interacting gas.
 Hall Effect I
• Electrons moving in an electric and a perpendicular
magnetic field
• Now we must carefully specify the vector force
F = q( E + (1/c) v x B ) (note: c → 1 for SI units)
(q = -e for electrons)

B Vector directions
shown for positive q
FE
v
FB

E
 Hall Effect II
• Relevant situation: current j = σ E = nqv flowing along
a long sample due to the field E
• But NO current flowing in the perpendicular direction
• This means there must be a Hall field EHall in the
perpendicular direction so the net force F⊥ = 0
F⊥ = q( EHall + (1/c) v x B ) = 0
B

v j
F⊥
z
j y
EHall E x
 Hall Effect III
• Since
F⊥ = q( EHall + (1/c) v x B ) = 0 and v = j/nq

then defining v = (v)x, EHall = (EHall )y, B = (B )z,

EHall = - (1/c) (j/nq) (- B ) Sign from cross product

and the Hall coefficient is

RHall = EHall / j B = 1/(nqc) or RHall = 1/(nq) in SI
B

F⊥ v j

EHall E
 Hall Effect IV
• Finally, define the Hall resistance as
Each of these quantities can
ρHall = RHall B = EHall / j be measured directly

which has the same units as ordinary resistivity

• RHall = EHall / j B = 1/(nq)
• Note: RHall determines sign of charge q

Since magnitude of charge is known RHall also

determines density n

• The sign of charge in several metals (Mg, Al) is

positive
Electrons act like gas - heat transport
• A electron is a particle that carries energy - just like a
molecule.
• Electrical conductivity shows the electrons move,
scatter, and equilibrate
• What is different from usual molecules?
Electrons obey the exclusion principle. This limits
scattering and helps them act like weakly interacting
gas.

hot cold

Heat Flow
 Heat Transport due to Electrons
• Definition (just as for phonons):
jthermal = heat flow (energy per unit area per unit time )
= - K dT/dx
• If an electron moves from a region with local
temperature T to one with local temperature T - ∆T, it
supplies excess energy c ∆T, where c = heat capacity
per electron. (Note ∆T can be positive or negative).
• On average :
∆T = (dT/dx) vx τ, where τ = mean time between
collisions
• Then jthermal = - n vx c vx τ dT/dx = - n c vx2 τ dT/dx

Flux
Density
 Electron Heat Transport - continued
• Just as for phonons:
Averaging over directions gives ( vx2 ) average = (1/3) v2
and
j = - (1/3) n c v2 τ dT/dx

• Finally we can define the mean free path L = v τ

and C = nc = total heat capacity,
Then
j = - (1/3) C v L dT/dx
and
K = (1/3) C v L = (1/3) C v2 τ = thermal conductivity

(just like an ordinary gas!)

 Electron Heat Transport - continued
• What is the appropriate v?
• The velocity at the Fermi surface = vF
• What is the appropriate τ ?
• Same as for conductivity (almost).

• Results using our previous expressions for C:

K = (π2/3) (n/m) τ kB2 T

• Relation of K and σ -- From our expressions:
K / σ = (π2/3) (kB/e)2 T

• This justifies the Weidemann-Franz Law that

K/σ ∝T
Electron Heat Transport - continued
• K∝σT
• Recall σ → constant as T → 0, σ → 1/T as T → large
50 Low T -- K
Thermal conductivity K

increases as heat
capacity increases
(v and L are ~ constant)
W/cm K

Approaches
high T limit
- K constant
0
0 100 T
Electron Heat Transport - continued
• Comparison to Phonons

Electrons dominate in good metal crystals

Comparable in poor metals like alloys

Phonons dominate in non-metals

 Summary
• Electrical Conductivity - Ohm’s Law
σ = (n q2/m) τ ρ = 1/σ
• Hall Effect
ρHall = RHall B = EHall / j
ρ and ρHall determine n and the charge of the carriers
• Thermal Conductivity
K = (π2/3) (n/m) τ kB2 T
Weidemann-Franz Law:
K / σ = (π2/3) (kB/e)2 T
• Metallic Binding
Kinetic repulsion
Coulomb attraction to nuclei
(not included in gas model - must be added)