Lecture 12 - The Electron Gas

Outline
Part II - Electronic Properties of Solids • Overview - role of electrons in solids
Lecture 12: The Electron Gas
(Kittel Ch. 6) • The starting point for understanding electrons in
solids is completely different from that for
understanding the nuclei ( But we will be able to
use many of the same concepts! )
• Simplest model - Electron Gas
Failure of classical mechanics
Success of quantum mechanics
Pauli Exclusion Principle, Fermi Statistics
Energy levels in 1 and 3 dimensions
• Similarities, differences from vibration waves
• Density of States, Heat Capacity
• (Read Kittel Ch 6)
Physics 460 F 2006 Lect 12 1 Physics 460 F 2006 Lect 12 2

Role of Electrons in Solids Characteristic types of binding

• 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
Closed-Shell Binding Ionic Binding
Metallic - more about this soon Van der Waals

• Electrons are responsible for important properties:

Electrical conductivity in metals
(But why are some solids insulators?)
Magnetism
Optical properties
....
Covalent Binding Metallic Binding
Physics 460 F 2006 Lect 12 3 Physics 460 F 2006 Lect 12 4

Starting Point for Understanding Electron Gas - History

Electrons in Solids
• Nature of a metal: • Electron Gas model predates quantum mechanics
Electrons can become
“free of the nuclei” and • Electrons Discovered in 1897
move between nuclei - J. J. Thomson
since we observe
electrical conductivity
• Electron Gas • Drude-Lorentz Model -
Simplest possible model Electrons - classical particles
for a metal - electrons are free to move in a box
completely “free of the
nuclei” - nuclei are replaced
by a smooth background --
“Electrons in a box”
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 Lecture 12 - The Electron Gas

Drude-Lorentz Model (1900-1905) Quantum Mechanics

• 1911: Bohr Model for H
• Electrons as classical particles moving in a box • 1923: Wave Nature of Particles Proposed
Prince Louie de Broglie
• Model: All electrons • 1924-26: Development of Quantum
contribute to conductivty. Mechanics - Schrodinger equation
Works! Still used! • 1924: Bose-Einstein Statistics for
Identical Particles (phonons, ...)
• But same model predicted • 1925-26: Pauli Exclusion Principle,
that all electrons contribute Fermi-Dirac Statistics (electrons, ...)
to heat capacity. Disaster. Paul Drude
Heat capacity is MUCH less • 1925: Spin of the Electron (spin = 1/2) Schrodinger
than predicted. G. E. Uhlenbeck and S. Goudsmit

Physics 460 F 2006 Lect 12 7 Physics 460 F 2006 Lect 12 8

Schrodinger Equation Schrodinger Equation - 1d line

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

∆
• E (k) = ( h2/2m ) k 2
Physics 460 F 2006 Lect 12 9 Physics 460 F 2006 Lect 12 10

Electrons on a line Electrons on a line

• Solution with Ψ (x) = 0 at x = 0,L • For electrons in a box, the energy is just the kinetic
energy which is quantized because the waves must fit
Examples of waves - same picture as for lattice into the box
vibrations except that here Ψ (x) is a continuous wave
instead of representing atom displacements E (k) = ( h2/2m ) k 2 , k = m π/L, m = 1,2, ...

E
Ψ

Approaches
continuum
0 L as L becomes large
k
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 Lecture 12 - The Electron Gas

Schrodinger Equation - 1d line Electrons in 3 dimensions

• E (k) = ( h2/2m ) k 2 , k = m π/L, m = 1,2, ... • Schrodinger Eq. In 3d with V = 0
-(h2/2m ) [d2/dx2 + d2/dy2 + d2/dz2 ] Ψ (x,y,z) = E Ψ
• Lowest energy solutions with Ψ (x) = 0 at x = 0,L (x,y,z)
• Solution
Ψ = 23/2 L-3/2 sin(kxx) sin(kyy) sin(kzz) ,
kx = m π/L, m = 1,2, …, same for y,z
E (k) = ( h2/2m ) (kx2 + ky2 + kz2 ) = ( h2/2m ) k2
E
Ψ (x)

Approaches
continuum
as L becomes large
x k
Physics 460 F 2006 Lect 12 13 Physics 460 F 2006 Lect 12 14

Electrons in 3 dimensions Density of States 3 dimensions

• Just as for phonons it is convenient to define Ψ with • Key point - exactly the same as for vibration waves -
periodic boundary conditions the values of kx ky kz are equally spaced - ∆kx = 2π/L ,
• Ψ is a traveling plane wave: etc.
Ψ = L-3/2 exp( i(kxx + kyy + kzz) , • Thus the volume in k space per state is (2π/L)3
kx = ± m (2π/L), etc., m = 0,1,2,.. and the number of states N per unit volume V = L3,
E (k) = ( h2/2m ) (kx2 + ky2 + kz2 ) = ( h2/2m ) k2 with |k| < k0 is
E N = (4π/3) k03 / (2π/L)3 ⇒ N/V = (1/6π2) k03
• ⇒ density of states per unit energy per unit volume is
D(E) = d(N/V)/dE = (d(N/V)/dk) (dk/dE)
Approaches Using E = ( h2/2m ) k2 , dE/dk = ( h2/m ) k
continuum ⇒ D(E) = (1/2π2) k2 / (h2/m ) k = (1/2π2) k / (h2/m )
as L becomes large = (1/2π2) E1/2 (2m / h2)3/2
k • (NOTE - Kittel gives formulas that already contain a
Physics 460 F 2006 Lect 12 15 Physics 460 F 2006 Lect 12 16
factor of 2 for spin)

Density of States 3 dimensions What is special about electrons?

• Fermions - obey exclusion principle
• D(E) = (1/2π2) E1/2 (2m / h2)3/2 ~ E1/2 • Fermions have spin s = 1/2 - two electrons (spin up
and spin down) can occupy each state
• Kinetic energy = ( p2/2m ) = ( h2/2m ) k2
D(E) EF • Thus if we know the number of electrons per unit
Empty volume Nelec/V, the lowest energy allowed state is for
Filled the lowest Nelec/2 states to be filled with 2 electrons
each, and all the (infinite) number of other states to be
empty.
• Thus all states are filled up to the Fermi momentum kF
and Fermi energy EF = ( h2/2m ) kF2 given by
E
Nelec/2V = (1/6π2) kF3 or Nelec/V = (1/3π2) kF3
⇒
kF = (3π2 Nelec/V )1/3 and EF = (h2/2m) (3π2 Nelec/V )2/3
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 Lecture 12 - The Electron Gas

Fermi Distribution Typical values for electrons?

• At finite temperature, electrons are not all in the lowest
energy states • Here we count only valence electrons (see Kittel table)
• Applying the fundamental law of statistics to this case
(occcupation of any state and spin only can be 0 or 1) • Element Nelec/atom EF TF = EF/kB
leads to the Fermi Distribution (Kittel appendix)
f(E) = 1/[exp((E-µ)/kBT) + 1] Li 1 4.7 eV 5.5 x104 K
µ Chemical potential
Na 1 3.23eV 3.75 x104 K
for electrons =
f(E) Fermi energy at T=0
1 Al 3 11.6 eV 13.5 x104 K
D(E)
1/2 kBT • Conclusion: For typical metals the Fermi energy (or
the Fermi temperature) is much greater than ordinary
E temperatures
Physics 460 F 2006 Lect 12 19 Physics 460 F 2006 Lect 12 20

Heat Capacity for Electrons Heat Capacity for Electrons

• Just as for phonons the definition of heat capacity is • Quantitative evaluation:
U = ∫0 dE E D(E) f(E) - ∫0 F dE E D(E)
C = dU/dT where U = total internal energy ∞ E

• For T << TF = EF /kB it is easy to see that roughly

U ~ U0 + Nelec (T/ TF) kB T so that • Using the fact that T << TF:
C = dU/dT = ∫0 dE (E - EF) D(E) (df(E)/dT)
∞
C = dU/dT ~ Nelec kB (T/ TF)
≈ D(EF) ∫0 dE (E - EF) (df(E)/dT)
∞
Chemical potential
µ for electrons
f(E)
1 D(E) • Finally, using transformations discussed in Kittel, the
integral can be done almost exactly for T << TF
→ C = (π2/3) D(EF) kB2 T (valid for any metal)
1/2 → (π2/2) (Nelec/EF) kB2 T (for the electron gas)
D(EF) = 3 Nelec/2EF for gas
E • Key result: C ~ T - agrees with experiment!
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Heat capacity Heat capacity

• Experimental results for metals
• Comparison of electrons in a metal with phonons C/T = γ + A T2 + ….
Phonons approach • It is most informative to find the ratio γ / γ(free)
classical limit
where γ(free) = (π2/2) (Nelec/EF) kB2 is the free electron
Heat Capacity C

C ~ 3 Natom kB
gas result. Equivalently since EF ∝1/m, we can
consider the ratio γ / γ(free) = m(free)/mth*, where mth*
is an thermal effective mass for electrons in the metal
T3 T Metal mth*/ m(free)
Electrons have Li 2.18
C ~ Nelec kB (T/TF)
Na 1.26
T K 1.25
Phonons dominate Al 1.48
Electrons dominate at high T because of
at low T in a metal reduction factor (T/TF)
Cu 1.38
• mth* close to m(free) is the “good”, “simple metals” !
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 Lecture 12 - The Electron Gas

Outline Next time

• Overview - role of electrons in solids
Determine binding of the solid • Continue free electron gas (Fermi gas)
“Electronic” properties (conductivity, … )
• The starting point for understanding electrons in • Electrical Conductivity
solids is completely different from that for
understanding the nuclei ( But we will be able to • Hall Effect
use many of the same concepts! )
• Simplest model - Electron Gas
Failure of classical mechanics • Thermal Conductivity
Success of quantum mechanics
Pauli Exclusion Principle, Fermi Statistics • (Read Kittel Ch 6)
Energy levels in 1 and 3 dimensions
• Similarities, differences from vibration waves
• Remember: EXAM Wednesday, October 11
• Density of States, Heat Capacity
• (Read Kittel Ch 6)
Physics 460 F 2006 Lect 12 25 Physics 460 F 2006 Lect 12 26

Comments on Exam
• Wed. October 11

• Closed Book
You will be given constants, etc.

• Three types of problems:

• Short answer questions

• Order of Magnitudes
• Essay questions
• Quantitative problems – not difficult

Physics 460 F 2006 Lect 12 27