Solid State Physics

Solid State Physics
Dr. Hong-Yi Chen

2017/5/26
National Taiwan Normal University

Department of Physics
88 TING-CHOU RD. SEC. 4, TAIPEI 116, TAIWAN
11
Basic Notion
1. Lattices
1-1 Crystal Structures
1-2 Reciprocal lattice
1-3 X-Ray Diffraction
1-4 Brillouin Zone
2. Bloch Theory
2-1 Bloch Theorem
2-2 Bloch Wave Function
2-3 Supercells
3. Phonons
3-1 Lattice Vibrations
3-2 Quantum Mechanics of Atomic Vibrations
3-3 Phonons
Summary Periodicity, Quasiparticles
Metal
4. Statistical Thermodynamics
4-1 Review of Statistics
4-2 Phonon Density of States
4-3 Lattice Specific Heat
4-4 Lattice Thermal Conductivity
5. Free Particle Theory
5-1 Drude Theory
5-2 Sommerfeld Theory
5-3 Electron Density of States
5-4 Electronic Specific Heat
5-5 Compressibility and Susceptibility
6. Classical Transport
6-1 Lorentz Theory
6-2 Boltzmann Equation
6-3 Transport Coefficient
6-4 Impurity Scattering
6-5 Phonon Scattering
7. Band Theory
7-1 Tight-Binding Method
7-2 Wannier Wave Function
7-3 Electronic Band Structure
7-4 Nearly Free Electron Model
12
7-5 Metal & Insulator
8. Fermi Liquid Theory
8-1 Jellium Model
8-2 Hatree-Fock Approximation
8-3 Random Phase Approximation
8-4 Landau Quasiparticles
8-5 Landau Fermi Liquid Theory
8-6 First-Principles Calculations
8-7 Stability of Fermi Liquid
Summary Basic Equations
Appendix Math background
13
Preface & Bibliography
Graduate Level
1. Prerequisite Knowledge: Quantum Mechanics, Statistical Mechanics
2. N. W. Ashcroft & N. D. Mermin, Solid State Physics (Saunders College).
3. Yuri Galperin, Introduction to Modern Solid State Physics (CreateSpace

Independent Publishing Platform).
4. J. M. Ziman, Principles of the Theory of Solids (Cambridge University Press).
5. Theoretical Physics Reference

http://www.theoretical-physics.net/dev/index.html
Undergraduate Level
1. Prerequisite Knowledge: Quantum Mechanics
2. Charles Kittle, Introduction to Solid State Physics (John Wiley & Sons).
3. Steven H. Simon, The Oxford Solid State Basics (Oxford University Press).
14
1-1 Lattice Structures
Tuesday, December 20, 2011 8:22 PM
A. CRYSTALLINE STRUCTURE
(1) A crystal is made up by repetition of one or more atoms (basis or building block).
(2) These basis are commonly referred to as points within a crystal lattice site.
OS:
These points don't tell you the position of an atom in a crystal. They are simply points 'in space'
oriented in such a way to build a crystal lattice.
(3) Any lattice point obtained from another point as with is

called periodic lattice.
OS:
For an arbitrary lattice point , there is an infinite array of points such that the lattice
appears exactly the same regardless of which point the arrangement is viewed from.
The collection of all vectors constitutes a set of discrete points is called Bravais [bravei] lattice (1850).
B. CONSTRUCT LATTICE
(1) The Bravais lattice can be made up by periodically repeating unit cells.
15
(2) Unit cell:
A unit cell has number of lattice points per unit cell . When , the unit cell is called
primitive unit cell.
OS:
A cell is translated by a SUBSET of vectors of the Bravais lattice.
A primitive unit cell is translated by ALL the vectors of the Bravais lattice.
The physical dimension of a unit cell is called lattice constant or lattice parameter referred to as , ,
and .
The volume of a unit cell is .
EXAMPLES:
1. Linear chain of identical atoms
Lattice constant
2. Linear chain with two kinds of atoms
Lattice constant
3. Antiferromagnetic chain
Nonmagnetic lattice constant:

Magnetic lattice constant:
4. Graphene:
16
Honeycomb lattice = Hexagonal lattice + 2-point basis
Lattice constant:
(3) Wigner-Seitz cell (1934)

A smallest possible primitive unit cell, which consist of one lattice point and all the surrounding space
closer to it than to any other point.
CONSTRUCTION:
1. One chooses any lattice point and draws connecting lines to its closest neighbors.
2. One constructs the perpendicular bisectors of the connecting lines.
3. The enclosed area is the Wigner-Seitz cell.
EXAMPLES:
Two-dimensional antiferromagnetic lattice
Lattice constant:
C. DISCRETE SYMMETRIES OF A UNIT CELL
(1) Discrete translation
17
Crystalline structure means spatial periodicity or discrete translational symmetry.
(2) Point group: inversion, rotation, and reflection
(3) The number of Bravais lattices is limited by symmetry of the unit cell
1. 2D lattice
2. 3D lattice (classified in 7 categories)
18
19
1-2 Reciprocal Lattice
201651 08:30
A. FOURIER SERIES OF BRAVAIS LATTICE PERIODIC FUNCTION
(1) Any function that is periodic in the lattice can be expanded in a Fourier series of the reciprocal
lattice vector .
PROOF:
1. Given a function defined in the volume , the Fourier transform and its inverse Fourier
transform over the finite system are
where is continuous in general.

2. Apply the periodic boundary conditions (Born-von Karman boundary conditions):
where
is discrtized
OS:
The distance between neighboring points in the discrete -space is inversely proportional to
the systems length along any direction. When is taken to innity and preserve the mass
density of the specic solid in question (thermodynamic limit), the values tend to a
continuum.
The inverse Fourier transform becomes a Fourier series and is the Fourier coefficient.
3. Assume is periodic with period :

where and
where is the volume of a unit cell.
1 10
The equation above gives zero unless
is periodic in -space
4. The discrete set of that satify can define a periodic array which is referred to as
the reciprocal lattice.
Introduce 3 new basis vectors (reciprocal vectors) such that forms the basis of the
reciprocal lattice and is defined by
An arbitrary point on the lattice is given by

which satisfy
is independent of the size of the finite system.

5. The inverse Fourier transform becomes
where Brillouin zone is a unit cell in the reciprocal lattice. The reciprocal lattice can be made up by
periodically repeating Brillouin zones.
6. Proof is preodic
(2) An infinite system with periodic translational symmetry can be approximated by a finite number of
lattice points with periodic boundary conditions.
B. RECIPROCAL LATTICE
1 11
B. RECIPROCAL LATTICE
(1) One way to satisfy is to construct such that they obey
is the volume of the unit cell.

The reciprocal lattice is a Bravais lattice, with basis vectors . If the vectors are primitive, then are
also primitive.
EXAMPLES:
Graphene
1 12
1-3 X-Ray Diffraction
Tuesday, May 14, 2013 4:08 PM
A. CRYSTAL DIFFRACTION
(1) X-Ray
X-rays interact with electronic shells of atoms in a solid. Electrons absorb and re-radiate X-rays. The
reflectivity of X-rays is of the order of , so that the penetration in the solid is deep.
Therefore, X-rays serve as a bulk probe.
OS:
Previous section has mathematically proved the reciprocal space and reciprocal lattice. In this
section, the reciprocal lattice will be introduced from the point of view of the experimental
results.
(2) Bragg diffraction (1913)

In crystalline materials, for certain wavelengths and incident directions, intense peaks of
scattered radiation were observed.
Bragg accounted for this by regarding a crystal as made out of parallel planes of lattices described
by Miller indices, spaced by distance apart.
Constructive interference occurs when the difference in path length is an integral number of wave
length , i.e.,
OS:
However, X-ray diffraction cannot see the atoms directly. It only sees Bragg peaks in different
positions and directions and of course their intensities after the X-ray is scattered from a single
crystal. Each Bragg peak in the diffraction pattern is related to the lattice planes. The lattice
planes can be defined with the help of Miller indices (hkl).
(3) Laue equation

OS:
Laue formulated an alternative theorem to the Bragg law for diffraction. This theorem is
beneficial because it does not require the assumptions used by Bragg, that reflection is specular
and involves parallel planes of atoms.
Max von Laue: Sharp peaks are observed only in the directions and at wavelengths for which the X-rays
scattered from all lattice points interfere constructively.
Two scatterers (lattice points) separated by a lattice translation vector . We assume that the
1 13
Two scatterers (lattice points) separated by a lattice translation vector . We assume that the
scattering is elastic, i.e. the wavelength of the incident and the scattered X-ray is the same as .
The path difference between the X-ray scattered from the two scatterers should be an integer number
of wavelengths.
Let
Constructive interference occurs when (diffraction condition)
Since , a general solution to the equation above is
with
with
Diffraction occurs when the change in wave vector equals a reciprocal lattice vector.
OS:
What is the necessary conditions for to form a reciprocal lattice?
(a) implies that is discritized.
(b) implies that has translational symmetry.
B. EQUIVALENCE BETWEEN BRAGG'S LAW AND LAUE CONDITION
(1) Miller indices (1839)

Miller indices are a symbolic vector that indicates the orientation of a plane or set of parallel planes of
atoms in a crystal.
Find the Miller indices:
1. Determine the intersection of the plane with primitive vectors as .
2. Take the reciprocals of the intercepts .
3. If fractions result, multiply each by the denominator of the smallest fraction.
4. Refers to a family of parallel planes labled as .
EXAMPLES:
Intercepts
Reciprocals
Miller indices
1 14
Intercepts
Reciprocals
Miller indices
Intercepts
Reciprocals
Miller indices
(2) Theorem: The reciprocal lattice vector is perpendicular to the lattice plane
described by Miller indices .
PROOF:
Suppose that the intercepts of a plane with primitive vectors are .
Considering two vectors and lie on the lattice plane.
The reciprocal lattice vector is perpendicular to the plane .
(3) Theorem: The distance between two adjacent parallel lattice planes is .
PROOF:
1 15
From the diffraction condition
The larger the , the closer the lattice planes, and less atoms on the plane.
(4) From Laue equation
Replacing to , which also satisfy the translational symmetry of the reciprocal lattice. We obtain
lying on the Bragg plane implies that diffraction occurs about planes which are perpendicular
bisectors of reciprocal lattice vectors.
Each reciprocal lattice point represents the various Bragg peaks (diffraction peaks).
(5) Ewald sphere construction (1913)

1. Construct a circle with radius
2. Wherever a point touches the circle, Bragg's law is obeyed and a diffracted beam will occur.
1 16
C. DIFFRACTION AMPLITUDE
(1) Scattering from a lattice
Scattering occurs due to the interaction of the incident X-ray with the electron charge distributed in a
solid with charge density . The amplitude of scattering by an infinitesimal volume is
proportional to the charge at this point, i.e. , and a phase factor acquired by the
scattered wave.
The total amplitude of the scattering is given by
The intensity is proportional to

The charge density that is periodic can be expanded in Fourier series of the reciprocal
lattice
where is the Fourier component of the charge density.
If , then , i.e. the intensity of a Bragg peak is determined by the Fourier component of
the charge density .
(2) Scattering from a lattice with basis

The scattering amplitude at the diffraction condition
1 17
where is the structure factor
It is convenient to write the charge density as the superposition of the charge densities associated with
each atom of a basis
where is the atomic form factor, which is determined by the charge density of atom in the basis.
EXAMPLES:
A bcc lattice contains two identical atoms
The atomic form factors are the same, i.e.
Diffraction peaks are observed, e.g. from (110), (200), (211) planes, but not from (100), (111),
(210) planes.
1 18
1 19
1-4 Brillouin Zone
A. BRILLOUIN ZONE (1930)
(1) The Brilliouin zone is defined by the area surrounded by the planes that are perpendicular bisectors of
the vectors from the origin to the reciprocal lattice points.
EXAMPLES:
Consider a two dimensional reciprocal lattice and a reciprocal vector . Draw a line, which is
orthogonal to and intercepts it in the midpoint.
It is easy to see that any vector connecting the origin and the plane should satisfy the diffraction
condition.
In the similar way, draw other lines, which satisfy the diffraction condition.
The enclosed area is called Brillouin zone. The vectors at the zone boundary can be Bragg reflected by
the crystal.
B. FIRST BRILLOUIN ZONE
(1) The first Brillouin zone is the smallest volume entirely enclosed by the planes that are perpendicular
bisectors of the reciprocal lattice vectors. The first Brillouin zone is the Wigner-Seitz primitive cell in the
reciprocal lattice.
The volume of the first Brillouin zone is
(volume of the unit cell)
OS:
1 20
EXAMPLES:
1. 1D chain
2. 2D rectangular lattice
(2) Symmetric points

1. Square lattice
1 21
2. Honeycomb lattice
C. BRILLOUIN ZONE FOLDING
(1) Modulated crystallography

1. Periodic crystal
2. Commensurately modulated aperiodic crystal

A superstructure is constructed by an integral number of unit cells larger than the original unit
cell.
The new periodicity with a characteristic wavevector is a rational fraction or multiple of the
lattice constant.
3. Incommensurately modulated aperiodic crystal
A structure can NOT repeat on a unit-cell boundary.
The new periodicity is irrational.
(2) The X-ray diffraction pattern

1. Periodic crystal: the reciprocal lattice points.
2. Commensurately modulated aperiodic crystal

The diffraction pattern is modulated and the standard periodic main reflections are surrounded
by satellite reflections.
The satellite locations are defined by a vector
All components of the vector are rational.

EXAMPLES:
1 22
3. Incommensurately modulated aperiodic crystal
The satellite peaks of vector, at least one component is irrational.
EXAMPLES:
(3) Brillouin zone folding

1. Real space
2. Reciprocal space (First Brillouin zone)
3. Reciprocal lattice vectors
4. Folding
EXAMPLES:
1. Structure of plane
2. Schematic of antiferromagnetic order. The solid line indicates the chemical unit cell, while the
dashed line indicates the doubled area of the antiferromagnetic unit cell.
1 23
3. Reciprocal space showing fundamental Bragg peak (filled circle) positions and antiferromagnetic
superlattice peak (open circle) at .
1 24
2-1 Bloch Theorem
A. HAMILTONIAN FOR PERIODIC POTENTIAL
(1) Lattice translation symmetry
With the periodic potential , the Hamiltonian is Invariance under lattice translation
(2) Lattice translation operator

1.
2. Product rule of
(3) The eigenvalues of translation operator are exponential.

PROOF:
commute with and have the common eigenfunctions
B. BLOCH [B-loch] CONDITION
(1) is linear in
PROOF:
Translations along different vectors add
, so is linear in .
(2) Bloch condition

The wave function with respect to the discrete translation symmetry is
PROOF:
Let
2 25
2-2 Bloch Wave Function
A. SCHRODINGER EQUATION IN THE PERIODIC POTENTIAL
(1) The Schrodinger equation in the reciprocal lattice
can be expanded in a Fourier series of the reciprocal lattice vector .
To solve the equation, we use plane waves as basis and expand the wave function in the following form
where we do not assume that has the periodicity of the lattice.

The Schrodinger equation becomes
Relabel
Central equation is the Schrodinger equation in Fourier series form for a periodic structure.
(2) Maps into the first Brillouin zone

Let where is the reciproacl lattice vector
Redefine
Relabel
(3) The wave function of the -representation is
2 26
The eigenenergy must also be labeled by
(4) Crystal momentum
is conserved in crystals and is only up to
B. BLOCH WAVE FUNCTION (1928)
(1) The Bloch wave function
The periodic wave function can be written as the product of a cell-invariant part and a cell-periodic
part .
Felix Bloch (Swiss physicist): The electrons can sneak by all ions in a metal because the wave differed
from the plane wave by a periodic modulation.
(2) Translation symmetry in reciprocal lattice

1. The Bloch function is periodic in -space, i.e.
PROOF:
2. The eigenenergy is periodic in -space, i.e.

PROOF:
2 27
(3) There are -points in the first Brillouin zone.
PROOF:
1. Born-von Karman boundary conditions
where are the total number of primitive cells in the crystal.
Applying Bloch's theorem gives
2. Volume per point in -space
The number of allowed -values in a Brillouin zone is equal to the number of unit cells in the crytsal.
2 28
2-3 Supercells
A. NON-PERIODIC SYSTEM
(1) An infinite lattice
(2) A defect removes periodicity
(3) Constructing a supercell
The supercell is replicated periodically throughout space.

The supercell must be large enough so that the systems contained within each one, which in reality are
isolated, do not interact significantly.
2 29
B. PERIODIC BOUNDARY CONDITIONS
(1) The infinite periodic lattice is modeled by a large number of supercells stacked together. Periodic
boundary condictions are chosen for approximating an infinite system by using a small part.
(2) Apply periodic boundary conditions (Born-von Karman boundary conditions) to the wave-functions.
, where is the total number of supercells.
Bloch theorem in primitive cell:
2 30
3-1 Lattice Vibrations
A. LATTICE VIBRATIONS
(1) Consider identical atoms of mass with periodic boundary condition. For small displacement on the
atom from its equilibrium position one can expand the potential energy near its minimal value
Let
OS:
The first term is a constant which can simply be absorbed in setting the zero of energy. By the
definition of equilibrium, the second term must vanish (the net force is zero at equilibrium). The
third term is quadratic in the displacements, so called harmonic term.
(2) The Hamiltonian in the harmonic approximation is
(3) Classical equation of motion

Let depends only on the relative positions of atoms and , i.e. on
B. ONE-ATOMIC LINEAR CHAIN
(1) Dispersion relation and band structure

Assume (spring constant)
Trial function
3 31
It is impossible to discriminate between and . Therefore, it is natural to choose the region
(the first Brillouin zone) to represent the dispersion law in the whole -space.
(2) Periodic boundary condition
The set of values is restricted to the first Brillouin zone,
The total number of values in the first Brillouin zone is .
(3) Near zone center (small approximation or long wave vibrations limit)
where is the sound velocity in a homogeneous elastic medium.
(4) Zone boundary

1. Phase velocity: the propagation of the equal phase planes
Group velocity: the energy transfer
3 32
2. At the boundary
The boundary modes can transfer energy.
C. DIATOMIC CHAIN
(1) Band folding

1.
Lattice vector
Reciprocal vector
Zone boundaries
2.
Lattice vector
Reciprocal vector
Zone boundaries
The dispersion curve lying outside the region must be folded back into the first
Brillouin zone.
(2) Dispersion relation
Assume
3 33
(3) At center
At boundaries
OS:
As , the potentials between atoms are not uniform. The potentials between atoms can be
described as a periodic potential well/barrier. For any periodic potential, Bragg refection at the
Brillouin zone boundaries allow vibrations to have ONLY a certain frequency. The periodic
potential will result in discrete energy band gaps at the zone boundary.
(4) Structure of vibrations
At very long waves limit,

1. For
All the atoms move next to synchronously, like in an acoustic wave in the homogeneous medium.
2. For
The center of mass remains unperturbed. In an ionic crystal such a vibration produce alternating
dipole moment. Frequency is in infrared.
D. 3D LATTICES
(1) Equation of motion
where is the polarization vector along directions and
3 34
where is the polarization vector along directions and
The dynamical matrix is
One gets the eigenvalue problem

Eigenvectors
Eigenvalues (normal modes)
The displacement can be written as
(2) Periodic boundary condition , satisfied for three primitive directions.

The wavevector is
where are the reciprocal lattice vectors.

The set of -values is restricted to the first Brillouin zone.
The total number of -values in the first Brillouin zone is
3 35
3-2 Quantum Mechanics of Atomic Vibrations
A. CLASSICAL APPROACH (NORMAL MODES)
(1) Define normal coordinates (Fourier transform)
(2) The Hamiltonian becomes
which is the sum of independent simple harmonic oscillators.

OS:
3 36
B. QUANTUM MECHANICAL APPROACH (PHONONS)
(1) Schrodinger equation
Eigenvalues
Eigenfunctions
where is Hermit [hur-mit] polynomial.

OS:
Quantum mechanical approach gives the quantized frequency , i.e. the vibration with
frequency can be considered as a particle with energy . The wavefunctions describe
the displacement of the th atom. The square of the amplitudes of the wavefunctions, i.e.
intensities, correspond to the size of the particles.
Phonon is referred to as a quasiparticle and represents an excited state in the quantum
mechanical quantization of the lattice vibrations.
Phonons are elementary excitations over the zero-point vibration energy
(2) Second quantization

Introducing the creation and annihilation operators
3 37
The Hamiltonian becomes
where is the occupation number operator for phonons with energy , is the
vibrational frequency in state and polarization .
The energy of one phonon is .
OS:
Second quantization approach gives the quantized intensities, i.e. the number of the particles
.
3 38
3-3 Phonons
A. NONINTERACTING PHONONS
Ignoring the interaction, the particle at th energy level is equivalent to put particles at the ground
state.
Displacement
OS:
Usually the summation of is difficult to calculate. We could transform the summation to the
integration by introducing an auxiliary function , the density of states.
B. ANHARMONIC OSCILLATOR
(1) The general Hamiltonian of the real crystal
where
is the harmonic term and
is the anharmonic term.
(2) Considering the anharmonic term as a small perturbation, the rate of the transition, i.e. the Fermi's
Golden Rule, is
OS:
When you solve an Hamiltonian for the harmonic oscillator you get a set of eigenstates which by
definition are orthogonal and thus you have phonons that don't interact. When you include a non
harmonic term to the Hamiltonian and treating it as a perturbation you get new eigenstates that
are a mixture of those the simple harmonic oscillator. This mixture is what it's called phonon-
phonon interaction.
C. PHONON-PHONON SCATTERING
(1) Anharmonic term
3 39
Let and
OS:
indicates the conservation of momentum
The value of is uniquely determined since must all lie within the rst Brillouin
zone. Now define
(2) Feynman diagrams:

1. : annihilates three phonons
2. : annihilates two phonons and creates a third phonon
3. : annihilates a phonon and creates two phonons
4. : creates three phonons
(3) Most phonon-phonon scattering conserves crystal momentum and contains or
3 40
1. Normal process: -values are very small compared to the reciprocal lattice vector .
2. Umklapp process (backscattering process): -values are close to and the sum of and is
outside the first Brillouin zone.
3 41
Summary Periodicity, Quasiparticles
A. PERIODICITY
(1) Lattice
A large number of supercells with periodic boundary condition repeats indefinitely to construct a
crystal lattice.
(2) Reciprocal lattice
(3) Bloch Electrons

A system has the periodic potential, and then the function is periodic in the reciprocal space,
B. QUASIPARTICLES
(1) The lattice vibrations can be described as a set of quasiparticles (phonons) with quasimomentum
and energy .
(2) They can be treated as the Bose particles with zero chemical potential, the only dierence being that in
all the interaction processes quasimomenta are conserved with the accuracy of .
C. TO BE
3 42
3 43
4-1 Review of Statistics
A. STATISTICAL ENSEMBLE (Gibbs 1902)
OS:
Ensemble: A large number of virtual copies of a system, have the same macrostate, but different
microstates. Different macrostate lead to different type of ensemble.
(1) Microcanonical ensemble (Isolated system)

1. An isolated system with the fixed volume , the fixed number of particles , and the fixed energy
.
2. The combinations of particles (identical and indistinguishable) distribute into the energy level
with degeneracies
3. Microcanonical partition function
OS:
Partition function: encode how the probabilities are partitioned among the different
microstates, based on their individual energies.
4. Boltzmann principle
Entropy is a measure of the number of possible microstates of a system in thermodynamic
equilibrium, consistent with its macrostate.
5. Temperature
(2) Canonical ensemble (Closed system + heat reservoir)

1. A closed system with the fixed volume and the fixed number of particles thermally contacts
to a heat reservoir to approach the thermal equilibrium.
2. Canonical partition function
3. Thermodynamics
(a) Internal energy
4 44
(b) Specific heat
Specific heat is changes in the internal energy with respect to temperature.
(c) Helmholtz free energy
(d) Entropy
(3) Grand canonical ensemble (Open system + heat reservoir + particle reservoir)
1. An open system with the fixed volume and thermally contacts to a particle reservoir and heat
reservoir to approach the thermal equilibrium.
2. Grand canonical partition function
3. Distribution function
The distribution functions are
4. Thermodynamics
4 45
4. Thermodynamics
(a) Thermodynamic potential
(b) Entropy
B. PHONON GAS
(1) The canonical partition function of an oscillator with energy is
(2) The mean energy of one oscillator is
OS:
The combinations of phonons distribute into the energy level with degeneracies
Internal energy
4 46
(3) The number of phonons is not conserved: they can be created or annihilated in course of interactions.
Therefore they should be determined from the condition of equilibrium, i.e. from the request of
minimum of free energy. As a result, for phonons . The Bose-Einstein function determines the
equilibrium number of phonons with a given frequency.
C. ELECTRON GAS
(1) At a finite temperature, some of the electrons will be excited to states above the Fermi energy. The
probability that a given energy state is occupied by fermions follows the Fermi function:
where is the chemical potential (the increased free energy needed to add an electron to the system).
(2) Thermodynamic potential
(3) Entropy
4 47
Notice that for goes to zero as goes to zero.
(4) Helmholtz free energy
4 48
4-2 Phonon Density of States
A. INTEGRAL OVER FREQUENCY
(1) Connection between summation and integral

For any function
we have
(2) The allowed (independent) values were given by
and are restricted to the first Brillouin zone, i.e. .

OS:
If , , and are integers, indicates the reciprocal lattice points.
The summations over can be converted to integrals as follows:
(3) Any summation over allowed values can be converted into an integral over frequency as follows:
Density of States : the number of normal modes per unit volume in the infinitesimal [in-fin-i-
tes-uh-muh l] range between and .
B. DENSITY OF STATES (DOS)
(1) Surface integral

Let be the surface in -space on which has the value .
4 49
The frequency change in going from the surface to the surface can be expressed
in terms of , an infinitesimal displacement in -space as
The volume element in -space can be written as
EXAMPLES:
1. Isotropic in 1D
2. Isotropic in 2D
3. Isotropic in 3D
(2) Volume integral
PROOF:
C. VAN HOVE SINGULARITY (1953)
(1) From the surface integral,
where is the group velocity

When , the integrand exists singularities. Those singularities are called van Hove
4 50
When , the integrand exists singularities. Those singularities are called van Hove
singularity. Since , the modes at values do not transfer energy.
(2) The singularities occur as the dispersion is flat at nearby the value.
The dispersions are flat at
1. the center of the Brillouin zone (minimum)
2. the zone boundaries (minimum or maximum)
3. along high symmetry directions (minimum, maximum, or saddle point)
D. PHONON DENSITY OF STATES
(1) One-atom linear chain
where
The function has an absolute maximum for or .
The function has an absolute minimum for .
The band width is

The DOS is
1. Surface integral
2. Volume integral
4 51
Fourier transform of a Bessel function
The singularities occur as gives
The dispersion is flat at the boundaries of the first Brillouin zone. The modes at do not
transfer energy.
(2) One-atom square lattice
The band width is

The DOS is
4 52
The singularities occur as ,
(3) One-atom cubic lattice
The band width is
4 53
4 54
4-3 Lattice Specific Heat
A. DULONG-PETIT LAW (1819)
(1) The empirical Dulong-Petit law
(2) Classical model

1. Equipartition theorem
2. Density of states
3. Internal energy
B. EINSTEIN MODEL (1907)
(1) Einstein assume:

1. The motion of each atom is described by a harmonic oscillator
2. Each atom vibrates with the same frequency , because without interaction between atoms the
dispersion curves of the various phonon branches (optical phonon) become simply constant.
OS:
The normal modes of vibration have a spectrum , where is restricted to the rst
Brillouin zone and is the polarization of the mode.
(2) Method: Density of states
4 55
(2) Method: Density of states
OS:
From the surface integral, the integrand diverges as .
Internal energy (in thermal equilibrium)
(3) Method: Partition function
(4) Limit
4 56
1. Low-temperature limit:
2. High-temperature limit:
C. DEBYE MODEL (1912)
(1) Debye assume:

1. Atoms vibrate collectively in a wave-like fashion
2. The phonon spectrum (acoustic phonon)
for all values of in the first Brillouin zone.
3. Debye replaced the Brillouin zone by a sphere of the same volume
(2) Density of states
where are the speed of a longitudinal and of a transverse sound wave.
4 57
where are the speed of a longitudinal and of a transverse sound wave.
(3) Internal energy
Let and and ignore the zero-point vibration energy,
where
(4) Limit
1. Low-temperature limit:
2. High-temperature limit:
4 58
4 59
4-4 Lattice Thermal Conductivity
A. THERMAL CONDUCTIVITY
(1) Fourier's Law (1822)
The ratio of the thermal current to the magnitude of the temperature gradient,
(2) Kinetic theory
1. The energy of phonon along the -direction
where is the mean free path

2. The energy flux of phonons is
where is the Maxwell-Boltzmann velocity distribution

3. The energy flux along the -direction
(mean free time between collisions, i.e. relaxation time)
4 60
(mean free time between collisions, i.e. relaxation time)
OS:
B. INSULATOR
OS:
is related to the scattering processes
is related to the phonon energy
(1) At high temperature,

1. constant
2. Scattering process:
Phonons with values close to a reciprocal lattice vector will be thermally excited.
The umklapp scattering processes will degrade the thermal current.

OS:
Phonons have high energy at high temperature. The high energy phonons correspond to
the large values.
The rate of collisions between phonons
(2) At intermediate temperature,
1.
Phonons with small values are excited.
The normal scattering processes do not degrade the thermal current.

4 61
(The conductivity rises more steeply with falling temperature.)
(3) At low temperature,
1.
Phonons with exist.
(4) The thermal conductivity of an insulator
4 62
5-1 Drude Theory
OS:
Treats electrons as a gas following Boltzmann statistics.
A. DC CONDUCTIVITY (OHM'S LAW)
(1) In the presence of an constant electric field
Drude (1900) proposed a collision mechanism by which electrons make collisions every second.
In each collisions all of the electron's forward velocity is reduced to zero and it must be accelerated
again. The result is a constant average velocity:
(2) The current density
where is the electron concentration
B. AC CONDUCTIVITY
Let and
5 63
C. ELECTRONIC THERMAL CONDUCTIVITY
(1) The energy per electron at equilibrium at is .
where is the thermal velocity
(2) Specific heat
5 64
D. WIEDERMANN-FRANZ LAW (1853)
At a given temperature the ratio of the thermal conductivity to the electrical conductivity was the same
for all metals.
OS:
This empirical law is named after Gustav Wiedemann and Rudolph Franz, who in 1853 reported
that has approximately the same value for different metals at the same temperature. The
proportionality of with temperature was discovered by Ludvig Lorenz in 1872.
E. PLASMA FREQUENCY
(1) Maxwell's equations
Assume
5 65
(2) The complex dielectric constant
In the limit
F. HALL EFFECT (1879)
(1) In the presence of a magnetic field (weak field) and an electric field
(2) Cyclotron frequency

The Lorentz force
Under the magnetic field, the electron moves circularly. Supposing the centrifugal force is equal to the
Lorentz force, the cyclotron frequency is
(3) The external magnetic field induce an effective electric field . The induced field is coupled to .
The Newton's equations become
5 66
(4) The conductivity tensor & resistivity tensor
(5) Hall resistivity
G. SPECIFIC HEAT
(1)
5 67
(2) Experimentally, one finds a value of about at room temperature, independent of the number of
valence electrons (rule of Dulong and Petit), as if the electrons do not contribute at all.
H. OUTCOME OF DRUDE MODEL
(1) Successes
Dc conductivity
Ac conductivity
Electronic thermal conductivity
Wiedermann-Franz law
Plasma frequency
Hall effect
(2) Shortcoming
Specific heat
5 68
5-2 Sommerfeld Theory
A. QUANTUM THEORY OF ELECTRON GAS (1928)
OS:
Arnold Johannes Wilhelm Sommerfeld (1868-1951)
(1) As the freely moving electrons cannot escape the surface of the material, they may be treated as
particles confined (trapped) in a box of size . The Schrodinger equation is
The plane wave solution is
(2) Box boundary condition (open boundary condition): vanishes at the boundary
where
Energy of the electrons inside the material is quantized and hence is discrete.
(3) Born-von Karman boundary conditions (periodic boundary condition):

OS:
Advantage: allows the travelling wave
where
The periodic boundary condition permits only certain discrete values of .
5 69
B. GROUND STATE CONFIGURATION
(1) Electrons fill the energy states
Place electrons from the energy level . Then continue to add electrons, subject to the Pauli
exclusion principle, and successively filling the energy levels of lowest energy that are empty.
(2) Fermi energy represents the sharp occupancy cut-off at for particles described by the
Fermi-Dirac statitics, i.e. the energy levels of are occupied subject to the Pauli exclusion
principle, and all those with are empty.
Different boundary conditions give the same Fermi wave vector and the same energy.
(3) Fermi surface is the locus of points in reciprocal space where

For 1D metal, the Fermi surface is two points at .
For 2D metal, the Fermi surface is a circle.
5 70
For 3D metal, the Fermi surface is a sphere.
The radius of the "sphere" is called the Fermi wave vector .
(4) Ground state energy

The total number of occupied states equal to the number of unit cells in the crytsal and the total
number of electrons .
1. Box BC:
2. Periodic BC:
OS:
5 71
The ground state energy
Average energy per electron is
EXAMPLES:
Typical value of metal
Fermi energy:
Fermi temperature:
At room temperature we are not very far from the ground-state configuration.
5 72
5-3 Electron Density of States
A. DENSITY OF STATES
(1) Density of States : the number of energy states per unit volume in the infinitesimal range
between and .
(2) Surface integral
Since
OS:
This form of shows that flat bands have high density of states, and steep bands have low
.
(3) Volume integral
B. SIMPLE METALS
(1) 1D
1. Countable -values
5 73
2. Surface integral
3. Volume integral
OS:
(2) 2D
5 74
2. Surface integral
3. Volume integral
(3) 3D
5 75
2. Surface integral
3. Volume integral
C. FINITE TEMPERATURE EFFECT
(1) Probability that a state with energy is occupied at is
At , the system is at the ground state.

At
1. In the limit,
2. In the limit,
falls off exponentially with increasing .
3. At
(2) The total number of occupied states at the finite temperature
where is the density of occupied states per unit volume and energy.
5 76
At
(3) The majority of the electrons in a metal fill states with energy far below the Fermi energy. Such
electrons have very little effect on the macroscopic properties. A small change in does not affect the
mean energies of the majority of the electrons, with , since these electrons lie in states which are
compeltely filled, and remained. These electrons contribute nothing whatsoever to the macroscopic
properties.
A relatively small number of electrons in the energy range of order , centered on , in which
is significantly different from and , do contribute to the macroscopic properties.
The fraction of active electrons lie in the tail region is
where is
The integral can be approximated as
5 77
The integral can be approximated as
5 78
5-4 Electronic Specific Heat
A. SOMMERFELD EXPANSION
(1) Internal energy
OS:
Cannot be integrated out, except the numerical method.
(2) Sommerfeld expansion (Integration technique)
PROOF:
1. Integration by parts
where is the total number of states per unit volume whose energy is less than
2. If the function is slowly varying compared to in the region , we can expand

in Taylor series as follows:
3. Let
5 79
where in metal, , the lower limit of the integral can be replaced by .
(3) Internal energy
B. ELECTRONIC SPECIFIC HEAT
(1) If a function is slowly varying around
(2) Using the identity
PROOF:
5 80
The internal energy becomes
(3) The electronic specific heat is
C. SPECIFIC HEAT OF METAL
(1) The total specific heat of a metal at low temperature takes the form
where is the eletronic specific heat and is due to lattice vibrations. As the temperature is
reduced, approaches zero far more rapidly than the eletronic specific heat.
EXAMPLES:
Low temperature specific heat of copper
(2) Explain the following figure
5 81
(2) Explain the following figure
1. Specific heat of metal
2. Specific heat of insulator & metal
OS:
James William Rohlf, Modern Physics from to , Wiley, 1994.
Strong experimental deviations from this number are observed for, for instance, , ,
, , and .
5 82
5-5 Compressibility and Susceptibility
A. COMPRESSIBILITY
(1) The equation of state of a Fermi gas
where the grand canonical potential
(2) The compressibility is defined by
At as
(3) The velocity of sound in solid is given by
where is the mass density.
where is the ionic mass and is the number of electrons per atom
5 83
where is the ionic mass and is the number of electrons per atom
B. PAULI PARAMAGNETISM (1925: SPIN RESPONSE)
(1) Susceptibility
where is the magnetic moment and is the magnetization
where is the external field
(2) In a metal,
1.
2. Apply an external field , energy levels shift
At equilibrium, electrons in the shaded region (up spin) go into lower energy states (down spin)
and flip spins.
The number of down spins is larger than the number of up spins. Overall, this imbalance causes an
overall magnetization.
At as
5 84
C. LANDAU DIAMAGNETISM (1930: ORBITAL RESPONSE)
(1) In the presence of a magnetic field and
The energy of a state is
The density of states is
The free energy is
(2) At
Let
For large , we use the Euler-Maclaurin formula
5 85
(3) The total susceptibility of a metal is
5 86
6-1 Lorentz Theory
A. DRUDE MODEL (REVIEW)
(1) Dc conductivity (Ohm's law)
where is the electron concentration
(2) Electronic thermal conductivity
(3) Wiedermann-Franz law (1853)
B. KINETIC THEORY OF ELECTRON GAS
OS:
Hendrik Antoon Lorentz (1853-1928)
Since Drude's simple model gave some results that agree fairly well with experiment, Lorentz
decided to use the full apparatus of kinetic theory to investigate the model more carefully. He did
not succeed in improving on Drude's model, but he did make use of the Boltzmann distribution
function and Boltzmann equation.
(1) A statistical description of a system can be explained by distribution function
In thermodynamic equilibrium, , where
is the local Maxwell-Boltzmann distribution.
(2) An external force acting on an electron of mass will change the velocity and position, i.e.
If no collisions take place between the electrons,
If collisions take place between the electrons, there will be a net difference in the interval . The
rate of change between final and initial distribution function is called collision integral, i.e.
As the limit yields
where is the non-equilibrium distribution function.

OS:
Non-equilibrium statistical mechanics
C. LINEAR BOLTZMANN EQUATION
(1) The total rate of change can be expanded as
The Boltzmann transport equation can be written as
6 87
The Boltzmann transport equation can be written as
(2) Relaxation time approximation

Collisions relax the distribution back to the equilibrium distribution or a local equilibrium distribution
exponentially with a single time constant
where is the thermal equilibrium distribution function and is the relaxation time.
D. CONDUCTIVITY
(1) Dc conductivity
Electrons in the constant electric field . The steady state Boltzmann equation is
The electrical current density is
The electrical conductivity tensor is
The diagonal electrical conductivity is
OS:
Useful formula
a)
b)
Method 1:
Method 2:
6 88
Method 2:
(2) Thermal conductivity

Electrons in a temperature gradient
The thermal current density is
The thermal conductivity tensor is
The diagonal thermal conductivity is
OS:
6 89
(3) Wiedermann-Franz law
6 90
6-2 Boltzmann Equation
A. BOLTZMANN EQUATION
(1) Non-equilibrium distribution function

In thermodynamic equilibrium, the local electron distribution function is given by the Fermi-Dirac
distribution.
When an external field is applied from outside, the electron distribution function is .
(2) Liouville [Liou-ville] equation

In the presence of an external field
The phase space volume along a stream line in phase space is constant.
OS:
Since and are independent, and the external fields are independent of , we can have a
conservative form because (in the absence of collisions) motion (of particles or along the
characteristics) is incompressible in the six-dimensional phase space
(3) Boltzmann equation

Liouville equation with scattering
OS:
The idea behind the Boltzmann transport equation is to divide the interactions of the particles
into two parts. One part, due to macroscopic forces and potentials, is described by a Hamiltonian.
The other part is due to the microscopic interactions between particlesthe collisions. The
"external" interactions satisfy Liouville's theorem. The collisions "create" and "destroy" particles.
That is, a particle undergoing a collision will "suddenly" disappear from its volume of phase space
(it's been destroyed) and reappear (be created) in a dierent volume of phase space.
B. RELAXATION-TIME APPROXIMATION
(1) Relaxation time ansatz

If the external field creates a non-equilibrium distribution , and the field is then suddenly
switched off, then from the moment of switching off
6 91
Scattering must serves to drive the non-equilibrium distribution back towards thermal equilibrium at
time where .
In the relaxation time approximation
The solution is
As
The relaxation time is therefore the time constant with which the non-equilibrium distribution relaxes
via scattering to the equilibrium state when the external perturbation is switched off.
(2) Stationary non-equilibrium distribution

When the uniform external field =constant is not zero ( is the potential), the steady state
distribution function is desired.
Assume the applied field is small, the small deviation from thermal equilibrium is
The stationary distribution can therefore be represented by a Fermi distribution shifted by from
the equilibrium position.
EXAMPLES:
Ohmic conduction in solids (DC external electric field)
(a) Effects of the Fermi surface
6 92
The great majority of the electrons cancel each other pairwise, electrons in the shaded area
remain uncompensated and produce the observed current.
(b) Effects of the distribution function
The new Fermi distribution only differs significantly from the equilibrium distribution
in the vicinity of the Fermi energy.
(3) Relaxation back to equilibrium

The stationary non-equilibrium distribution is represented as a displaced Fermi sphere.
1. Inelastic scattering
Since the states and are at different energy states, the relaxation back to equilibrium must
involved inelastic scattering.
2. Elastic scattering
For purely elastic scattering, the Fermi sphere would simply expand. The equilibrium can only be
achieved by inelastic scattering into states .
6 93
6-3 Transport Coefficient
Transport is the phenomenon of currents flowing in responds to applied fields.
A. LINEAR CONDUCTIVITY
(1) Small deviation from thermal equilibrium

The equation of motion of an electron
In the relaxation time approximation, the Boltzmann equation becomes
Let
First, compute the differential of
The linearized Boltzmann equation
(2) Coefficients of transport (matrices)

Consider a system in the presence of a constant electric field and temperature gradient but no
magnetic field
In stationary states
1. Electric current density
2. Thermal current density
6 94
They are of the form
The electric conductivity tensor

The thermal conductivity tensor
B. CONDUCTIVITY OF METALS
(1) Electrical conductivity
1. At zero temperature ( )
Only electrons in the vicinity of the Fermi energy are relevant for current transport in a metal.
6 95
OS:
Drude conductivity
The dissipative part of the conductivity is
The peak at is known as the Drude peak

2. At
OS:
The diagonal conductivity is
(a) Method 1:
Using Sommerfeld expansion
(b) Method 2:
Integration by parts
6 96
(2) The thermal conductivity is defined as the ratio of the thermal current to under conditions of
zero electrical current.
6 97
(3) Wiedermann-Franz law
C. ONSAGER RECIPROCAL RELATION (1931)
Transport phenomena, such as the flow of electric current in solids, involve two characteristic
mechanisms with opposite effects: the driving force of the external fields and the dissipative effect of
the scattering of the carriers by phonons and defects.
The Onsager relation is a result of fluctuation-dissipation theorem, plus time reversal symmetry.
6 98
6-4 Impurity Scattering
A. ELASTIC SCATTERING
(1) Beyond the relaxation time approximation
is the transition rate for an electron at (occupied state) (unoccupied state) calculated
by Fermi's golden rule.
Transition out of the state
Transition into the state
Collision term for static potential:
(2) In thermal equilibrium
The detailed balance
Scattering rate to lower energy states is larger than scattering to higher energy states
(3) Elastic scattering
B. SCATTERING BY IMPURITIES
(1) From the Dirac perturbation theory, the transition probability ("Fermi golden rule") is
where is the sum over individual impurity potential
and indicates the conservation of energy.
6 99
Because the positions of the impurities are random, the distance between them is much greater than
interatomic spacing . So we can average over their positions
where the first term is the one with , and the second term is the ones with .
Neglect the second term, the collision integral becomes
Assume the small deviation from thermal equilibrium
(2) The Boltzmann equation in the presence of a constant electric field and in the relaxation time
approximation
OS:
Examine under what circumstances the relaxation time approximation is possible.
(3) Relaxation time
6 100
(3) Relaxation time
The Born approximation for differential scattering cross section
where is the Fermi velocity

The factor indicates that forward scattering does not contribute to the scattering
rate, i.e., the forward scattering does not degrade the current.
C. SCATTERING BY IONIZED ATOM
(1) The Coulomb potential
The differential scattering cross section
OS:
As diverges logarithmically
(2) Thomas-Fermi screening

A weak local electrostatic potential will induce a change in the local electronic density
The Poisson equation becomes
Free electrons will rearrange themselves so as to screen an impurity potential. At long range, the
effective (screened) potential decays exponentally, rather than as .
6 101
(3) The transport lifetime for screened Coulomb scattering
where is the effective Bohr radius
(4) The resistivity
For and
6 102
6-5 Phonon Scattering
A. INELASTIC SCATTERING
(1) Collision integral

1. with momentum
2. with momentum
OS:
and indicate the conservation of energy.
(2) Matrix elements
1. The matrix elements of absorption of a phonon
2. The matrix elements of emission of a phonon
OS:
Since for , only the longitudinal acoustic phonon are coupled to the electrons
The electron-phonon interaction will be treated to the lowest order of the perturbation theory
(Born approximation). The transition probabilities depend on the occupation number of phonons
and absorption/emission processed involve different combinations of these numbers. The
principle of microscopic reversibility tells us that the possibility of a process between two states
must be independent of the direction in which the process runs, i.e., and
(3) The contribution of these processes to the collision integral and changing the summation index from
is
6 103
OS:
The collision term vanishes in equilibrium
B. BLOCH-GRUNEISEN [grin'eisen] FORMULA
(1) Bloch ansatz

The phonon distribution remains in equilibrium even though the phonons scatter electrons and vice
versa.
(Bose distribution)
OS:
Phonon equilibrium can be achieved via anharmonic eects (i.e. phonon-phonon scattering),
or by scattering of phonons from impurities or crystalline defects.
(2) Linearize the collision integral

OS:
The arguments of the -functions are
In the static potential limit (Born-Oppenheimer approximation):
(3) Apply a constant electric field for an isotropic metal and relaxation-time approximation [c.f. 6-2-B]
6 104
OS:
At the Fermi surface , the Boltzmann equation is
(4) Integrating over angle

Scattering is of the small-angle type
OS:
6 105
(5) In general
1. implies that the resistance is due to scattering of electrons by phonons (as it is for simple
metals)
2. implies that the resistance is due to s-d electron scattering (as is the case for transition
metals)
3. implies that the resistance is due to electron-electron interaction.
C. MATTHEISEN RULE
(1) The phonon and defect scattering mechanism are independent.
(2) Temperature dependence of resistivity in metals
6 106
Historical Perspective - Band Theory
A. SUMMARY
1928 maximilian Strutt: The Matthieu differential equation can describe the motion of a particle along
the direction of sinusoidally changing potential energy (first attempt to solve the Schrdinger equation
for a periodic potential) Allowed solutions of the Matthieu equation fill certain finite areas in the plane
of particle energy potential amplitude.
1928-1931 Bloch/Wilson/Peierls move on to solids and invent band theory. Convincing explanation for
metallic, insulating, and semiconducting behaviour in solids.
1937 Bristol conference on electrical conduction mechanisms - data presented for series of transition
metal oxides (most famous example ) which seems to imply drastic breakdown in band theory. First
identification of strongly correlated materials.
1949-1954 Series of paper by Mott provides conceptual explanation.
1960s Hubbard models. New types of strongly correlated materials identified.
1970s Advent of proper computers + density functional theory. People try to do real band theory
calculations. They don't work too well.
1980s People discover high Tc superconductivity and suddenly transition metal oxides become
fashionable again. People try to do band theory calculations. They don't work too well.
1990s People try to do band theory calculations. Some of them work a little better.
B. BAND THEORY (1928-PRESENT)
After Schrodinger, Heisenberg, Bohr, Born, Dirac and Jordan finish inventing quentum theory, people
like Bloch, Wilson and Rudolf Peierls start applying it to solids, and they come up with band theory. They
found that, because the phase of the wave function can vary from site to site without violating the
boundary condition, bands of allowed energy states exist that may be spread over several eV. They
introduced the wave vector that labels the individual levels in a band and describes the frequency and
direction of the phase modulation. And essentially, they showed that a material can be classified as a
metal or an insulator according to whether the highest occupied electron level lies within a band or at
the bottom of a band gap.
A problem arose in some conference in 1937. De Boer and Verwey presented some conductivity data
for some insulating transition metal oxides, and said "Look, this proves that Bloch/Wilson band theory
breaks down.." Why? Well let's take the paradigmatic one: nickel oxide . The valence band is
made up of 3d states. What can split the 3d band? In those days the answer was the crystal field. is
cubic so the d manifold splits into an lower triplet and an upper doublet, which for group theoretical
reasons are known as the and states respectively. There are electrons so we fill up the bands
and the Fermi level is right in the middle of the eg states. So, this must be a metal, according to
Bloch and Wilson. Rudolf Peierls comments that this must be due to 'strong correlations' between the
electrons which causes them to become localized, hence completely violating the band theory picture
which is taken to refer to completely delocalized electrons. Professor Nevill Mott, who was the
chairman, goes away to think about it. Thirteen years later in 1949 he begins to publish a series of
articles which, conceptually at least, solves the problem.
As you may know, he considered a crystal in which you can vary the lattice constant. Actually a one-
dimensional lattice of hydrogen atoms but you can think of any metallic crystal you want. Itinerant
electrons can move from site to site in a metal. Increase the lattice constant up to a couple of miles. We
then just have an array of independent atoms sitting around in space. So somewhere along the way,
there must be transition point between localized and itinerant behaviour. In the 1D hydrogen metal, it
must be the case that short-ranged charge fluctuations occur, leading in particular to configurations
with two electrons with opposite spins on the same site. These fluctuations cost some energy, and
therefore short-ranged correlations tend to suppress the formation of delocalized states and this tends
to make the electrons prefer to be localized on each site. Now, Mott showed that we can expect
7 107
to make the electrons prefer to be localized on each site. Now, Mott showed that we can expect
complete localization when some characteristic Coulomb energy is of the order of the band width,
defined through the overlap between orbitals. Now, if this happens, only activated conductivity is
possible, which means that a gap must have arisen in the one-electron density of states near the Fermi
level. Fine.
In the 1960s people wanted to study this and they developed various simple models which lead to
localized and itinerant behaviour in the appropriate limits. For example, the Hubbard model, which
Peter talked about. You have a second-quantized Hamiltonian with a parameter , which approximates
the strong on-site Coulomb interaction and a parameter , which is a kinetic term describing the motion
of electrons between neighbouring sites. And people have managed to extract lots of important
information from this.
I should mention that one thing that wasn't realized in the 1940s was that many of these interesting
materials like were antiferromagnetic: they have local magnetic moments which order below a
certain temperature. When this was realized, Slater came up with a different idea to Mott for explaining
the insulating behaviour, as follows: when we form an antiferromagnet, we double the size of the unit
cell, hence we halve the size of the first Brillouin zone, and gaps open up at the new zone boundaries.
See any second year solid-state course. (This is in fact not true).
So when computers arrive, and Hohenberg, Kohn and Sham invent density functional theory, and
people started trying to do proper calculations and they predict and other antiferromagnetic
insulators to be non-magnetic metals. Then they discover spin polarization and they predict them to be
ferromagnetic metals. So band theory breaks down and leads to lots of confusion. Then in 1987 high
cuprates arrive, which in their undoped state turn out to be two-dimensional antiferromagnetic Mott
insulators. People really want to understand these so they do band theory calculations and they find
ferromagnetic metals. So there really does appear to be a big problem.
C. TWO VIEWS
In one view, electrons are viewed as "free" at first. The effect of the crystal potential is the formation of
the energy band. In this view, the energy available for electrons become narrow as the crystal potential
is considered.
In another view, electrons are viewed as "localized" first, each valence electron belonging to a local
environment, i.e. atom/ion/molecule in a basis. The crystal potential makes these local states unstable,
making it possible for electrons to hop and explore the entire crystal. In this view, the energy available
for electrons become wide as the total crystal potential is considered.
These two views, which may be called the "itinerant" view and the "localized" view, are equivalent
within the band theory. They become distinguished more sharply when electron-electron interactions
are considered. We will discuss this when we discuss magnetism later.
D. BREAKDOWN IN BAND THEORY?
Why is there a problem with one-electron band theory?

Why do people think band theory or one-electron calculations break down for strongly correlated
materials? Because they do, if you use LDA/GGA calculations etc.. But the LDA is not band theory. And
the LDA does not break down because we don't include some mysterious magic Coulomb interaction
which spontaneously arises in some new state of matter as is sometimes claimed. It's because we do
include something spurious which isn't really there, which would be removed if only we treated the
non-local exchange properly. If you do a Hartree-Fock band calculation, then the bands split in just the
way you expect from a Hubbard type consideration of the on-site interactions, as we've seen. So its not
really correct to say that one-electron bands have no meaning in strongly correlated materials.
Why else do people believe this? Because most text books say so. Many authors get confused between
the words 'correlation' in the quantum chemistry sense and the phrase 'strongly correlated', particularly
if they have a background in electronic structure theory. They think strong correlation is related to
7 108
if they have a background in electronic structure theory. They think strong correlation is related to
everything that is not in the Hartree-Fock Hamiltonian - but as we've seen that kind of correlation in
Mott insulators is just a short range screening effect which will change the numerical results, but will
not change the qualitative features of the ground state that we can calculate.
7 109
7-1 Tight-Binding Method
A. LINEAR COMBINATION OF ATOMIC ORBITALS
(1) Crystal Hamiltonian

The crystal potential can be approximated as a sum of atomic potentials
where is the potential due to one unit cell alone
Let
is periodic
In a crystal, the single-particle Hamiltonian can be written as
where encodes all the differences between the true potential in the
crystal and the potential of an isolated atom.
The single particle states are
The term in the equation above is assumed to be small and can be treated perturbatively.
(2) Atomic orbitals

The Schrodinger equation for an electron in an isolated atom is
where is the atomic orbital (wave function)
These wave functions decay rapidly away from and so the overlap integral between wave
functions located on separate atomic sites in the crystal is small.
EXAMPLES:
The atomic orbitals in a 1D crystal
7 110
The translation vectors are
The nearest neighbor vectors are
(3) Linear combination of atomic orbitals (LCAO) (John Lennard-Jones, 1929)

In a periodic potential, the single particle state must obey Bloch's condition, i.e.
where is a lattice translation vector
Clearly, a single orbital does not satisfy Bloch's theorem, but we can easily make a LCAO
where there are lattice sites and the factor of ensures the Bloch state is normalized.
PROOF:
(4) Normalization of LCAO wave function
and
7 111
B. CALCULATION OF THE BAND STRUCTURE
(1) Single -band

Assume that a crystal has one atom in the unit cell and where only atomic -orbitals contribute to
the crystal states.
Energy band (dispersion relation)

The energy of a state is given by
(2) We classify the sum over according to the distance between two atoms:
1. zero distance
2. nearest neighbor distance
Empirically, we do not attempt to evaluate the overlap integral. Instead we adjust to match
experiments.
The energy dispersion is
C. ONE-ATOM BASIS
(1) Single -band in a 1D crystal
The 2 nearest neighbors are
7 112
The dispersion relation describes how the energy varies with the crystal momentum .
The bands width depends upon the degree of overlap in the atomic orbitals from which they arise.

The 4 nearest neighbors are and

Face centered cubic crystal
The 12 nearest neighbors are , , and
OS:
Tight-binding approximation gives the correct band structure. However, such a method does not
show the band gap which comes from the interaction between a periodic potential and electron.
D. TWO-ATOM BASIS
(1) Polyacetylene [pali-Uh-set-l-een]

The carbon atom has the electronic conguration . In conjugated polymers the two
orbitals in the plane (i.e., and ) will combine with the orbital to give an hybridization.
The structure of polyacetylene: the backbone contains conjugated double bonds.
7 113
Metal:
Each carbon atom contributes a single -orbital.
(2) Nearest neighbors (overlap integral in a unit cell)
The LCAO wave function
where and atoms in the unit cell.

The translation vector for is
The crystal states are
The dispersion relations are
With 2 atoms in the unit cell, we get 2 valid solutions at each , i.e. 2 bands.
For the nearest neighbors or
7 114
Since polyacetylene is a 1D crystal and is in the -direction.
Band folding:
(3) Constant energy contour & Fermi surface
Fermi surface is a pair of points at
(4) Next nearest neighbors (overlap integral between unit cells)

The translation vectors for are
The dispersion relation is
Similarly,
7 115
OS:
The difference between intra-cell overlap integral and inter-cell overlap integral can be
considered as a periodic potential which cause the band gap at the zone boundary.
7 116
7-2 Wannier Wave Function
A. WANNIER [Wan-nier] FUNCTIONS (1937)
(1) A Bloch function is periodic in by reciprocal lattice vector , can be expressed by a Fourier
representation with non-zero coecients only for Bravais-lattice vectors .
The Wannier function depends only on the difference .
(2) Wannier function is a localized function centered on the real-space lattice site .
PROOF:
Using periodic boundary condition
Considering the case
(3) The orthogonality relation
7 117
Wannier functions corresponding to centered on different lattice sites are orthogonal.
B. SECOND QUANTIZAZTION REPRESENTATION
(1) Wannier basis
Orthonormal
Completeness
(2) The tight-binding Hamiltonian is
1. For , i.e.
is close to the atomic eigenvalue and plays the role of a reference energy.
2. For
is called the hopping integral (or just hopping), and can be viewed as a kinetic energy due to
tunneling across a potential barrier between two lattice sites. depends only on the distance
between sites .
(3) Let and be the creation and annihilation operators on lattice site .
maps state on site onto the state on site
electron hops from site to site
maps state on site onto the state on site

electron density on site
7 118
(4) Diagonalization
Let and
C. MONOVALENT SQUARE LATTICE
(1) Band structure

Nearest-neighbor hopping: or
(2) Constant energy contour & Fermi surface

1. Near point
7 119
The constant energy contour is a circle.
2. Near point
The constant energy contour breaks into four disjoint components which encircle the corners of
the point.
(3) Half-filling
1. Fermi surface
The Fermi surface flattens out along the diagonal directions.
GRAPHICALLY PROOF:
The band filling is the ratio of the surface area enclosed by the Fermi surface to the area of
the complete Brillouin zone. The square Fermi surface for corresponds to a half-filled
band.
2. Density of states
7 120
Large density of states near the Fermi energy (logarithmic divergent)
point
OS:
Next-nearest-neighbor hopping
D. GRAPHENE
(1) Honeycomb lattice
1. Primitive lattice vectors
2. Reciprocal lattice vector
7 121
2. Reciprocal lattice vector
3. Sublattices
Three nearest-neighbors of an A-sublattice atom
(2) The nearest-neighbor tight-binding Hamiltonian is
where is the creation operator for an atom on the A(B) sublattice.
(3) The Hamiltonian in terms of is
where
The eigenvalues of are given by
7 122
The eigenvalues of are given by
(4) Dirac points

1. The degeneracy implies that the discriminant between and vanishes, i.e.
Since must be a real number,
By adding and subtracting reciprocal lattice vector , there are 6 essentially equivalent
degeneracies at the corners of the first Brillouin zone.
2. For close to point
Let
Extract an overall constant factor
Similarly
The eigenvalues are a function only of the magnitude of
(5) Density of states
7 123
OS:
7 124
7-3 Electronic Band Structure
A. CURVE OF ENERGY BAND
(1) Inverse slope of bands

Density of states is proportional to the inverse slope of the band:
Steep bands small DOS
Flat bands large DOS
determines properties:
: always nonmetallic
: often metalic
(2) Slope of bands

The mean velocity of an electron described by energy and wave vector is
(3) Curvature of bands

The effective mass of a charge carrier near a band minimum or maximum is inversely proportional to
the curvature of the band:
Parabolic approximation near minimum or maximum:
7 125
Parabolic approximation near minimum or maximum:
B. SYMMETRY OF ENERGY BAND
(1) Point-group symmetry: rotation with respect to axes and reflection across lines
Let be the operator for a point-group symmetry operation
Suppose one has solved the Schrodinger equation and obtained the Bloch state with energy
Replace by
Thus is also a Bloch state with the same energy as

From the Bloch theorem
The energy of is .
Therefore:
NOTE:
1. If is a symmetry of the potential such that in real-space , then the energy bands
also enjoy the symmetry of potential such that in -space: .
2. Degeneracies in the energy bands can therefore arise from crystal point-group symmetries.
(2) Inversion symmetry
Suppose one has solved the Schrodinger equation and obtained the Bloch state with energy
Replace by
We found a Bloch wavefunction with the same energy as

(3) Time-reversal symmetry

Suppose one has solved the time dependent Schrodinger equation and obtained the Bloch state
7 126
Suppose one has solved the time dependent Schrodinger equation and obtained the Bloch state
with energy
Let
We found a Bloch wavefunction with the same energy as

Replace by
This means that is the time-reversal state corresponding to the state .
The function is the time-reversal Bloch state corresponding to with the same energy as
.
Kramer's theorem (Kramer's degeneracy 1930): if time-reversal symmetry is not broken, all eigenstates
are at least doubly degenerate.
C. SPIN-ORBIT INTERACTION AND SYMMETRY
(1) Bloch states with spins:

The Bloch function can be written generally as a superposition of up and down spin states,
Lattice translation symmetry:
(2) Spin-orbit interaction:

An electron moving in an electric field sees an effective magnetic field
The electron has a magnetic moment related to its spin angular momentum by
where the Pauli matrices are
The interaction between the electron spin and the effective magnetic field adds a new term to the
Hamiltonian,
7 127
In the presence of spin-orbit coupling, spin is not a good quantum number
(3) Point-group symmetry

Let be the operator for a point-group symmetry operation
The Schrodinger equation
Replace by
Define a unitary spin rotation operator that operates in the Hilbert space of spins and rotates spin
states in the sense of the operator
Consider a spinor pointing in the direction
or
Introduction spin rotation operator corresponding to the rotation generated by the matrix
The new state has the same energy as

From Bloch theorem
(4) Inversion symmetry
The Schrodinger equation
Replace by
7 128
Replace by
The new state has the same energy as

From Bloch theorem
Since the total angular momentum operators are invariant under spatial inversion
So has the same angular momentum as

Therefore, we can write
(5) Time-reversal symmetry

The time-dependent Schrodinger equation
Solution:
Replace by
Try a transformation with the unitary matrix with the equation
where
where
The time-reversed Bloch state has the same energy as the original state.
From Bloch theorem
So the new solution is a Bloch state with wavevector
The total angular momentum operator
PROOF:
7 129
PROOF:
The new solution is also an eigenfunction of with an eigenvalue . Therefore, the new solution is
the Bloch state
with the same energy as

OS:
Time-reversal operator:
D. CRYSTAL SYMMETRY BROKEN
(1) Inversion symmetry broken

Rashba spin-orbital interaction breaks the inversion symmetry
Replace by
OS:
The Rashba effect, discovered in 1959 by a Soviet-American theoretical physicist Emmanuel
Rashba.
(2) Time-reversal symmetry broken

Magnetic field breaks the time-reversal symmetry
7 130
Replace by
7 131
A. NONDEGENERATE PERTURBATION
(1) Central Equation in the first Brillouin zone
Treat the periodic potential as a weak perturbation
We shall expand the solution as a Taylor series in :
(2) Substituting these expansions into the central equation gives
(3) Solve the equation above order by order in .

1. Order
The solutions ( empty lattice) have the form
All parabolic bands of the type centered around the reciprocal lattice vectors .
2. Order
a. For , only survives the sum
Let
b. For and
For a fixed and , and , , we can use nondegenerate
7 132
For a fixed and , and , , we can use nondegenerate
perturbation theory.
3. Failure of non-degenerate perturbation theory
In non-degenerate perturbation theory, the zero-order energy is non-degenerate.
Near the zone boundary
B. DEGENERATE PERTURBATION
(1) Assume that energy levels are close together within

1. For , one has
2. For , one has
Leading order in
(2) Suppose
Let
7 133
C. ENERGY GAP
(1) For close to (near the zone center)
The free electron approximation remains a good approximation near the zone center of the Brillouin
zone.
(2) For close to (near the zone boundary)
Similarly
OS:
Free-electron states near the zone boundary (dotted-line)
(3) Energy gap

In nearly degenerate case
7 134
is on the Bragg plane. The weak periodic potential has its major effects on only those electron levels
whose wave vector are close to the Bragg plane.
Group velocity at Bragg plane ( )
Bragg reflection at zone boundaries produce energy gaps (Peierls, 1930)

At
D. REDUCED ZONE SCHEME
(1) for BZ and BZ

PROOF:
is outside the BZ and is inside the BZ.
Both and are lattice-periodic, so is

is a Bloch function
(2) Band index
is multi-valued function of . Each branch of forms an energy band.

Bloch functions need band index
for BZ
single-valued
E. FERMI SURFACE
(1) Empty lattice
7 135
(1) Empty lattice
Suppose that the periodic crystal potential is vanishingly small. Then impose periodic structure without
distorting free electron dispersion curves
The constant energy surfaces are circular. For a monovalent element, the volume of the Fermi surface is
half that of the Brillouin zone.
(2) Nearly free electrons

1. With the crystal potential, the energy inside the first Brillouin zone is lower close to the zone
boundary. So the Fermi surface is extended towards the zone boundary as it gets close.
2. The Fermi surface cross the Brillouin zone boundary of a square lattice.
As a free-electron Fermi surface completely encloses the first Brillouin zone, the portions of the
Fermi surface in the second Brillouin zone is mapped back into the first Brillouin zone so that the
energy surface is continuous.
(3) Fermi surface is orthogonal to the zone boundary
7 136
At the zone boundary
7 137
7-5 Metal & Insulator
A. ELECTRIC FIELD ON ELECTRONS IN BANDS
(1) Quantum treatment of electric field
where
Assume the electric field is applied at time
The time evolution is
Since the term breaks the invariance of the lattice translation, the effect of the translation
operator is
and
Therefore
Although obeys Bloch's theorem with a time-dependent wave vector
is not an eigenfunction of .
If the electric field is turned off at time , without causing an interband transition (adiabatic
approximation), at subsequent times the electron will be found in an eigenstate of corresponding to
the wave vector . Since the turned off time is arbitrarily, the time evolution as if the electron were
continually visiting the states of with its wave vector varying in time is according to the equation of
motion
(2) Partial-filled band

When applied a field, the Fermi surface is shifted.
metal
(3) Filled band
7 138
(3) Filled band
Bragg reflection:
On crossing the zone boundary, the group velocity changes direction the electron is reflected.
When applied a field, electrons' -values increased.
Electrons at the zone boundary are Bragg reflected back to the other side of the zone.
insulator
A filled band does not carry current (Peierls, 1929)
EXAMPLES:
Divalent metal in two dimension: The area of -space needed to accommodate all the electrons is
equal to the area of the first Brillouin zone.
(a) Small gap
The filled states are in both the first and second zones.
metal
(b) Large gap
The whole of the first Brillouin zone are filled.

insulator
B. MAGNETIC FIELD ON ELECTRONS IN BANDS
Quantum treatment of magnetic field
7 139
(1) Quantum treatment of magnetic field
Peierls [Pei-erls/pay-earls] substitution
The gauge-invariance of the Schrodinger equation requires us to transform the wave function amplitude
at a site as
where
To include magnetic fields in lattice model, the integration path is chosen to be the shortest distance
over nearest neighbor bond.
Since is assumed approximately uniform at the lattice scale,
Peierls substitution for lattices
(2) The change in is perpendicular to both and
The electron stays on the constant energy surface
7 140
(3) Near the top of a band
The electrons are Bragg reflected at the edges of the Brillouin zone
The electrons orbit, in -space, the opposite way round occupied or unoccupied states.
The behavior looks like that of an opposite charged particle - a hole.
(4) Electrons in the second zone
Using the periodic nature of the system and redrawing the Fermi surface
This is electron-like behavior.
C. METAL & INSULATOR
(1) Difference between conductor and insulator (Wilson, 1931)

Metal: at least one band is partially occupied.
Insulator: all bands are either full or empty.
7 141
Insulator: all bands are either full or empty.
(2) Insulators exhibit an energy gap for singleelectron excitations as a results of electronion or electron
electron interactions.
1. Insulators can be understood in terms of a singleelectron theory:
(a) Band insulator (Bloch insulator): due to the interaction between electron and periodic
potential of the ions.
(b) Peierls insulator: due to the interaction between electron and static lattice deformations,
leading to a commensurate charge-density wave of the electrons.
(c) Anderson insulator: due to the interaction between electron and disorders, such as
impurities and lattice imperfections.
(d) Topological insulator: due to the interaction between electrons' spin and orbital.
2. Insulators arise from electron-electron interactions.
(a) Mott insulator: due to the strong correlation effects induced by large on-site Coulomb
interactions.
D. PEIERLS TRANSITION (1955)
(1) Monovalent 1D crystal
1. One atom per unit cell

The nearest-neighbor tight-binding Hamiltonian is
The eigenvalues are
The DOS is
7 142
(2) Lattice deformation (distortion)
where
The eigenvalues are
1. If
At
7 143
2. If
At
(3) Peierls instability

The ground state energy for the lattice distortion is
where
OS:
The ground state energy for free electrons is
The lattice deformation (dimerization) has an energy that is lower by a logarithmic factor. The elastic
energy gains lead to a lattice with short and long distances between neighboring atoms, so that the
bonding between atoms alternates on going along the chain.
Peierls' theorem: a one-dimensional equally spaced chain with one electron per ion is unstable.
E. CHARGE DENSITY WAVE
(1) Fermi surface nesting

There are two parallel pieces of a Fermi surface, such that a single q-vector can connect many points.
7 144
1D metal: Perfect nesting because the Fermi surface consists of two points at .
2D metal: NO good nesting because the Fermi surface is a circle. However, systems with stronger
interactions (or quasi 1D bands) can have Fermi surface nesting.
2D square lattice: Perfect nesting with at half filling.
(2) Charge density wave driven by nesting

OS:
As a disclaimer, not all charge density waves are driven by nesting, and not all Fermi surface
topologies with a good nesting condition result in a CDW instability.
A charge density wave (CDW) is a periodic modulation of charge density, and an accompanying
distortion of the crystal lattice.
The electrons near can lower their energy and open up a gap at wavevector (corresponding
to the Fermi surface nesting).
OS:
This won't work for a wavevector connecting two states deep in the Fermi sea (orange) because
the opening of a gap will raise the energy of electrons above the gap by an equal amount that
electrons below the gap lower their energy.
A 1D metal is always unstable to the Peierls distortion and introduces a new periodicity (CDW).
F. POLYACETYLENE
(1) Trans-polyacetylene
Two nearest-neighbors of an A-sublattice atom
The Hamiltonian is
7 145
The eigenvalues are
(2) Charge density wave

1. For
Fermi wave vector . The polyacetylene is a metal.

2. For
The lattice is dimerized and the eective unit-cell dimension is . A spatially periodic CDW is
formed by the Fermi surface nesting .
The Fermi points and the 1st BZ coincide. A gap opens up in the band at the Fermi level. Bragg
scattering of the electron states at the Fermi points causes an electronic band gap to open at .
The polyacetylene is an insulator.

OS:
Is there a Fermi surface of the gapped polyacetylene?
If is defined as the energy separating the highest occupied from the lowest unoccupied
level, then it is not uniquely specified in a solid with an energy gap, since any energy in the
gap meets this test. People nevertheless speak of the Fermi energy. What they mean is
the chemical potential, which is well defined at any non-zero temperature. As , the
7 146
the chemical potential, which is well defined at any non-zero temperature. As , the
chemical potential of a solid with an energy gap approaches the energy of the middle of the
W
correct of colloquial definition, does not have a solution in a solid with a gap,
which therefore has no Fermi surface!
7 147
8-1 Many-Body Hamiltonian
A. THE MANY-BODY HAMILTONIAN
(1) The many-body Hamiltonian
Where
(2) Born-Oppenheimer approximation: the time scale of the motion of electrons is much larger than the
nuclei and thus the response time of the electrons to any change in the positions of the nuclei is
considered immediate.
(3) Jellium model

The positive ions behave like a rigid jelly with uniform density of positive charge. Jellium is just a
collection of electrons, into which ions are introduced as a spatially uniform background to maintain
overall charge neutrality, i.e.
The jellium Hamiltonian can then be written as
where
(4) There are two competing forces: the Coulomb energy versus the kinetic energy.
8 148
The competition between the two forces determines the properties of the material.
B. CRITERION
(1) Bandwidth
1. Wide bands:
The Coulomb interaction is well screened and the kinetic energy prevails. The system can be well
described by the one-electron theory based on Bloch's theorem.
2. Narrow bands:
The Coulomb interaction tends to localize the electrons and the system is an insulator at half
filling. The Mott insulating state is often found in the transition-metal oxides.
(2) Electron density

The ratio between Coulomb energy and kinetic energy is
where
is the average distance between electrons.

PROOF:
The kinetic energy per electron is
The average volume occupied by one electron is
1. High density limit

weakly correlated system
In this regime, the free electron approximation (ignoring interactions) is a good approximation.
Electrons localized in -space (Fermi liquid behavior)

2. Low density limit
8 149
2. Low density limit
strongly correlated system
In this regime, electrons want to say as far away from each other as possible to reduce the
interaction energy. In 2D, they form a close pack structure (a triangular lattice), called Wigner
crystal.
Electrons localized in real space (Wigner crystal)
8 150
8-2 Hatree-Fock Approximation
A. VARIATIONAL PRINCIPLE
(1) A function for which is stationary, i.e., , is the eigenfunction of the energy.
PROOF:
Use the Lagrange multiplier
The Lagrange multiplier is equal to the energy eigenvalue.

States whose expectation energy is stationary with respect to any variation in the wave function
are the solutions of the Schrodinger equation.
(2) Ground state energy: given a Hamiltonian with a discrete spectrum of eigenvalues whose lowest
eigenvalue is and given any wave function , we necessarily have
PROOF:
where are orthonormal set of eigenfunctions of .
Since the second term is either positive or zero, .

If the ground state is non-degenerate, the inequality is strict: only if
No trial function will have an expected energy value lower than the ground state energy of the
system.
B. HARTREE APPROXIMATION (1928)
(1) Hartree product

The total wave function is a product of orthonormalized single-particle wave functions, called atomic
orbitals.
where
(2) Hartree equation
The expectation value of the energy is
8 151
Renamed the dummy integration variables
Use the Lagrange multiplier
Each pair is counted only once.
The equation looks like a Schrodinger equation in which in addition to the Coulomb potential there is a
Hartree potential:
We obtain the Hartree equations
Each electron is governed by a single-particle Schrodinger equation experiencing the Coulomb potential
from the nuclei and from the other electrons.
OS:
In a real system, one electron feel the electric field induced by other electrons. This field varies
with time , because other electrons are moving. The Hartree approximation assumes that we can
substitute this varying electric by its average value, which is time-independent. Therefore, in the
Hartree approximation, we treat all other electrons as a static (not moving) and uniform
background. This charge background generate a static field, which shift the energy of our
electron. Because we only consider the average field, this approximation is also known as the
mean-field approximation.
C. HARTREE-FOCK APPROXIMATION (1930)
(1) The Slater determinant of electrons
The exchange of two particles is equivalent to the exchange of two columns which produces a change of
sign.
A wave function is differed from this by a single orbital
A wave function is differed by two orbitals
8 152
A wave function is differed by two orbitals
A wave function is differed by three orbitals
(2) Slater-Condon rule

1. Overlap integral
2. One-body operator
One body operators have non zero matrix elements only between two determinantal wave

3. Two-body operator
Two body operators have non zero matrix elements only between two determinantal wave

PROOF:
1. Overlap integral
Determinant expansion by minors along the first row
8 153
Suppose the determinants differ in one single particle state ( -th orbitals)
If and
If and
OS:
Expanding determinant along the -th column
2. One-body operator
Suppose the determinants differ in one wave function ( -th orbitals)
8 154
Suppose the determinants differ in two wave function ( -th and -th orbitals)
3. Two-body operator
Suppose the determinants differ in one wave function ( -th orbitals)
8 155
where
Suppose the determinants differ in two wave function ( -th and -th orbitals)
where
Suppose the determinants differ in three wave function ( -th, -th, and -th orbitals)
(3) Hartree-Fock equation
The self-interaction of an electron with itself in the bracket cancels out
(4) Let the Hartree potential
8 156
and the exchange potential
(It is typical of a nonlocal interaction.)
The Coulomb repulsion between the electrons leads to two terms, called the Hartree term describing a
uniformly spread charge distribution, and the Fock term resulting from the exchange hole.
D. STABILITY OF METALS
(1) In a metal, ions are introduced as a spatially uniform background and electrons are considered as free
electron gas, called jellium model.
Free electron wave function
The total electro-static energy of electron gas
charge neutrality
(2) The single particle energy becomes
The exchange energy (Fock term) is
Let
OS:
8 157
OS:
where is the Lindhard dielectric function

Let
8 158
The exchange interaction substantially lowers the energy. The metal is stable in HF approximation.
(3) Properties of the exchange interaction

The energy resulting from the Coulomb repulsion between the electrons
The pair correlation function (two-particle correlation function) of the uniform electron gas is
1. Consider :
2. Consider :
8 159
where
Exchange potential keeps electrons with the same spin apart, implying that the stability of metals relies
purely on quantum effect.
(4) Correlation energy

The total ground state Hartree-Fock energy is the sum of the kinetic energy and the Fock term.
The total energy per electron is
This estimate is roughly in agreement with the Alkali metals. The delocalized electrons are responsible
for the cohesion of the positive background yielding a stable solid.
The energy correction beyond HF approximation is called correlation energy.
1. High density electron gas:
OS:
M. Gell-Mann and K. A. Brueckner, Phys. Rev. 106, 364 (1957)
2. Low density electron gas:
8 160
OS:
W. J. Carr Jr., Phys. Rev. 122, 1437 (1961)
(5) Restricted Hartree-Fock and unrestricted Hartree-Fock calculations:

The wave functions are composed of two groups, spin-up and spin-down functions which have the same
spatial wave functions.
E. FAILURE OF HF APPROXIMATION
(1) The energy dispersion has a logarithmic singularity in the slope at
The Fermi velocity is
(2) The density of states at the Fermi level is zero called Coulomb gap.
(3) The failure of the HF approximation for jellium is caused by the nonlocality of exchange operator (Fock
term).
8 161
8-3 Random Phase Approximation
A. TIME DEPENDENT PERTURBATION
(1) Consider a time- and position-dependent weak external potential in an electron gas
Now restrict to one Fourier component in the spatial and time dependence of the potential
Let
where includes the adiabatic switching on of the potential.
Assuming the phase are random such that interference terms vanish on the average. The electrons
response to the Fourier components independently
(2)
(3) Dielectric constant
Let us consider that we put a time dependent potential in an electron gas
where and
In the presence of such a potential, we can use perturbation theory, namely the wave function
changes from to
where
Now let us consider the change in charge density due to this change in wave functions, we assume that
the electron gas can be approximated by a jellium model.
If , no charge fluctuation
Since the perturbation is real
8 162
The unperturbed
This charge distribution gives rise to a potential-energy field acting on electrons. This potential
satisfies the Poisson's equation
If we assume
To make our calculation self-consistent
where is the actual enternal potential and is the induced potential.
Dielectric constant
(4) Random phase approximation

The electrons response to the Fourier components independently
If we express by the Fourier integral
The effective potential seen by an electron is
EXAMPLES:
For a free electron gas
B. THOMAS-FERMI SCREENING (STATIC SCREENING)
(1) If we consider a static perturbation

For example, if we put an impurity with charge , in an electron gas, then the impurity produce a
potential
C. FRIEDEL OSCILLATION
8 163
(1)
A more complex treatment (which I won't go through here) involves calculating the Lindhard response
function of the electronic system, which describes the rearrangement of charge density in response to a
perturbation. This can be calculated for an arbitrary Fermi surface topology, and is shown below for
circular/spherical Fermi surfaces (free electron gas). This is a common way of showing that CDWs are
certain to occur in one dimension (diverging susceptibility=diverging response at ), but not
energetically favorable in 2 or 3 dimensions unless the Fermi surface has some 1D character.
8 164
8-4 Landau Quasiparticles
Friday, August 09, 2013 10:08 AM
A. NON-INTERACTING FERMIONS
(1) Ground state

Energy levels are filled following Fermi-Dirac distribution.
The ground state is electrons filled up to the Fermi surface.
(2) Excitation
Add one electron with momentum to ground state. The new electron occupies an eigenstate of the
system with momentum .
Let the difference in momentum

1.
2.
x -lived without decaying.

Excitations from the ground state is obtained by changing the occupation numbers of the single particle
levels, i.e. by changing the distribution function,
For discrete momentum states, can only take the values because of the Pauli principle.
8 165
B. INTERACTING FERMIONS
(1) Ground state

OS:
The coulomb repulsion force some electrons out of the Fermi surface in a very complicated way,
making the new ground state difficult to analyse with usual perturbation theory.
Gell-Mann & Low theorem (1951)
The ground state of an interacting theory can be related to the ground state of the corresponding non-
interacting theory with adiabatically switching on the interactions.
As the interactions are slowly turned on, the non-interacting states are assumed to smoothly and
continuously evolve into interacting states, and that this evolution takes place without hitting any
singular behavior. Such a singularity would signal an instability of the ground state and should be
viewed as a phase transition. Thus, if there are no phase transitions, there should be a smooth
connection between non-interacting and interacting states.
(2) Excitation (Landau 1957)

Add one electron with momentum to ground state of the interacting system. The additional electron
can not scatter into an occupied momentum state below the Fermi surface. The decay of the electron
state above the Fermi energy happens through scattering by creating particle-hole excitations.
Therefore, it changes its momentum from to , and then a hole appears at and a second
electron with wavevector is created outside the Fermi surface. All of them should satisfy the
conservation of energy and momentum, i.e.,
(3) Lifetime
OS:
The Fermi function guarantee that the state is indeed occupied by an electron, while the final
states and are empty and therefore available for occupation after the scattering
event.
We start by writing the expression for the dynamic structure factor,
Let be the energy spectrum for individual electron-hole pairs
and be the energy loss of the decaying electron.

For when is parallel to
8 166
Now we can carry out the integral
OS:
The momenta included by the region dened by and , which is the
crescent above the lower sphere. The shaded region (orange color) is found by overlaying two
fermi spheres and displacing one sphere by .
and where
Since
8 167
for slightly above the Fermi surface.
The excitations are asymptotically stable. Landau named these long-lived excitations "quasi-particles".
As the interaction is turned on, the one particle excitations of the ideal Fermi gas evolve into
quasiparticle excitations of a Fermi liquid.
OS:
Quasiparticle doesn't mean "not really a particle", it means "more than just a particle".
8 168
8-5 Landau Fermi Liquid Theory
Friday, August 09, 2013 10:08 AM
A. LANDAU FERMI LIQUID
(1) Quasiparticle concept

A quasiparticle is the adiabatic evolution of the non-interacting fermion into an interacting
environment.
The quasiparticles obtained are not the exact stationary states of the system, but a superposition of
a large number of exact stationary states of the system with a narrow spread of energy.
(2) The Basic Assumption:

1. The weakly excited states of a Fermi liquid greatly resemble those of a weakly excited Fermi gas.
These states can be described with a set of elementary excitations with spin and momenta
close to the Fermi surface.
2. There is a one to one correspondence between the number of states of a perfect gas to that of a
normal Fermi liquid.
B. ONE-TO-ONE MAPING
(1) identical fermions in a volume at .
If the distribution function is changed by an infinitesimal small quantity , the total energy of the
system is changed by an amount
The functional derivative of the energy with respect to the distribution function is the kinetic energy of
a particle with wave vector
For zero temperature, is necessarily positive for and negative for since all the
energy levels are occupied below and are empty above it in the absence of interaction.
(2) The interaction is switched on adiabatically, that is without exchange of energy with the surroundings.
It is further assumed that the interaction is only repulsive because the ground state of an attractive
system may be radically different from that of the perfect gas.
Assumption:
1. The excitation spectrum of a Fermi liquid has the same structure as the excitation spectrum of a
perfect Fermi gas.
8 169
perfect Fermi gas.
2. The states of an ideal gas are transformed to those of a real gas as the interaction gradually
increases; the time development of each state can then be studied by means of perturbative
treatment.
OS:
A system with a non-degenerate stationary state cannot make a transition to another state
under the action of an infinitely slow perturbation.
(3) Since the states in the eigenstate basis vectors of the noninteracting system of the real system are in
general unstable and damp out after a certain time period , the adiabatic switching on of interaction
should require a time much shorter than . However, if the ,
state is no longer an eigenstate of the system. It is therefore necessary that the time period should be
large which implies that the excited states have a long lifetime. This thus limits the excited states to lie
in a low level close to the ground state.
C.
(1) When an additional particle of wave vector with is added to a Fermi gas in the ground state
and then the interaction is turned on, an eigenstate of the Fermi liquid is obtained. A quasi-particle of
wave vector
long near the Fermi surface. Thus the concept of quasi-particle is only valid in the neighbourhood of
. Similarly, a quasi-hole is the removal of a particle of wave vector with . Though the
same distribution function now characterizes the real states, it gives the distribution of quasi-
particles and not of real particles. It is assumed that the distribution of quasiparticles is spatially
homogeneous.
(2) The distribution of the quasiparticles in the ground state is thus still given by and the concept of
Fermi surface is retained
The excitation of the system is measured by . The excitation of the system is

measured by . As is appreciable only near the Fermi surface the quasi-
particles are well defined only in this region and poorly defined elsewhere. In other words, a quasi-
particle is an elementary excitation in the neighborhood of and gives no information about the
ground state of the real particles in the interior of the Fermi surface. The energy of the real system is
now a functional of ; i.e. .
(3) If is altered by an amount , the variation of energy to the first order is give by
where is interpreted as the energy of the quasiparticle. The relation is only valid when the number
of quasi-particles added or removed is small compared to the total number of particles in the system.
The energy of the whole system is the sum of the energies of the quasi-
between the energy of the ground state with particles and ( )
chemical potential of the system,
Instead, Landau proposed the following expansion for the total energy
The variation of the total energy is given by
8 170
Thus
where is the symmetric function , called Landau parameter.
(4) Since the quasiparticles are fermions, they obey Fermi-Dirac distribution
For low temperature, we find
8 171
8-6 First-Principles Calculations
A. DENSITY FUNCTIONAL THEORY
P. Hohenberg and W. Kohn, Inhomogeneous Electron Gas, Phys. Rev. 136, B864 (1964).
(1) Many-body problem
1. The usual approach to Schrodinger's equation can be summarized as
One among the observables is the particle density
2. The density functional approach can be summarized as
OS:
The DFT states that for ground states can be inverted: given a groundstate density it is
possible, in principle, to calculate the corresponding ground-state wave function
. This means that is a functional of . Consequently, all ground-state
observables are functionals of , too. If can be calculated from and vice versa, both
functions are equivalent and contain exactly the same information. At first sight this seems
impossible: how can a function of one (vectorial) variable be equivalent to a function of
(vectorial) variables ? How can one arbitrary variable contain the same information
as arbitrary variables?
(2) Hohenberg-Kohn theorem

1. The potential is unique functional of the ground state density
One-to-one mapping .
PROOF:
Suppose and give the same ground state density
a. If
b. If
Add two equations above, we would obtain , a contradiction. There

cannot be two different that give the same for their ground state.
2. The universal functional
The ground state energy
does not depend on the external potential and is the same for all electronic system.
OS:
The explicit form of the functional is the major challenge of DFT, i.e., the biggest
obstacle is the lack of an accurate expressions for the kinetic energy functional.
3. The true ground state density minimizes the energy function with the constraint
8 172
If is not the ground state density, then
PROOF:
Lagrange multiplier
B. KOHN-SHAM APPROACH
W. Kohn and L.J. Sham, Self Consistent Equations Including Exchange and Correlation Effects, Phys. Rev.
140, A1133 (1965).
(1) Kohn-Sham electrons

According to the Hohenberg-Kohn theorem, the one-to-one mapping is independent of the electron-
electron interaction , i.e.,
(2) Kohn-Sham approach

1. Non-interacting system
Two ways to calculate the density
(a) Schrodinger equation
(b) Euler-Lagrange equation
where
2. Real system
where the exchange-correlation energy
Euler-Lagrange equation
8 173
where
3. Kohn-Sham equation (to be solved self-consistently)
Approximate the system locally as homogeneous electron gas (Local Density Approximation: LDA)
Ansatz for
4. Total electronic energy
8 174
Summary Basic Equations
A. HARTREE EQUATION
B. HARTREE-FOCK EQUATION
C. KOHN-SHAM EQUATION
8 175
Appendix Math Background
A. LAGRANGE MULTIPLIERS
(1) Simple example

Maxmize the function subject to the constraint
(2) Inelegant approach

1. Solve the constraint equation for as a function of
2. Substitute into , yielding
3. Find the extrema of by differentiation
(3) Elegant approach

1. Write the constraint as
2. Define
where is a constant, independent of and

3. Minimize freely with no restriction between and
4. Enforce the condition

( x )
This method avoids differentiating square root, etc. This is especially important if we cannot solve the
constraint equation analytically.
8 176
Appendix QM Background
A. TIME DEPENDENT PERTURBATION
http://www.physicspages.com/tag/time-dependent-perturbation-theory/
B. SUDDENT CHANGE OF HAMILTONIAN (QUENCH)
C. ADIABATIC CHANGE OF HAMILTONIAN
D. HARMONIC PERTURBATION
E. DISCRETE-CONTINUOUS TRANSITION (FERMI'S GOLDEN RULE)
F. CONTINUOUS-CONTINUOUS TRANSITION
8 177

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Solid State Physics

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Solid State Physics

Dr. Hong-Yi Chen

National Taiwan Normal University

1. Prerequisite Knowledge: Quantum Mechanics, Statistical Mechanics

2. N. W. Ashcroft & N. D. Mermin, Solid State Physics (Saunders College).

3. Yuri Galperin, Introduction to Modern Solid State Physics (CreateSpace

4. J. M. Ziman, Principles of the Theory of Solids (Cambridge University Press).

5. Theoretical Physics Reference

1. Prerequisite Knowledge: Quantum Mechanics

(3) Any lattice point obtained from another point as with is

Nonmagnetic lattice constant:

(3) Wigner-Seitz cell (1934)

C. DISCRETE SYMMETRIES OF A UNIT CELL

(1) Discrete translation

(2) Point group: inversion, rotation, and reflection

2. 3D lattice (classified in 7 categories)

A. FOURIER SERIES OF BRAVAIS LATTICE PERIODIC FUNCTION

where is continuous in general.

3. Assume is periodic with period :

where is the volume of a unit cell.

An arbitrary point on the lattice is given by

is independent of the size of the finite system.

(1) One way to satisfy is to construct such that they obey

is the volume of the unit cell.

(2) Bragg diffraction (1913)

(3) Laue equation

B. EQUIVALENCE BETWEEN BRAGG'S LAW AND LAUE CONDITION

(1) Miller indices (1839)

Considering two vectors and lie on the lattice plane.

The reciprocal lattice vector is perpendicular to the plane .

(4) From Laue equation

(5) Ewald sphere construction (1913)

(1) Scattering from a lattice

The intensity is proportional to

where is the Fourier component of the charge density.

(2) Scattering from a lattice with basis

The atomic form factors are the same, i.e.

A. BRILLOUIN ZONE (1930)

B. FIRST BRILLOUIN ZONE

(2) Symmetric points

C. BRILLOUIN ZONE FOLDING

(1) Modulated crystallography

2. Commensurately modulated aperiodic crystal

The new periodicity is irrational.

(2) The X-ray diffraction pattern

2. Commensurately modulated aperiodic crystal

The satellite locations are defined by a vector

All components of the vector are rational.

(3) Brillouin zone folding

2. Reciprocal space (First Brillouin zone)

3. Reciprocal lattice vectors

A. HAMILTONIAN FOR PERIODIC POTENTIAL

(1) Lattice translation symmetry

(2) Lattice translation operator

(3) The eigenvalues of translation operator are exponential.

commute with and have the common eigenfunctions

B. BLOCH [B-loch] CONDITION

(2) Bloch condition

A. SCHRODINGER EQUATION IN THE PERIODIC POTENTIAL

(1) The Schrodinger equation in the reciprocal lattice

can be expanded in a Fourier series of the reciprocal lattice vector .

where we do not assume that has the periodicity of the lattice.

(2) Maps into the first Brillouin zone

(3) The wave function of the -representation is