Solid State Physics
Dr. HongYi Chen
2017/5/26
National Taiwan Normal University Department of Physics 88 TINGCHOU RD. SEC. 4, TAIPEI 116, TAIWAN
1 第 1 頁
─Basic Notion─
1. 
Lattices 
11 Crystal Structures 12 Reciprocal lattice 13 XRay Diffraction 14 Brillouin Zone 

2. 
Bloch Theory 
21 Bloch Theorem 22 Bloch Wave Function 23 Supercells 

3. 
Phonons 
31 Lattice Vibrations
32 Quantum Mechanics of Atomic Vibrations 33 Phonons
Summary
Periodicity, Quasiparticles
─Metal─
4. 
Statistical Thermodynamics 
41 Review of Statistics 

42 Phonon Density of States 43 Lattice Specific Heat 44 Lattice Thermal Conductivity 

5. 
Free Particle Theory 
51 Drude Theory 

52 Sommerfeld Theory 

53 Electron Density of States 54 Electronic Specific Heat 55 Compressibility and Susceptibility 

6. 
Classical Transport 
61 Lorentz Theory 62 Boltzmann Equation 63 Transport Coefficient 64 Impurity Scattering 65 Phonon Scattering 

7. 
Band Theory 
71 TightBinding Method 72 Wannier Wave Function 73 Electronic Band Structure
1 第 2 頁
74 Nearly Free Electron Model 75 Metal & Insulator
8. Fermi Liquid Theory
81 Jellium Model
82 HatreeFock Approximation 83 Random Phase Approximation 84 Landau Quasiparticles 85 Landau Fermi Liquid Theory
86 FirstPrinciples Calculations 87 Stability of Fermi Liquid
Summary 
Basic Equations 
Appendix 
Math background 
1 第 3 頁
─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.theoreticalphysics.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).
1 第 4 頁
11 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. 
1 第 5 頁
(2)
Unit cell:
A unit cell has number of lattice points per unit cell primitive unit cell.
OS:
. When
, the unit cell is called
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:
1 第 6 頁
C.
(3)
Honeycomb lattice = Hexagonal lattice + 2point basis Lattice constant:
WignerSeitz 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 WignerSeitz cell.
EXAMPLES:
Twodimensional antiferromagnetic lattice
Lattice constant:
DISCRETE SYMMETRIES OF A UNIT CELL
(1)
Discrete translation
1 第 7 頁
Crystalline structure means spatial periodicity or discrete translational symmetry.
1. 2D lattice
2. 3D lattice
(classified in 7 categories)
1 第 8 頁
1 第 9 頁
A.
12 Reciprocal Lattice
2016年5月1日
下午 08:30
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
transform over the finite system are
where
is continuous in general.
, the Fourier transform and its inverse Fourier
2. Apply the periodic boundary conditions (Bornvon Karman boundary conditions):
where
is discrtized
OS:
The distance between neighboring points in the discrete
the system’s length along any direction. When
density of the speciﬁc solid in question (thermodynamic limit), the continuum.
space is inversely proportional to
is taken to inﬁnity and preserve the mass
values tend to a
The inverse Fourier transform becomes a Fourier series and
is the Fourier coefficient.
3. is periodic with period where Assume 
: 
and 
where is the volume of a unit cell. 
1 第 10 頁
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) reciprocal lattice and is defined by
such that
forms the basis of the
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.
(2)
6.
Proof
is preodic
An infinite system with periodic translational symmetry can be approximated by a finite number of lattice points with periodic boundary conditions.
1 第 11 頁
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 also primitive.
EXAMPLES:
Graphene
.
If the vectors
1 第 12 頁
are primitive, then
are
A.
13 XRay Diffraction
Tuesday, May 14, 2013
4:08 PM
CRYSTAL DIFFRACTION
(1) 
XRay Xrays interact with electronic shells of atoms in a solid. Electrons absorb and reradiate Xrays. The 

reflectivity of Xrays is of the order of Therefore, Xrays serve as a bulk probe. OS: 
, so that the penetration in the solid is deep. 

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, Xray diffraction cannot see the atoms directly. It only sees Bragg peaks in different positions and directions and of course their intensities after the Xray 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 Xrays scattered from all lattice points interfere constructively.
1 第 13 頁
B.
Two scatterers (lattice points) separated by a lattice translation vector
scattering is elastic, i.e. the wavelength of the incident and the scattered Xray is the same as
. We assume that the
.
The path difference between the Xray scattered from the two scatterers should be an integer number of wavelengths.
Let Constructive interference occurs when
Since
(diffraction condition)
, 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. 
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 第 14 頁
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 第 15 頁
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 第 16 頁
C.
DIFFRACTION AMPLITUDE
(1) 
Scattering from a lattice 



Scattering occurs due to the interaction of the incident Xray 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. scattered wave. The total amplitude of the scattering is given by 
, and a phase factor acquired by the 

The intensity is proportional to The charge density that is periodic lattice 
can be expanded in Fourier series of the reciprocal 

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 第 17 頁
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 第 18 頁
1 第 19 頁
14 Brillouin Zone 

Tuesday, May 14, 2013 
4:08 PM 

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 condition. vector connecting the origin and the plane should satisfy the diffraction 

In the similar way, draw other lines, which satisfy the diffraction condition. 



The enclosed area is called Brillouin zone. The vectors the crystal. at the zone boundary can be Bragg reflected by 

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 WignerSeitz primitive cell in the reciprocal lattice. The volume of the first Brillouin zone is (volume of the unit cell) 

OS: 
1 第 20 頁
EXAMPLES:
1. 1D chain
2. 2D rectangular lattice
(2)
Symmetric points
1. Square lattice
1 第 21 頁
C.
2. Honeycomb lattice
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 lattice constant. 
is a rational fraction or multiple of the 

3. Incommensurately modulated aperiodic crystal 

A 
structure can NOT repeat on a unitcell boundary. 



The new periodicity is irrational. 

(2) The Xray 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
EXAMPLES:
vector are rational.
1 第 22 頁
3. Incommensurately modulated aperiodic crystal
(3)
The satellite peaks of EXAMPLES:
vector, at least one component is irrational.
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 第 23 頁
3. Reciprocal space showing fundamental Bragg peak (filled circle) positions and antiferromagnetic
superlattice peak (open circle) at
.
1 第 24 頁
21 Bloch Theorem 

Tuesday, December 20, 2011 
8:30 PM 

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 [Bloch] 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 第 25 頁
A.
22 Bloch Wave Function
Tuesday, December 20, 2011
8:30 PM
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 The Schrodinger equation becomes 
has the periodicity of the lattice. 

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 第 26 頁
B.
The eigenenergy must also be labeled by
(4)
Crystal momentum
is conserved in crystals and
is only up to
BLOCH WAVE FUNCTION (1928)
(1) 
The Bloch wave function 

and a cellperiodic 

The periodic wave function can be written as the product of a cellinvariant part 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 PROOF:
2. The eigenenergy
PROOF:
is periodic in
space, i.e.
is periodic in
space, i.e.
2 第 27 頁
(3) 
There are 
points in the first Brillouin zone. 
PROOF: 
1. Bornvon Karman boundary conditions where Applying Bloch's theorem gives
are the total number of primitive cells in the crystal.
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 第 28 頁
A.
23 Supercells
Tuesday, December 20, 2011
8:30 PM
NONPERIODIC SYSTEM
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 第 29 頁
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 (Bornvon Karman boundary conditions) to the wavefunctions. 
, where
is the total number of supercells.
Bloch theorem in primitive cell:
2 第 30 頁
31 Lattice Vibrations 

Tuesday, December 20, 2011 8:26 PM 

A. 
LATTICE VIBRATIONS 

(1) 
Consider identical atoms of mass 

atom from its equilibrium position with periodic boundary condition. For small displacement on the 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. 
ONEATOMIC LINEAR CHAIN 



(1) 
Dispersion relation and band structure 

Assume (spring constant) 

Trial function 
3 第 31 頁
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 第 32 頁
C.
2. At the boundary
The boundary modes can transfer energy.
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 Brillouin zone. 
must be folded back into the first 

(2) 
Dispersion relation 
Assume
3 第 33 頁
D.
(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
1. For
limit,
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.
3D LATTICES
(1)
Equation of motion
3 第 34 頁
(2)
where
is the polarization vector along
The dynamical matrix is
directions and
One gets the eigenvalue problem Eigenvectors
Eigenvalues
(normal modes)
The displacement can be written as
Periodic boundary condition
The wavevector
is
, satisfied for
where The set of
The total number of
are the reciprocal lattice vectors.
values is restricted to the first Brillouin zone.
values in the first Brillouin zone is
three primitive directions.
3 第 35 頁
A.
32 Quantum Mechanics of Atomic Vibrations
Tuesday, December 20, 2011
8:26 PM
CLASSICAL APPROACH (NORMAL MODES)
(1) 
Define normal coordinates (Fourier transform) 
(2) 
The Hamiltonian becomes 
which is the sum of OS:
independent simple harmonic oscillators.
3 第 36 頁
B.
QUANTUM MECHANICAL APPROACH (PHONONS)
(1) 
Schrodinger equation 

Eigenvalues 

Eigenfunctions 

where 
is Hermit [hurmit] polynomial. 

OS: 

Quantum mechanical approach gives the quantized frequency frequency can be considered as a particle with energy , i.e. the vibration with 

. 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 zeropoint vibration energy 

(2) 
Second quantization 
Introducing the creation
and annihilation
3 第 37 頁
operators
The Hamiltonian becomes
where
vibrational frequency in state The energy of one phonon is OS:
is the occupation number operator for phonons with energy
and polarization
.
.
,
is the
Second quantization approach gives the quantized intensities, i.e. the number of the particles
.
3 第 38 頁
33 Phonons 

Tuesday, December 20, 2011 
8:22 PM 

A. 
NONINTERACTING PHONONS 

Ignoring the interaction, the particle at th energy level is equivalent to put state. 
particles at the ground 

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. 
PHONONPHONON SCATTERING 

(1) 
Anharmonic term 
3 第 39 頁
Let 
and 
OS: 
The value of zone. Now define 
indicates the conservation of momentum is uniquely determined since 
must all lie within the ﬁrst Brillouin 
The Hamiltonian 
becomes 
(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 phononphonon scattering conserves crystal momentum and contains or 
3 第 40 頁
outside the first Brillouin zone.
3 第 41 頁
Summary Periodicity, Quasiparticles 

Tuesday, December 20, 2011 
8:22 PM 

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 diﬀerence being that in 

all the interaction processes quasimomenta are conserved with the accuracy of 
. 

C. 
TO BE 
3 第 42 頁
3 第 43 頁
A.
41 Review of Statistics
Tuesday, December 20, 2011
8:29 PM
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 with degeneracies 
particles (identical and indistinguishable) distribute into the energy level 

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 第 44 頁
(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 第 45 頁
B.
4.
Thermodynamics
(a) 
Thermodynamic potential 
(b) 
Entropy 
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
Internal energy
phonons distribute into the energy level
4 第 46 頁
with degeneracies
C.
(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 equilibrium number of phonons with a given frequency.
. The BoseEinstein function determines the
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 第 47 頁
(4)
Notice that for
goes to zero as
Helmholtz free energy
goes to zero.
4 第 48 頁
42 Phonon Density of States 

Tuesday, December 20, 2011 
8:26 PM 

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 [infini 

tesuhmuh l] range between 
and 
. 

B. 
DENSITY OF STATES (DOS) 

(1) 
Surface integral 

Let be the surface in space on which 
has the value 
. 


4 第 49 頁
C.
The frequency change
in terms of
in going from the surface
to the surface
, 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: 
VAN HOVE SINGULARITY (1953)
(1)
From the surface integral,
where
is the group velocity
4 第 50 頁
can be expressed
D.
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 The dispersions are flat at
value.
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) 
PHONON DENSITY OF STATES
(1)
Oneatom linear chain
where
The function has an absolute maximum for
The function has an absolute minimum for
The band width is The DOS is
1. Surface integral
2. Volume integral
4 第 51 頁
.
or
.
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 transfer energy.
(2)
Oneatom square lattice
The band width is The DOS is
4 第 52 頁
do not
The singularities occur as
(3)
Oneatom cubic lattice
The band width is
,
4 第 53 頁
The singularities occur as
,
4 第 54 頁
43 Lattice Specific Heat 

Tuesday, December 20, 2011 
8:26 PM 

A. 
DULONGPETIT LAW (1819) 

(1) 
The empirical DulongPetit 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 ﬁrst 

Brillouin zone and is the polarization of the mode. 
4 第 55 頁
(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 第 56 頁
C.
1. Lowtemperature limit:
2. Hightemperature limit:
DEBYE MODEL (1912)
(1) 
Debye assume: 

1. Atoms vibrate collectively in a wavelike 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 
4 第 57 頁
where
are the speed of a longitudinal and of a transverse sound wave.
(3) 
Internal energy 

Let 
and 
and ignore the zeropoint vibration energy, 

where 



(4) 
Limit 

1. 
Lowtemperature limit: 

2. 
Hightemperature limit: 
4 第 58 頁
4 第 59 頁
A.
44 Lattice Thermal Conductivity
Tuesday, December 20, 2011
8:26 PM
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 MaxwellBoltzmann velocity distribution
3. The energy flux along the
direction
4 第 60 頁
B.
(mean free time between collisions, i.e. relaxation time)
OS:
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. 

2. 
Scattering process: 
Phonons with small
values are excited.
The normal scattering processes do not degrade the thermal current. The rate of collisions between phonons
4 第 61 頁
(The conductivity rises more steeply with falling temperature.)
(3) 
At low temperature, 

1. 

2. 
Scattering process: 

Phonons with 
exist. 

The rate of collisions between phonons 

(4) 
The thermal conductivity of an insulator 
4 第 62 頁
51 Drude Theory 

Tuesday, December 20, 2011 
8:29 PM 

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 第 63 頁
C.
ELECTRONIC THERMAL CONDUCTIVITY
(1) 
The energy per electron at equilibrium at 
is 
. 



where 
is the thermal velocity 

(2) 
Specific heat 
5 第 64 頁
D. 
WIEDERMANNFRANZ 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 第 65 頁
F.
(2)
The complex dielectric constant
In the limit
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 Newton's equations become 
. The induced field 
is coupled to 
. 
5 第 66 頁
G.
(4) 
The conductivity tensor 
& resistivity tensor 
(5) 
Hall resistivity 
SPECIFIC HEAT
(1)
5 第 67 頁
H.
(2)
Experimentally, one finds a value of about
valence electrons (rule of Dulong and Petit), as if the electrons do not contribute at all.
at room temperature, independent of the number of
OUTCOME OF DRUDE MODEL
(1) 
Successes 
Dc conductivity 

Ac conductivity 

Electronic thermal conductivity 

WiedermannFranz law Plasma frequency 

Hall effect 

(2) 
Shortcoming 
Specific heat 
5 第 68 頁
A.
52 Sommerfeld Theory
Tuesday, December 20, 2011
8:30 PM
QUANTUM THEORY OF ELECTRON GAS (1928)
OS:
Arnold Johannes Wilhelm Sommerfeld (18681951)
(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) 
Bornvon Karman boundary conditions (periodic boundary condition): 
OS:
Advantage: allows the travelling wave
where
The periodic boundary condition permits only certain discrete values of
5 第 69 頁
.
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 cutoff at 
for particles described by the 

FermiDirac 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 第 70 頁
(4)
For 3D metal, the Fermi surface is a sphere.
The radius of the "sphere" is called the Fermi wave vector
.
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 第 71 頁
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 groundstate configuration.
5 第 72 頁
53 Electron Density of States 

Tuesday, December 20, 2011 
8:30 PM 

A. 
DENSITY OF STATES 

(1) 
Density of States between and 
: the number of energy states per unit volume in the infinitesimal range . 



(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 第 73 頁
2. Surface integral
3. Volume integral
(2)
2D
OS:
1. Countable
values
5 第 74 頁
2. Surface integral
3. Volume integral
(3)
3D
1. Countable
values
5 第 75 頁
C.
2. Surface integral
3. Volume integral
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 第 76 頁
(3)
At
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
mean energies of the majority of the electrons, with
compeltely filled, and remained. These electrons contribute nothing whatsoever to the macroscopic properties.
does not affect the
, since these electrons lie in states which are
A relatively small number of electrons
is significantly different from
and
, centered on
, do contribute to the macroscopic properties.
in the energy range of order
, in which
The fraction of active electrons lie in the tail region is
where
is
5 第 77 頁
The integral can be approximated as
5 第 78 頁
A.
54 Electronic Specific Heat
Tuesday, December 20, 2011
8:30 PM
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 第 79 頁
B.
where in metal,
(3)
Internal energy
ELECTRONIC SPECIFIC HEAT
, the lower limit of the integral can be replaced by
.
5 第 80 頁
C.
The internal energy becomes
(3)
The electronic specific heat is
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
5 第 81 頁
(2)
Explain the following figure
1. Specific heat of metal
2. Specific heat of insulator & metal
OS:
James William Rohlf, Modern Physics from
Strong experimental deviations from this number are observed for, for instance,
to
, Wiley, 1994.
,
, and
.
5 第 82 頁
,
,
A.
55 Compressibility and Susceptibility
Tuesday, December 20, 2011
COMPRESSIBILITY
8:30 PM
(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.
5 第 83 頁
B.
where
is the ionic mass and
is the number of electrons per atom
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, 
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 第 84 頁
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 EulerMaclaurin formula 
5 第 85 頁
(3)
The total susceptibility of a metal is
5 第 86 頁
61 Lorentz Theory 

Tuesday, December 20, 2011 8:29 PM 

A. 
DRUDE MODEL (REVIEW) 

(1) 
Dc conductivity (Ohm's law) 

where 
is the electron concentration 

(2) 
Electronic thermal conductivity 

(3) 
WiedermannFranz law (1853) 

B. 
KINETIC THEORY OF ELECTRON GAS 

OS: 

Hendrik Antoon Lorentz (18531928) 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 MaxwellBoltzmann 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 rate of change between final and initial distribution function is called collision integral, i.e. 
. The 

As the limit yields 

where 
is the nonequilibrium distribution function. 

OS: 

Nonequilibrium statistical mechanics 

C. 
LINEAR BOLTZMANN EQUATION 

(1) 
The total rate of change can be expanded as 
6 第 87 頁
D.
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
CONDUCTIVITY
is the thermal equilibrium distribution function and
is the relaxation time.
(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:
6 第 88 頁
(2)
Method 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 第 89 頁
(3)
WiedermannFranz law
6 第 90 頁
62 Boltzmann Equation 

Tuesday, May 14, 2013 
4:08 PM 

A. 
BOLTZMANN EQUATION 

(1) 
Nonequilibrium distribution function In thermodynamic equilibrium, the local electron distribution function is given by the FermiDirac distribution. 

When an external field is applied from outside, the electron distribution function is 
. 

(2) 
Liouville [Liouville] 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 sixdimensional 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 particles—the 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 diﬀerent volume of phase space. 

B. 
RELAXATIONTIME APPROXIMATION 

(1) 
Relaxation time ansatz 

If the external field creates a nonequilibrium distribution , and the field is then suddenly 

switched off, then from the moment of switching off 
6 第 91 頁
(2)
Scattering must serves to drive the nonequilibrium distribution back towards thermal equilibrium at
. In the relaxation time approximation
time
where
The solution is
As The relaxation time
via scattering to the equilibrium state when the external perturbation is switched off.
is therefore the time constant with which the nonequilibrium distribution relaxes
Stationary nonequilibrium distribution
When the uniform external field distribution function is desired.
=constant is not zero (
is the potential), the steady state
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 the equilibrium position.
EXAMPLES:
Ohmic conduction in solids
(a) Effects of the Fermi surface
6 第 92 頁
(DC external electric field)
from
The great majority of the electrons cancel each other pairwise, electrons in the shaded area remain uncompensated and produce the observed current.
(3)
(b) Effects of the distribution function
The new Fermi distribution
in the vicinity of the Fermi energy.
only differs significantly from the equilibrium distribution
Relaxation back to equilibrium The stationary nonequilibrium distribution is represented as a displaced Fermi sphere.
1. Inelastic scattering
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