Solid State Theory

Introduction to Solid State Physics
David M. Broun
Department of Physics
Simon Fraser University
Quantum Materials Program
Canadian Institute for Advanced Research
ii
D. M. Broun SFU/CIFAR QM
Contents
Table of Contents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
List of Figures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
List of Tables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
ii
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xv
1 Introduction
1.1 The free Fermi gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.2 Sommerfeld free electrons . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.3 The classical to quantum crossover . . . . . . . . . . . . . . . . . . . . . . .
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2 Thermodynamics and statistical mechanics

2.1 Review of thermodynamics . . . . . . . . . . . . . . . . . . .
2.2 Maxwell relations . . . . . . . . . . . . . . . . . . . . . . . .
2.3 Review of statistical mechanics . . . . . . . . . . . . . . . .
2.4 Statistical mechanics of ideal quantum gases . . . . . . . . .
2.4.1 Example: statistics of an impurity in a semiconductor
2.4.2 Example: interacting electrons in a metal . . . . . . .
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3 Thermal properties of the Fermi gas

3.1 Specific heat of an electron gas . . . . . . . . . . . . . . . . . . . . . . . . .
3.2 The Sommerfeld expansion . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3 Specific heat of the ideal Fermi gas . . . . . . . . . . . . . . . . . . . . . . .
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4 Review of single-particle quantum mechanics

4.1 Single-particle quantum mechanics . . . . . . . . . . . . . . . . . . . . . . .
4.2 The harmonic oscillator . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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5 Many-particle quantum systems

5.1 Quantum mechanics of many-particle systems . . . . .
5.2 Second quantization . . . . . . . . . . . . . . . . . . .
5.2.1 Occupation number representation . . . . . . .
5.2.2 Representation of states in second quantization
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iii
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iv
CONTENTS
5.2.3
5.2.4
5.2.5
Representation of operators in second quantization . . . . . . . . . .

Field operators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Examples of second quantized operators . . . . . . . . . . . . . . . .
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6 Applications of second quantization

6.1 The tight-binding model . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6.2 The jellium model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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7 The
7.1
7.2
7.3
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51
HartreeFock approximation
A model two-electron system. . . . . . . . . . . . . . . . . . . . . . . . . . .
The HartreeFock approximation . . . . . . . . . . . . . . . . . . . . . . . .
HartreeFock theory for jellium . . . . . . . . . . . . . . . . . . . . . . . . .
8 Screening and the random phase approximation

8.1 Screening . . . . . . . . . . . . . . . . . . . . . .
8.2 ThomasFermi theory . . . . . . . . . . . . . . .
8.3 The density operator . . . . . . . . . . . . . . . .
8.4 The random phase approximation . . . . . . . . .
8.5 Collective excitations of the electron gas . . . . .
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11 The nearly free electron model and tight binding

11.1 Degenerate electrons in a periodic potential . . . . . . . . . . . . . . . . . .
11.2 The tight binding method . . . . . . . . . . . . . . . . . . . . . . . . . . . .
11.2.1 Introduction to tight binding . . . . . . . . . . . . . . . . . . . . . .
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9 Scattering and periodic structures

9.1 The Born approximation . . . . . . . . . . .
9.2 Periodic structures . . . . . . . . . . . . . .
9.2.1 Convolution as a means of replication
9.2.2 The convolution theorem . . . . . . .
9.3 The reciprocal lattice . . . . . . . . . . . . .
10 The
10.1
10.2
10.3
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nearly free electron model

Blochs theorem . . . . . . . . . . . . . . . . .
Free electron in 1D as a Bloch wave . . . . .
Nearly free electrons . . . . . . . . . . . . . .
10.3.1 Properties of UG . . . . . . . . . . . .
10.4 The Schrodinger equation in momentum space
10.5 The periodic potential as a weak perturbation
10.5.1 The nondegenerate case . . . . . . . .
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CONTENTS
12 The tight-binding approximation

12.1 Degenerate tight-binding theory . . . . . . . . . . . . . . . . . . . . . . . . .
12.1.1 Example 1: s-like band in a face-centred cubic crystal . . . . . . . . .
12.1.2 Example 2: p-like bands in a face-centred cubic crystal . . . . . . . .
13 Energy bands and electronic structure
13.1 Review of the nearly free electron model . . . . .
13.2 Free electron Fermi surfaces in 2D . . . . . . . . .
13.3 Electrons and holes . . . . . . . . . . . . . . . . .
13.4 Metals, semimetals, insulators and semiconductors
14 Electronic structure calculations
14.1 Orthogonalized plane waves and pseudopotentials
14.1.1 Example: the need for pseudopotentials . .
14.2 Orthogonalized plane waves . . . . . . . . . . . .
14.3 Relativistic effects . . . . . . . . . . . . . . . . . .
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15 Density functional theory

15.1 The HohenbergKohn theorem . . . . . . . . . . . . . .
15.1.1 Proof of the HohenbergKohn theorem . . . . .
15.1.2 Proof of the second HohenbergKohn theorem .
15.2 Application of the HohenbergKohn theorem . . . . . .
15.3 The KohnSham equations . . . . . . . . . . . . . . . .
15.4 The local density approximation . . . . . . . . . . . . .
15.5 ThomasFermi as a density functional theory . . . . .
15.6 What can be calculated with density functional theory?
16 The
16.1
16.2
16.3
dynamics of Bloch electrons I

Energy bands and group velocity . . . . . . . . .
Rules of the semiclassical model . . . . . . . . . .
The kP method . . . . . . . . . . . . . . . . . . .
16.3.1 First order terms: . . . . . . . . . . . . . .
16.3.2 Second order terms: . . . . . . . . . . . . .
16.4 Consequences of the semiclassical model . . . . .
16.4.1 Electrical current . . . . . . . . . . . . . .
16.4.2 Thermal current . . . . . . . . . . . . . .
16.4.3 Filled bands . . . . . . . . . . . . . . . . .
16.4.4 Electrons and holes . . . . . . . . . . . . .
16.5 Semiclassical motion in a uniform dc electric field
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105
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111
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119
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vi
CONTENTS
17 The dynamics of Bloch electrons II

17.1 Semiclassical motion in a uniform magnetic field
17.1.1 The cyclotron frequency . . . . . . . . .
17.2 Limits of validity of the semiclassical model . .
17.3 Magnetic breakdown . . . . . . . . . . . . . . .
18 Quantum oscillatory phenomena
18.1 Quantum mechanics of the orbital motion . .
18.2 Degeneracy of the Landau levels . . . . . . . .
18.3 Landau levels in a periodic potential . . . . .
18.4 Visualizing Landau quantization . . . . . . . .
18.5 Quantum oscillations as a Fermi surface probe
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19 Electronic structure of selected metals

19.1 Construction of free-electron Fermi surfaces . . . . . .
19.1.1 Free-electron Fermi surfaces in two dimensions .
19.1.2 Free-electron Fermi surfaces in three dimensions
19.2 The alkali metals . . . . . . . . . . . . . . . . . . . . .
19.3 The noble metals . . . . . . . . . . . . . . . . . . . . .
19.4 Divalent metals . . . . . . . . . . . . . . . . . . . . . .
19.5 The trivalent and tetravalent metals . . . . . . . . . . .
19.6 Transition metals . . . . . . . . . . . . . . . . . . . . .
20 Strongly correlated systems & semiconductors
20.1 Interactions and the Hubbard U . . . . . . . . .
20.2 Measuring the Hubbard U . . . . . . . . . . . .
20.3 3d transition metals . . . . . . . . . . . . . . . .
20.4 Semiconductor structures . . . . . . . . . . . . .
20.5 Semiconductor chemistry . . . . . . . . . . . . .
20.6 Bonding, nonbonding and antibonding states . .
20.7 Electronic structure . . . . . . . . . . . . . . . .
20.7.1 Spinorbit coupling . . . . . . . . . . . .
20.8 Other semiconductors . . . . . . . . . . . . . . .
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129
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139
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149
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156
157
158
160
161
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163
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164
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169
170
171
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CONTENTS
vii
21 Semiconductors
21.1 Homogeneous semiconductors . . . . . . . . . . . . . . . .
21.1.1 Carrier density in thermal equilibrium . . . . . . .
21.1.2 The nondegenerate case . . . . . . . . . . . . . . .
21.1.3 The intrinsic case . . . . . . . . . . . . . . . . . . .
21.1.4 The extrinsic case . . . . . . . . . . . . . . . . . . .
21.1.5 Impurities . . . . . . . . . . . . . . . . . . . . . . .
21.1.6 Population of impurity levels in thermal equilibrium
21.1.7 Thermal equilibrium carrier density . . . . . . . . .
21.1.8 Transport in nondegenerate semiconductors . . . .
21.2 Inhomogeneous semiconductors . . . . . . . . . . . . . . .
21.2.1 The p-n junction . . . . . . . . . . . . . . . . . . .
21.3 The p-n junction as a rectifier . . . . . . . . . . . . . . . .
22 The
22.1
22.2
22.3
22.4
22.5
22.6
Boltzmann transport equation

The distribution function . . . . . .
The continuity equation . . . . . .
The Boltzmann equation . . . . . .
The linearized Boltzmann equation
The relaxation time approximation
Transport properties of metals . . .
22.6.1 Electrical conductivity . . .
22.6.2 Thermal conductivity . . . .
22.7 The WiedemannFranz law . . . .
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23 Time-dependent perturbation theory

23.1 Time-dependent perturbation theory
23.2 Sudden perturbations . . . . . . . . .
23.3 Adiabatic perturbations . . . . . . .
23.4 Periodic perturbations . . . . . . . .
23.5 Fermis golden rule . . . . . . . . . .
23.6 The Kubo formula . . . . . . . . . .
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24 Density response of the electron gas

24.1 Time and space dependent perturbations
24.2 Density response . . . . . . . . . . . . .
24.3 Energy loss . . . . . . . . . . . . . . . .
24.4 Screening and the dielectric function . .
24.5 Properties of the RPA dielectric function
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175
175
175
176
177
178
178
179
180
180
181
181
184
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187
187
189
189
190
191
192
192
193
193
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195
195
197
197
197
198
199
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203
203
205
206
207
208
viii
CONTENTS
25 Electrons in one dimension

25.1 One dimensional conductors . .
25.2 The Peierls instability . . . . .
25.2.1 Static lattice distortions
25.2.2 The energy balance . . .
25.3 Kohn anomalies . . . . . . . . .
25.4 Nesting of the Fermi surface . .
25.5 Spincharge separation . . . . .
25.6 The LuttingerTomonaga model
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26 Collective modes and response functions

26.1 Response functions . . . . . . . . . . . .
26.2 Collective modes . . . . . . . . . . . . .
26.3 Inelastic scattering . . . . . . . . . . . .
26.4 Causality . . . . . . . . . . . . . . . . .
26.5 Optical conductivity . . . . . . . . . . .
26.6 Oscillator strength sum rule . . . . . . .
27 The
27.1
27.2
27.3
27.4
27.5
27.6
27.7
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electron spectral function

The Schrodinger representation . . . . . .
The Heisenberg representation . . . . . . .
Particles and quasiparticles . . . . . . . .
A single free particle . . . . . . . . . . . .
The spectral function . . . . . . . . . . . .
Interacting systems . . . . . . . . . . . . .
Angle resolved photoemission spectroscopy
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28 Landaus Fermi Liquid theory

28.1 The noninteracting Fermi gas . . . . . . . . . . .
28.2 Excited states . . . . . . . . . . . . . . . . . . . .
28.2.1 Heat capacity . . . . . . . . . . . . . . . .
28.2.2 Pauli spin susceptibility . . . . . . . . . .
28.3 Landau quasiparticles . . . . . . . . . . . . . . . .
28.4 Quasiparticle decay rate . . . . . . . . . . . . . .
28.5 Landaus Fermi liquid theory . . . . . . . . . . . .
28.5.1 Interactions between quasiparticles . . . .
28.6 Experimental consequences of Fermi liquid theory
28.6.1 Heat capacity . . . . . . . . . . . . . . . .
28.6.2 Spin susceptibility . . . . . . . . . . . . .
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211
211
212
212
213
215
217
217
217
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221
221
221
222
223
225
227
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229
229
229
230
230
232
233
235
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239
239
241
242
242
243
244
246
246
247
248
248
CONTENTS
29 Superconductivity I phenomenology
29.1 Superconductivity . . . . . . . . . . . .
29.2 Perfect conductivity . . . . . . . . . .
29.3 The MeissnerOchsenfeld effect . . . .
29.4 The London theory . . . . . . . . . . .
29.5 Flux trapping and quantization . . . .
29.6 The Josephson effect . . . . . . . . . .
30 Superconductivity II pairing theory
30.1 The Cooper problem . . . . . . . . . .
30.2 The origin of the attractive interaction
30.3 BardeenCooperSchrieffer theory . . .
30.4 The Bogoliubov transformation . . . .
ix
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31 Superconductivity III exotic pairing

31.1 Conventional superconductors . . . . . . . .
31.2 Pairing glue . . . . . . . . . . . . . . . . . .
31.3 Andersons theorem . . . . . . . . . . . . . .
31.4 Unconventional pairing in specific materials
31.4.1 Cuprate superconductivity . . . . . .
31.4.2 Heavy fermion superconductivity . .
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251
251
251
252
253
255
255
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259
259
261
263
264
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267
267
267
269
270
270
274
CONTENTS
List of Figures
1.1
1.2
1.3
Allowed momentum states in two dimensions . . . . . . . . . . . . . . . . . .

The Fermi sea . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Evaporative cooling of trapped atoms . . . . . . . . . . . . . . . . . . . . . .
2.1
2.2
2.3
2.4
Gibbs energy surface . . . . . . . . . . . . . . . . . . . . . .

Dopant energy levels in a semiconductor . . . . . . . . . . .
Statistics of the dopant states with and without interactions
Quasiparticle distribution functions . . . . . . . . . . . . . .
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8
14
15
16
3.1
3.2
Density of states of the electron gas . . . . . . . . . . . . . . . . . . . . . . .

The Fermi function . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
18
20
4.1
Energy eigenstates of the harmonic oscillator. . . . . . . . . . . . . . . . . .
28
6.1
Tight binding on a square lattice . . . . . . . . . . . . . . . . . . . . . . . .
41
7.1
7.2
7.3
HartreeFock self consistency loop . . . . . . . . . . . . . . . . . . . . . . . .

HartreeFock function . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Energy dispersion in the HartreeFock model . . . . . . . . . . . . . . . . . .
50
52
53
8.1
8.2
The response of the electron gas to an external charge. . . . . . . . . . . . .

Excitations of the electron gas . . . . . . . . . . . . . . . . . . . . . . . . . .
57
61
10.1 Bragg scattering. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

10.2 The extended zone scheme . . . . . . . . . . . . . . . . . . . . . . . . . . . .
10.3 The reduced zone scheme . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
69
71
72
11.1
11.2
11.3
11.4
11.5
77
78
79
80
81
Degenerate energy bands . . . . . . . . . . . . .

Band gaps in the energy dispersion . . . . . . .
States at the zone boundary . . . . . . . . . . .
Construction of energy bands in one dimension .
Free electron bands of the FCC structure . . . .
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3
4
5
xii
LIST OF FIGURES
11.6 Fermi surface construction in two dimensions . . . . . . . . . . . . . . . . . .
11.7 A model of a one-dimensional metal. . . . . . . . . . . . . . . . . . . . . . .
11.8 Orthogonalization of atomic orbitals . . . . . . . . . . . . . . . . . . . . . .
82
83
84
12.1 s-like band in a FCC crystal . . . . . . . . . . . . . . . . . . . . . . . . . . .

12.2 p-like bands in a FCC crystal . . . . . . . . . . . . . . . . . . . . . . . . . .
91
93
13.1
13.2
13.3
13.4
13.5
13.6
13.7
13.8
Bragg planes and reciprocal lattice vectors . . . . . . . . . . .

Energy dispersion in one and two dimensions . . . . . . . . . .
Brillouin zones of the square lattice . . . . . . . . . . . . . . .
Fermi surface of a tetravalent square lattice . . . . . . . . . .
Second and third zone Fermi surface pockets of the tetravalent
The Harrison construction in three dimensions. . . . . . . . .
Schematic views of the density of states . . . . . . . . . . . . .
Broadening of atomic levels into energy bands . . . . . . . . .
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square
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lattice
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98
98
99
100
101
102
103
104
14.1 Pseudopotentials and pseudowavefunctions . . . . . . . . . . . . . . . . . . . 107

14.2 Pseudopotentials and pseudowavefunctions for silver . . . . . . . . . . . . . . 108
16.1 The hierarchy of length scales in a Bloch wavepacket. . . . . . . . . . . . . . 120
16.2 Displacement of the Fermi surface in k-space . . . . . . . . . . . . . . . . . . 127
16.3 Bloch oscillations of the electron velocity . . . . . . . . . . . . . . . . . . . . 128
17.1
17.2
17.3
17.4
17.5
17.6
Cyclotron orbits in a magnetic field . . . . . . . .

The relation between real and k-space orbits . . .
Construction for calculating the cyclotron period
The energy dispersion near a Bragg plane . . . . .
The conditions for magnetic breakdown . . . . . .
A Fermi surface undergoing magnetic breakdown
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130
131
132
135
136
137
18.1
18.2
18.3
18.4
18.5
Quantum states in a strong magnetic field .

Oscillations of the thermodynamic potential
Periodicity of quantum oscillations in inverse
De Haasvan Alphen oscillations in SrRu2 O4
The Fermi surface of SrRu2 O4 . . . . . . . .
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143
146
146
147
147
19.1
19.2
19.3
19.4
19.5
Bragg planes and Brillouin zones in two dimensions . . . .

Constructing the two dimensional Fermi surface . . . . . .
Free-electron Fermi spheres for the FCC structure . . . . .
Free-electron Fermi surfaces for FCC structures of different
Free-electron Fermi surfaces for BCC structure . . . . . . .
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valence
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150
151
152
152
153
. . .
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field
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. . .
LIST OF FIGURES
xiii
19.6 Free-electron Fermi surfaces for HCP structure . . . .

19.7 The periodic table showing crystal structures at room
19.8 The periodic table showing crystal structures at room
19.9 Band structure of sodium . . . . . . . . . . . . . . .
19.10First Brillouin zone of the BCC structure . . . . . . .
19.11The Fermi surface of copper . . . . . . . . . . . . . .
19.12Band structure of copper . . . . . . . . . . . . . . . .
19.13The Fermi surface of beryllium . . . . . . . . . . . .
19.14Band structure of calcium . . . . . . . . . . . . . . .
19.15The Fermi surface of aluminium . . . . . . . . . . . .
19.16Free electron Fermi surfaces for the FCC structure . .
. . . . . . . . .
temperature I .
temperature II
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153
154
155
156
157
157
158
159
159
160
161
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164
164
167
168
169
170
171
172
173
173
The density of states of a doped semiconductor. . . . . . . . . . . . . . . .

Two views of the spatially varying electronic structure in a p-n junction. .
Carrier density, charge density and potential in a p-n junction . . . . . . .
The currentvoltage characteristic of a p-n junction, showing diode action.
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176
182
183
185
20.1 Density of states in a Mott insulator . . . . . . . . . . .

20.2 Ionization processes and the Hubbard U . . . . . . . . .
20.3 The diamond structure . . . . . . . . . . . . . . . . . . .
20.4 sp3 hybridization . . . . . . . . . . . . . . . . . . . . . .
20.5 Bonding and antibonding orbitals . . . . . . . . . . . . .
20.6 The band structure of silicon . . . . . . . . . . . . . . . .
20.7 Constant energy surfaces in germanium and silicon . . .
20.8 Spinorbit interaction and semiconductor band structure
20.9 The band structure of germanium . . . . . . . . . . . . .
20.10The band structure of GaAs . . . . . . . . . . . . . . . .
21.1
21.2
21.3
21.4
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22.1 Evolution of electron states in the semiclassical phase space . . . . . . . . . . 188

22.2 Electron distributions for electrical and thermal currents . . . . . . . . . . . 191
22.3 The WeidemannFranz law . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
24.1 Static susceptibility in one, two and three dimensions . . . . . . . . . . . . . 209
24.2 Friedel oscillations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
25.1
25.2
25.3
25.4
Free electrons in one dimension . . . . .

Dimerization in a one-dimensional solid .
Phonon softening and the Kohn anomaly
Fermi surface nesting . . . . . . . . . . .
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212
214
215
216
xiv
LIST OF FIGURES
26.1 Inelastic scattering as a probe of collective excitations . . . . . . . . . . . . . 223
26.2 Contours for evaluating the Fourier transform. . . . . . . . . . . . . . . . . . 224
26.3 Contours used for evaluating the Cauchy integral. . . . . . . . . . . . . . . . 225
27.1
27.2
27.3
27.4
27.5
27.6
Electron spectral function of a noninteracting system . .

Electron spectral function of an interacting system . . .
The energetics of photoemission . . . . . . . . . . . . . .
Experimental geometry for angle-resolved photoemission
Synchrotron-based photoemission experiment . . . . . . .
ARPES spectra for Sr2 RuO4 . . . . . . . . . . . . . . . .
28.1
28.2
28.3
28.4
28.5
28.6
The ground state distribution function. . . . . . . . . . . . . . . . . . . . . .

Particle and hole excitations near the Fermi surface . . . . . . . . . . . . . .
Partial spin polarization of a Fermi gas by the application of a magnetic field.
The adiabatic principle for the noninteracting case . . . . . . . . . . . . . . .
Kinematics of quasiparticle decay . . . . . . . . . . . . . . . . . . . . . . . .
Polarizations of the distribution function . . . . . . . . . . . . . . . . . . . .
240
241
243
244
245
248
29.1
29.2
29.3
29.4
29.5
The superconducting transition of mercury . . . . . .

The MeissnerOchsenfeld effect. . . . . . . . . . . . .
Superconducting ring containing a Josephson junction
Multiple branches of the Cooper pair kinetic energy .
Ground state supercurrent in superconducting ring .
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252
253
256
257
257
30.1
30.2
30.3
30.4
30.5
Effective interaction in an elastic solid . . . . . . . . . . . . . . .

Dynamic overscreening as a source of electronelectron attraction
Coefficients of the BCS variational wavefunction . . . . . . . . . .
Excitation energies of the normal and superconducting states. . .
Density of states in a BCS superconductor . . . . . . . . . . . . .
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262
262
265
266
266
31.1
31.2
31.3
31.4
31.5
31.6
Magnetic fluctuations as a pairing glue . . . . . . .

Dopingtemperature phase diagrams of the cuprates
Cuprate structure and antiferromagnetism . . . . .
d-wave pairing by antiferromagnetic fluctuations . .
d-wave density of states and superfluid density . . .
Quantum critical superconductivity in CePd2 Si2 . .
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268
270
271
272
273
274
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233
234
235
236
237
238
List of Tables
12.1 Some two-centre integrals . . . . . . . . . . . . . . . . . . . . . . . . . . . .
12.2 Complete table of two-centre integrals . . . . . . . . . . . . . . . . . . . . .
xv
95
96
xvi
LIST OF TABLES
Lecture 1
Introduction
While research in other areas of physics focuses on extremes of size and energy, condensed
matter physics explores the middle ground. At first sight, this might seem like a strange
place to make new discoveries, as the fundamental particles (electrons and nuclei) have been
known for over 100 years and the basic equation that governs their behaviour can be written
down directly:
elec =
H
X P2
X KZI e2
X ~2
1 X Ke2
1 X KZI ZJ e2
I
2
+
+
+
, (1.1)
2m i
2MI
|ri RI | 2 i6=j |ri rj | 2 I6=J |RI RJ |
i
I
i,I
where K = 1/40 , ri and RI label the coordinates of the electrons and nuclei respectively,
and ZI and MI are the nuclear charge and mass. This equation controls so much of what
goes on in the universe that some people call it The Theory of Nearly Everything. If we
were taking a reductionist approach, in which we were trying to find the simplest unified
description of a basic phenomenon, our task would essentially be done. However, it is one
thing to have identified the fundamental particles (electrons and nuclei) and the hamiltonian responsible for their evolution, and quite another to solve the equation, even for a
small number of particles, with sufficient accuracy to predict and understand the behaviour
that emerges. It is these emergent properties of condensed matter that make the subject so
interesting. Phenomena such as superconductivity and the fractional quantum Hall effect
(FQHE) were not predicted by solving Eq. 1.1, but were understood after the experimental
discoveries using approximate models and cleverly chosen wavefunctions. In both superconductivity and the FQHE, the characteristic physical properties are highly nonintuitive and,
in the latter case, the fundamental particles are strikingly different from those of Eq. 1.1
they are excitations with one third the charge of the electron.
There are two basic approaches to understanding electrons in solids, each with its own merits,
both of which we will look at during this course. The first is more traditional, and involves
making approximations to the full Schrodinger equation of the solid and then developing
schemes for carrying out calculations. This is the approach we will begin with. The second
method is more concerned with phenomena than calculations, and is therefore less prejudiced
about possible outcomes. This approach goes by the name of Collective Phenomena and
seeks to understand the new excitations that emerge in many body systems, excitations that
often have all the properties of real particles i.e. they are weakly interacting, with well
LECTURE 1. INTRODUCTION
defined charge and statistics. This will be the topic of later parts of the course.
1.1
The free Fermi gas
We can make several simplifying although not particularly well justified approximations to
Eq. 1.1. We can assume the ion cores are stationary, and throw away their dynamics. This
is called the BornOppenheimer approximation. It is often quite valid, although in making
it we will always miss out on some important things, such as the physics of lattice vibrations
and the phonon-mediated interactions responsible for conventional superconductivity.
The next approximation we make is to assume the electrons move independently of each
other, by removing the Coulomb interaction between them. With this approximation, Eq. 1.1
separates into a sum of identical Hamiltonians, one for each electron:
X
elec H
indep =
i,
H
H
(1.2)
i
2
X KZI e2
i = ~ 2i
+ const.
H
2m
|ri RI |
I
(1.3)
This equation is the basis for the one-electron band theory of solids, although it is quite a bad
approximation, and without interactions between electrons we miss out on many interesting
properties, such as magnetism.
As a final level of approximation, we can hammer the ion cores out flat and assume the
electrons move in a constant potential that confines them to the interior of the sample. This
is the basis of the Sommerfeld theory of metals, in which the only parts of the original
problem we keep are the electron kinetic energy and Fermi statistics.
X
indep H
free =
i,
H
H
(1.4)
i
2
i = ~ 2i + const.
H
2m
1.2
(1.5)
Sommerfeld free electrons
We begin by calculating the ground state properties of N free electrons confined to a volume
V . Because the electrons do not interact with one another, we can find the N -electron ground
state by calculating the single particle energy levels and then filling these levels subject to
the constraints of the Pauli exclusion principle. The Schrodinger equation for a single free
electron is
~2 2
(r) = (r),
(1.6)
2m
where (r) is the single electron wavefunction. By imposing suitable boundary conditions we
can represent the confinement of the electron to a volume V . One possibility is to insist that
the wavefunction (r) vanish at the boundary of the solid. This is not the most convenient
1.2. SOMMERFELD FREE ELECTRONS
ky
kx
2/L
Figure 1.1: The allowed states in momentum space of a two-dimensional solid of area
A = L2 . Periodic boundary conditions cause the states to be spaced by k = 2/L. The
k-space area per state is (2)2 /L2 , shown as the shaded region.
choice, as it leads to solutions that are standing waves, and we would eventually like to
describe transport properties in terms of the single electron states. A better choice is to use
periodic boundary conditions. Without any loss of generality, we choose our solid to be a
cube of side L = V 1/3 . The periodic boundary condition is then
(r + L
x) = (r + L
y ) = (r + L
z ) = (r),
(1.7)
where x, y and z are unit vectors along the axes of the cube. We now solve the single particle
Schrodinger equation, subject to this boundary condition, and find
1
k (r) = eikr spin function,
V
(1.8)
with energy
~2 k 2
.
(1.9)
2m
(The spin function represents the two possibilities spin up and spin down.)
k (r) is also an eigenfunction of the momentum operator, with momentum p = ~k, and
corresponds to an electron moving with velocity v = m~ k.
Substitution of k (r) into the boundary condition gives
k =
eikx L = eiky L = eikz L = 1.
(1.10)
This will only be satisfied by certain discrete values of k, given by:

kx L = 2nx , ky L = 2ny , kz L = 2nz ,
(1.11)
Figure 1.2: (After A. J. Schofield [1]) For temperatures small compared to the Fermi
temperatuer TF the electron gas is a filled Fermi sea in momentum space. The low energy
excitations of the system are electronhole pairs, formed by exciting an electron across the
Fermi surface. The energy available for creating these excitations, kB T , is much smaller than
the Fermi energy EF = kB TF .
where nx , ny and nz are integers.

Figure 1.1 shows the allowed k values plotted in two dimensions. They are separated by
2/L. The area per point is therefore (2/L)2 . In three dimensions, the volume per point is
(2/L)3 = 8 3 /V . This will be important when counting up the contribution of each state
to the bulk physical properties.
Because in this model the electrons are noninteracting, we can build up the N -electron
ground state by placing the electrons in the one-electron levels, subject to the Pauli exclusion
principle. This limits the occupation of each level (each k-state) to one electron of each spin.
The lowest energy configuration is a sphere of filled states centred on k = 0, as shown
in Fig. 1.2. The radius of the sphere in k-space is called the Fermi wave vector kF . The
magnitude of kF is determined by the condition that the sphere contain N electrons.
X
2
1 = N,
(1.12)
|k|<kF
where the factor of 2 accounts for the two possible spin states. k-space summations will often
appear in our calculations. These are easiest to evaluate by converting them to integrals over
the continuous variable k. In order that an integral over a volume of k-space containing a
single k-point (i.e. k-space volume = (2)3 /V ) return the correct value (i.e. 1), we multiply
the integral by a prefactor V /(2)3 . In problems where there is spin degeneracy, we also
include a factor of 2.
Z
X
V
d3 k.
(1.13)
2
2
3
(2)
k
ief history of
Brief
laser-cooling:
history of laser-cooling:
eriments
thre
that
changed
everything
erything5
1.3. THE
CLASSICAL
TO QUANTUM
CROSSOVER
+2
Kap
& Dira
electron
fro
0
1933
magnetic field gradient
J =2
+2
+2
+1
+1
rf 0
rf 0
+1
J =2
mJ = 2
J =2
mJ = 2
mJ = 2
Figure 1.3: (After K. Madison) The evaporative cooling process used to form BoseEinstein
condensates in the nanokelvin temperature range. mJ denotes the magnetic sublevels of a
J = 2 atomic species. A spatially varying magnetic field gives rise to spatially varying Zeeman energies, which are used to confine the mJ = +2 species in a magnetic trap. Radiowaves
ptical Trap of frequency
Magneto-optical
Trapin certain
Magneto-optical
are resonant,
positions, with Trap
the energy-level spacing of the magle, Chu,Raab,
& Pritchard
Prentiss,
Cable,
Chu,
Raab,
& Pritchard
Prentiss,
Cable,out
Chu,
& Pritchard
netic
trap. The
most
energetic
atoms are kicked
of the
trap first, lowering the average
energy. The radiofrequency is gradually reduced, kicking out more atoms and cooling those
remaining.
system
degenerate
and a macroscopic
an ideaEventually
borrowedthefrom
thebecomes
community
working
to achieve fraction
BEC of the
atoms enter the ground-state of the trap.
with atomic hydrogen
For the free Fermi gas, this leads straight away to the condition on kF .
V 4 3
k
(2)3 3 F
2 13
3 N
=
V
(1.14)
N = 2
kF
(1.15)
Points to note about the free Fermi gas:

the Fermi velocity vF = ~kF /m is much greater than the classical thermal velocity of
the electron v = (3kB T /m)1/2 .
the Fermi energy EF = ~2 kF2 /2m corresponds to a Fermi temperature TF = EF /kB that
is tens of thousands of Kelvin in most metals. At room temperature we are therefore
not very far from the ground-state configuration.
1.3
The classical to quantum crossover
For a system of identical particles it is convenient to think of the crossover from classical to
quantum statistics in terms of the thermal de Broglie wavelength. The de Broglie wavelength
is given by Plancks constant over the average momentum, h/p. Fora particle with a typical
thermal energy, the thermal de Broglie wavelength is dB = h/ 3mkB T . dB grows as
the particles are cooled, and is much larger for electrons than atoms due to the difference
in mass. The crossover from classical to quantum behaviour occurs when dB exceeds the
average spacing between particles, d n1/3 . Why does this occur? Well, for a system to
cease behaving classically, the particles must be able to explore their quantum statistics.
They do this by coherently exchanging places with a neighbouring particle, hence the need
for dB > d.1 When two fermions exchange places, the many-particle wavefunction changes
sign. For bosons, the sign is unchanged.
Electrons are so light that at densities found in a typical solid they form a quantum fluid
up to temperatures of the order of 104 K. Solids melt before the quantum-to-classical
crossover is reached.
Atoms are much heavier, so there is a chance of observing the classical to quantum
crossover. For noble gas atoms such as neon and argon, the liquids freeze before
dB can exceed the average atomic spacing. Solidification fixes the atoms in place
and effectively prevents the particle exchanges required for the atoms to explore their
quantum nature.
Helium on the other hand is much lighter, which lengthens dB and lowers the freezing
temperature. In fact, at ambient pressure, helium does not freeze and remains a liquid
down to T = 0. It therefore becomes a quantum fluid. Helium comes in two isotopes,
3
He, a fermion, and 4 He, a composite boson. What is quite remarkable is the difference
in properties that arises solely from the quantum statistics. At T = 2.15 K, 4 He becomes
a Bose superfluid. 3 He, on the other hand, is a Fermi liquid with TF 100 mK and,
below T 2 mK, a p-wave superfluid with Cooper pairs of 3 He atoms. This is the
strongest isotope effect of any element.
At even lower temperatures we enter the realm of trapped atom optics, shown in
Fig. 1.3. Using laser and radio-frequency cooling it is now possible to cool below
1 nanokelvin. The goal in this field is to make the atoms enter the quantum limit, by
increasing dB beyond the interparticle spacing. However, this must be done carefully.
Cooling by simply removing the hot atoms is not sufficient the particle density
decreases faster than dB can increase. Collisions between atoms, although rare, are
required to keep the system in thermal equilibrium in order to achieve more efficient
cooling. Atoms with even numbers of protons, neutrons and electrons Bose condense
on reaching the quantum limit. Fermion condensation is more difficult, and has only
just been achieved in addition to temperatures well into the quantum regime, it
requires an attractive interaction between the atoms in order to form Cooper pairs.
Using trapped atoms, experimentalists have been able to resolve a long standing issue
the time taken to form a Bose condensate. Interestingly, it is the time taken for a
pair of particles to interchange.
Incoherence occurs when the wavefunction of the quantum particle gets out of phase. The distance over
which this occurs is inversely proportional to the spread in wavevector, and the spread in wavevector is due
to thermal smearing.
Lecture 2
Thermodynamics and statistical
mechanics
There are many good books on this subject. One of the classic textbooks is Fundamentals of Statistical and
Thermal Physics, by Frederick Reif [2]. This short review is based on Chapter 2 of Quantum Theory of
Many Particle Systems, by Fetter and Walecka [3].
2.1
Review of thermodynamics
The change in internal energy E of a system can be related to small, independent changes
in the entropy S, volume V and particle number N , by the fundamental thermodynamic
relation
dE = T dS pdV + dN.
(2.1)
This shows that the internal energy is a thermodynamic function of these three variables,
E = E(S, V, N ). The temperature T , pressure p and chemical potential are given by
partial derivatives of E:

T =
E
S

p=
VN
E
V

=
SN
E
N

.
(2.2)
SV
In order to prevent confusion the variables that are kept constant must be explicitly specified
when differentiating.
The internal energy is useful for studying adiabatic (isentropic) processes. However, we
usually perform experiments at fixed temperature, so it is often better to make a Legendre
transformation to the variables (T, V, N ) or (T, p, N ). The resulting functions are called
the Helmholtz free energy F (T, V, N ) = E T S and the Gibbs free energy G(T, p, N ) =
E T S + pV . The differentials of these functions are
dF = SdT pdV + dN, and
dG = SdT + V dp + dN,
(2.3)
(2.4)
LECTURE 2. THERMODYNAMICS AND STATISTICAL MECHANICS
V
S
Figure 2.1: The internal energy E is a surface is SV N space. (Particle number N is

suppressed in this diagram.) Temperature and pressure are derivatives of the internal energy
with respect to S and V . Because E is a well-behaved function of S and V , it does not matter
which order second partial derivatives are taken in. This leads to the Maxwell relations.
showing that F and G are indeed thermodynamic functions of the specified variables. The
chemical potential is given by:

F
G
=
=
.
(2.5)
N T V
N T p
Gibbs had the clever idea of representing thermodynamic functions graphically. In Fig. 2.1,
the particle number coordinate N is suppressed and the internal energy E sketched as a
function of S and V . Temperature and pressure are given by the gradient of the surface, and
Legendre transforms change the shape of the surface and map it onto different coordinates.
Another important set of independent variables is (T, V, ), which is appropriate for variable
N . This is useful when our experimental system is able to exchange particles with a reservoir,
as is the case when we make electrical measurements. A further Legendre transformation
leads to the thermodynamic potential or grand potential
(T, V, ) = F N = E T S N,
(2.6)
d = SdT pdV N d.
(2.7)
which has differential

In terms of , the entropy, pressure and particle number are given by:

p=
N =
.
S=
T V
V T
T V
(2.8)
2.2. MAXWELL RELATIONS
Although E, F, G and provide equivalent ways of describing the same system, their independent variables differ in one important way. The set (S, V, N ) consists entirely of extensive
variables, which scale with the size of the system, while (T, p, ) are all intensive variables.
This allows us to obtain an important result. If we scale the size of the system by , we have
E = E(S, V, N ).
(2.9)
Differentiating with respect to we obtain

E
E
E
+V
+N
= T S pV + N.
E=S
S V N
V SN
N SV
(2.10)
From this, the remaining thermodynamic functions are found to be

F = pV + N
= pV
G = N
(2.11)
In particular, we see that the chemical potential is the Gibbs free energy per particle,
and that the thermodynamic potential per unit volume is the negative of the pressure. The
Gibbs free energy is particularly important for studying phase transitions.
2.2
Maxwell relations
Maxwell relations provide a very useful application of the above ideas, stemming from a
basic property of differentiable functions of several variables. To demonstrate this, consider
changes in the internal energy with respect to entropy and volume.
dE = T dS pdV
(2.12)
On purely mathematical grounds we can write:

E
E
dE =
dS +
dV
S V
V S
(2.13)
from which we saw above that

T =
E
S

and p =
V
E
V

.
(2.14)
We can differentiate again to get:

T
E
=
V S
V S V S

p
E
=
S V
S V S V
(2.15)
(2.16)
We are differentiating a well behaved surface, so it does not matter what order we take the
derivatives in. As a result, we have the Maxwell relation:

T
p
=
.
(2.17)
V S
S V
10
This illustrates the basic principle. There are many other Maxwell relations, some more
useful that others. Particularly important are the ones involving entropy, which is not
directly accessible in experiments. For example:

p
S
=
(2.18)
V T
T V

S
V
=
(2.19)
p T
T p
Relations like the last one are particularly powerful. It relates the volume coefficient of
thermal expansion to a derivative of the entropy. From the third law of thermodynamics we
know that the entropy vanishes as T 0. This must occur at all pressures, so S/p must
also vanish. As a result we see that the coefficient of thermal expansion goes to zero in this
limit for very fundamental reasons.
2.3
Review of statistical mechanics
Macroscopic thermodynamics, although useful, merely correlates bulk properties of the system. The microscopic content of the theory is introduced through statistical mechanics,
which relates the thermodynamic functions to the hamiltonian. For a many particle system that is free to exchange particles with its environment, it is useful to work with the
grand canonical ensemble at chemical potential and temperature T = 1/kB . The grand
partition function ZG is defined:
XX
ZG
e(Ej N )
(2.20)
N
XX
N
hN j|e(HN ) |N ji
(2.21)
Here, states are labelled by particle number N , with j running over all energy eigenstates
for each fixed N , allowing the partition function to be written in terms of the quantum
and N
.1 A common shorthand is the use of the trace operator, where Tr(A)
operators H
In this notation, the
denotes the sum over all states of the quantum expectation value hAi.
grand partition function is

ZG = Tr e(HN ) .
(2.22)
A fundamental result from statistical mechanics relates the grand partition function to the
thermodynamic potential :
(T, V, ) = kB T ln ZG = ZG1 = e .
1
(2.23)
This contains a subtle but important point. Although we are about to specialize to the case of noninteracting particles where the energies of the single particle states are additive i.e. they simply add up to
give the total energy Ej that appears in the partition function this is usually not the case. Any realistic
hamiltonian contains interactions between the particles, requiring us to solve a different problem for each N
in order to find a new set of eigenstates |N ji and a new set of eigen-energies {Ej }. This is very difficult to
do in practice.
2.4. STATISTICAL MECHANICS OF IDEAL QUANTUM GASES
11
This result allows equilibrium thermodynamic quantities to be calculated from the grand
partition function.
It is also useful to define the statistical operator G , whose expectation value in any state is
the probability, in thermal equilibrium, of finding the system in that state.
G = ZG1 e(HN )
= e
(2.24)
)
(H+
N
(2.25)
the ensemble average hOi

can be obtained in the following way:
For any operator O,

= Tr G O
hOi
(2.26)

= Tr e(H+N ) O
(2.27)

Tr e(HN ) O

(2.28)
=
)
N
Tr e(H
2.4
Statistical mechanics of ideal quantum gases
We now apply these ideas to noninteracting Bose and Fermi gases, in which the total energy
of the many-particle states can be computed by adding up the energies of the occupied
one-particle states.2 For this calculation it is convenient to work in the occupation number
representation, where |N ji P|n1 ...n i. Here, the ni denote the number of particles in
each single-particle state, and i ni = N . There is an important difference in the labelling
scheme: previously j ranged over the true N -particle eigenstates, but now i runs over all
the single-particle states. While the set {|n1 ...n i} is a valid basis set for the many-particle
problem, only in the noninteracting case are these the eigenstates of the system. We can
0:
now calculate the grand partition function for the noninteracting hamiltonian H

0 N
)
(H
ZG = Tr e
= e0 (T,V,)
(2.30)
X

=
(2.31)
hn1 ...n |e(N H0 ) |n1 ...n i
n1 ...n
"
=
hn1 ...n | exp
n1 ...n
!#
ni
i ni
|n1 ...n i,
(2.32)
0 and N
, and replaced
where we have used the fact that the |n1 ...n i are eigenstates of H
them by their eigenvalues. The exponential is now a c number and can be factored into a
2
Remember, this is not possible in the presence of interactions. In that case, adding a particle to an
N -particle system does not in general increase the total energy by the energy of the single particle state .
EN +1 6= EN +
(2.29)
12
product of exponentials, and the partition function can be factored into a product of traces,
one for each mode:
X
X
ZG =
hn1 |e(n1 1 n1 ) |n1 i...
hn |e(n n ) |n i
(2.33)
=
n1
Tri e(i )ni
(2.34)
i=1
For bosons the sum over ni runs over all nonnegative integers:
ZG =
e(i )
n
(2.35)
i=1 n=0
1e

(i ) 1
!
xn = (1 x)1 , |x| < 1
(2.36)
n=0
i=1
From this we immediately obtain the thermodynamic potential:

0 (T, V, ) = kB T ln
1 e(i )
1
(2.37)
i=1
= kB T
ln 1 e(i )
BoseEinstein
(2.38)
i=1
We now calculate the mean number of particles:

0
hN i =
T V
X
e(i )
= kB T
1 e(i )
i=1
=
X
i=1
1
e(i ) 1
(2.39)
(2.40)
BoseEinstein
n0i ,
(2.41)
(2.42)
i=1
where n0i is the mean occupation number in the ith state.

For fermions, the Pauli exclusion principle limits the occupation numbers to be either zero
or one. We have
ZG =
=
X
1
Y
i=1 n=0
e(i )
n
1 + e(i )
(2.43)
(2.44)
i=1
13
and
0 (T, V, ) = kB T

ln 1 + e(i ) .
FermiDirac
(2.45)
i=1
The mean number of particles is
hN i
n0i
i=1
2.4.1
i=1
1
e(i )
+1
FermiDirac
(2.46)
Example: statistics of an impurity in a semiconductor
We will look at the simplest example of correlation beyond the independent electron approximation, and show how it modifies the FermiDirac distribution. Imagine we have a
single donor impurity atom in a semiconductor, and that this atom has available a single
orbital, which can be empty, contain one electron of either spin, or be doubly occupied. In
this example, the two singly occupied states are degenerate, and we label their energy 1 .
This energy will lie just below the bottom of the conduction band. In the first instance, we
ignore interactions between the electrons, so that the energy of the doubly occupied state is
just 21 , as shown in Fig. 2.2.
We now calculate the mean occupation number:
ZG =
XX
N
hN j|e(HN ) |N ji
(2.47)
= 1 + 2 e(1 1) + e(21 2)
2
= 1 + e(1 )
= kB T ln ZG

= 2kB T ln 1 + e(1 )

hN i =
T V
e(1 )
1 + e(1 )
1
= 2 (1 )
e
+1
(2.48)
(2.49)
(2.50)
(2.51)
(2.52)
(2.53)
= 2kB T
(2.54)
This is what we expect: twice the mean occupation number of a single state at energy 1 .
What happens when we include the Coulomb repulsion between electrons? If we call this
energy U , we get a new energy level diagram, with the energy of the doubly occupied state
shifted to 21 +U . For donor impurities, it is often the case that the doubly occupied state lies
well above the bottom of the conduction band, preventing two electrons from ever occupying
the impurity orbital at the same time. We must therefore exclude the doubly occupied state
14
Noninteracting electrons
Interacting electrons
N=2
E = 2 1+U
Conduction
Band
Donor Level
N=2
E = 2 1
Valence
Band
N=1
E = 1
N=1
E = 1
N=0
E=0
N=0
E=0
Figure 2.2: Donor impurities in a semiconductor give rise to donor levels just below the
bottom of the conduction band. In the absence of Coulomb repulsion the energy of the
doubly occupied donor level is just 21 . In reality, the Coulomb interaction contributes an
additional energy U , lifting the energy of the doubly occupied level well above the bottom
of the conduction band. This greatly modifies the statistics of the impurity level.
from our set of eigenstates |N ji. We calculate the average occupation number again:
ZG =
XX
N
hN j|e(HN ) |N ji
(2.55)
= 1 + 2 e(1 )
= kB T ln ZG

= kB T ln 1 + 2e(1 )

hN i =
T V
(2.56)
(2.57)
(2.58)
(2.59)
2e(1 )
1 + 2e(1 )
1
= 2 (1 )
e
+2
(2.60)
= kB T
(2.61)
The two situations, interacting and noninteracting, are plotted in Fig. 2.3 and we can see
right away that correlation effects make them quite different.

2
-10
15
nnoninteracting
ninteracting
-5
( )/kBT
10
Figure 2.3: The average occupation number of the donor level is shown in the interacting
and noninteracting cases. Interactions substantially modify the statistics, with Coulomb
repulsion blocking double occupancy.
2.4.2
Example: interacting electrons in a metal
Another example of how interactions modify quantum statistics is provided by electrons in a

metal. Figure 2.4 shows what happens when interactions are switched back on in the Fermi
gas. Parts (a) and (b) show the result we derived above for the Fermi function. At finite
temperature, the distribution function ne smoothly drops from 1 to 0 in an energy range of
a few kB T about the chemical potential. At zero temperature the drop is abrupt. What
happens in a real metal, where there is a strong Coulomb repulsion between the electrons?
Something like what is shown in Fig. 2.4(c). Note that we are still at zero temperature, but
the distribution function has substantial rounding in the vicinity of the chemical potential.
An abrupt drop remains, but is reduced in magnitude. The zero-temperature distribution
function represents the lowest energy configuration of the electrons and takes into account
both the electronelectron repulsion and the electron kinetic energy. The system is clearly
not described by FermiDirac statistics. Why then do we spend so much time talking about
metals as if they were noninteracting electron systems, and why do we use Fermi statistics
to calculate their thermal properties? The answer is subtle, and lies in the fact that for
many systems the true eigenmodes retain many of the properties of noninteracting electrons.
That is, they are weakly interacting, have definite charge, and well-defined quantum statistics. Such states are called electron quasiparticles and in many cases (for systems where the
balance between kinetic and potential energy is not too delicate) resemble electrons with
modest mass renormalization. Figure 2.4 (d) sketches nqp , the distribution function of the
interacting electrons in the quasiparticle basis. It is a zero-temperature FermiDirac distribution. We will go into more detail about this when we get to Landaus Fermi-liquid theory
in Lecture 28.
16
ne
(a)
ne
T=0
noninteracting
(b)
nqp
T=0
interacting
(c)
ne
T>0
noninteracting
T=0
interacting
(d)
Figure 2.4: The Fermi function, which gives the average occupation number of noninteracting electron states, is shown at finite temperature in (a) and at T = 0 in (b). The T = 0
electron occupation number is shown in (c) in the presence of interactions, and is nothing
like the Fermi function. However, in many cases an interacting electron system has fermionic
normal modes that closely resemble electrons. These are called quasiparticles, and at low
temperatures have a Fermi distribution, like that shown in (d).
Lecture 3
Thermal properties of the Fermi gas
References: Most solid-state text books include a chapter on the thermal properties of the free Fermi gas.
For instance, see: Ashcroft and Mermim [4], Chapter 2; Reif [2], Chapter 9; or Marder [5], Chapter 6.
3.1
Specific heat of an electron gas
We would like to calculate the specific heat at constant volume, cV , of a system of N

noninteracting electrons in a volume V . The specific heat is defined to be:
cV

1 E
=
V T V N

T S
=
,
V T V N
(3.1)
(3.2)
where E is the internal energy. In the independent electron approximation the single particle
energies are additive, and the average internal energy hEi is the sum over all occupied levels
of the single particle energy:
X
hEi = 2
k f (k ),
(3.3)
k
where the factor of 2 comes from the spin degeneracy. In our problem, we have the additonal
constraint of maintaining, on average, a fixed number of electrons.
hN i = 2
f (k ),
(3.4)
which we impose by adjusting the chemical potential . (This is the reason the chemical
potential was introduced in the first place.) In the expressions for hEi and hN i, the quantity
being summed depends on k only through the single-particle energy k . It therefore makes
sense to introduce the density of states D(), which is defined so that
D()d number of states per unit volume with energy between and + d.
17
(3.5)
18
LECTURE 3. THERMAL PROPERTIES OF THE FERMI GAS

D()
D()d
+d
Figure 3.1: The density of states (D.O.S.) is the number of states per unit energy, per unit
volume.
We will give a precise definition of D() shortly. In the meantime, lets write down expressions, per unit volume, for the two thermally averaged quantities we need:
Z
Z
2 X
2 V
dk
hN i
f (k )
dk f ((k)) =
n
=
f ((k))
(3.6)
3
V
V k
V (2)
4 3
Z
Z
hEi
2 X
2 V
dk
u
=
k f (k )
dk (k)f ((k)) =
(k)f ((k)) (3.7)
3
V
V k
V (2)
4 3
These are both integrals of the form
Z
dk
F ((k)) =
4 3
d(cos )
1
Z
0
k 2 dk
F ((k)) =
4 3
Z
0
k 2 dk
F ((k)),
2
(3.8)
where the integrand F ((k)) depends on k only through the energy and, therefore, only on
the magnitude of k. Lets make the definition:
Z
k 2 dk
F ((k))
2
dD()F (),
(3.9)
so that
D()d =
k 2 dk
.
2
(3.10)
Since k 2 , we have (taking the logarithmic derivative)

d
dk
d

=2
=2 .

k
dk
k
(3.11)
3.2. THE SOMMERFELD EXPANSION
19
Rearranging for D(), we get

D() =
k2 k
k 2 dk
=
2 d
2 2
2m ~2 k 2 k
= 2 2
~ 2m 2
m
m
= 2 2 k.
(D.O.S. at Fermi surface = 2 2 kF .)
~
~
(3.12)
(3.13)
(3.14)
2 2
k
Using the free electron dispersion relation (k) = ~2m
, this can also be written:
r
2m
m
D() = 2 2
.
~
~2
(3.15)
The final form for our thermal averages is:

Z
electron density: n
=
dD()f ()
(3.16)
dD()f ()
(3.17)
energy density: u =
These integrals are quite complicated to evaluate, but we can make a great simplification
in the low temperature limit. (And remember, low temperature in a metal means T
TF , where the Fermi temperature TF is typically tens of thousands of kelvin.) In the zero
temperature limit, the Fermi function becomes a step function, and the integrals are very
simple:
Z F
dD()
(3.18)
n0 =
Z F
u0 =
dD(),
(3.19)
where F = (T = 0). At low temperatures T TF , the Fermi function differs from a step
function only in the vicinity of the chemical potential. We can then make an expansion in
powers of T . This procedure is called the Sommerfeld expansion.
3.2
The Sommerfeld expansion
Say that we want to integrate

Z
H()f ()d,
(3.20)
where H() vanishes as and is polynomial in as +.

Ideally, we want to work with the derivative of the Fermi function, because the derivative
is localized near the Fermi surface ( = ), and we know that this is where all the action
occurs. Therefore, let
Z
dK()
= H().
(3.21)
K() =
H(0 )d0 , so that
d
20

1
f(x)
-df(x)/dx
-30
-20
-10
x = ()/kBT
Figure 3.2: The Fermi function f (x) = 1/ (1 + ex ) and its derivative. df /dx is sharply
peaked within a thermal energy of x = 0.
Now integrate the original expression by parts:

Z
Z
+
H()f ()d = [K()f ()] +

f
d.
K()

(3.22)
The term in brackets vanishes: K() 0 as , and f () goes to zero exponentially
quickly as +.
Now expand K() about the chemical potential:

X
( )n dn K()
K() = K() +
(3.23)
n
n!
d
=
n=1
Substituting into the original expression, we get:

Z
Z
Z
X
f
( )n dn K()
f
H()f ()d = K()
d +
d.
n

n!
d

=
n=1
(3.24)
Now

Z
Z
f
K()
d = K() {f () f (+)} = K() =

H()f ()d.
(3.25)

Also, since f
is an even function of (), only terms with even n survive the integration.

Finally,

Z

dn K()
dn1
dn
0
0
=
H(
)d
=
H()|= H (n1) ().
(3.26)

dn
dn
dn1
=
We can therefore write:

Z
Z
H()f ()d =
=
H()d +
H()d +
(2n1)
n=1
(2n1)
( )2n
(2n)!
()
n=1
2n
()(kB T )

f
d

x2n
f
dx
(2n)!
x
(3.27)
(3.28)
3.3. SPECIFIC HEAT OF THE IDEAL FERMI GAS
21
This is a rapidly converging power series in even powers of T . The coefficients of the first
few terms are:

Z 2
f
2
x
dx =
,
(3.29)
x
6
2!

Z 4
x
f
7 4
dx =
.
(3.30)
x
360
4!
The final result, up to fourth order in T is:
2
7 4
H()d + (kB T )2 H 0 () +
H()f ()d =
(kB T )4 H 000 () + O
6
360
3.3
T
TF
6
(3.31)
Specific heat of the ideal Fermi gas
To begin, lets calculate the temperature dependence of the chemical potential, and show
that it is weak, even at room temperature.
Z
D()f ()d H() = D().
(3.32)
n
=
Using the Sommerfeld expansion:

4
T
2
2 0
n
=
D()d + (kB T ) D () + O
6
TF
4
Z F
Z
T
2
2 0
=
D()d +
D()d + (kB T ) D () + O
6
TF
0
F
Z F
2
D()d + ( F )D(F ) + (kB T )2 D0 (F ),

6
0
Z
(3.33)
(3.34)
(3.35)
where we are assuming that the temperature dependence of is weak (we must verify this
below) in order to make the approximation F in the higher order terms. The first term
is just the electron density at T = 0, n0 . Rearranging, we get
n
n0 = ( F )D(F ) +
2
(kB T )2 D0 (F ).
6
(3.36)
We want to keep the average electron density fixed, so n

n0 = 0, implying
= F
2
D0 (F )
(kB T )2
.
6
D(F )
(3.37)
For electrons in 3 D, D() 1/2 , so that

D0 (F )
d ln D()
1
=
=
.

D(F )
d
2F
=F
(3.38)
22
Therefore
1
2
(kB T )2
6
2F

2 !
2 T
1
,
12 TF
= F
(3.39)
= F
(3.40)
which is a very small shift in chemical potential at room temperature.

Now to calculate the internal energy:
Z
D()f ()d H() = D().
u =
(3.41)
Using the Sommerfeld expansion again:

4
Z
2
T
2
0
u =
D()d + (kB T ) [D () + D()] + O
6
TF
Z F
2
D()d + ( F )F D(F ) + (kB T )2 [F D0 (F ) + D(F )]
6
0

2
2
2 0
= u0 + F ( F )D(F ) + (kB T ) D (F ) + (kB T )2 D(F ),
6
6
(3.42)
(3.43)
(3.44)
where u0 is the energy density at zero temperature. We have already shown that the term
in braces is just n
n0 , which must vanish. Therefore,
2
(kB T )2 D(F ).
6
We obtain the specific heat from the temperature derivative

u
2
cV =
= kB2 T D(F ).
T N V
3
(3.45)
u = u0 +
(3.46)
We can write down a useful expression for the density of states, just by knowing how the
total energy depends on the density of electrons. Since k 2 , and n k 3 (in 3-D), we
know that n 3/2 . This implies that
3 d
dn
3n
dn
=
or
D() =
.
(3.47)
n
2
d
2
Therefore, the density of states at the Fermi level, which determines many of the important
low temperature properties such as specific heat and Pauli susceptibility, is given by:

dn
3n
D(F ) =
=
.
(3.48)

d =F
2F
We have then that
cV
2 2 3n
k T
3 B 2F
2 3kB n T
=
.
3 2 TF
=
(3.49)
(3.50)
3.3. SPECIFIC HEAT OF THE IDEAL FERMI GAS
23
Compare this to the specific heat of a classical gas:

3
kB T n,
from the equipartition theorem
2
cl
u
3
=
= kB n.
T N V
2
ucl =
(3.51)
ccl
V
(3.52)
The specific heat of the Fermi gas,

cV = ccl
V
2 T
,
3 TF
(3.53)
is reduced by a factor 3 TTF , emphasizing that in degenerate Fermi systems, all the action
indeed takes place within a thermal energy kB T of the Fermi surface.
24
Lecture 4
Review of single-particle quantum
mechanics
References: One of the best books on single-particle quantum mechanics is Principles of Quantum Mechanics, by R. Shankar [6]. This develops the abstract approach in a very clear way and has a good mathematical
introduction on linear algebra. Chapter 2 of Taylor and Heinonen [7] also has a good review of single-particle
quantum mechanics and Dirac notation, done in a way that leads naturally to the second quantized formalism
used for many-particle systems.
4.1
Single-particle quantum mechanics
The next few lectures will set up the mathematical framework necessary for describing the
quantum mechanics of many-particle systems. In particular we will show that all physical
information can be obtained using operators instead of wavefunctions. It is a good idea to
begin this task with a review of single-particle quantum mechanics, as a foundation for the
many-particle formalism and to see precisely how the two differ.
Quantum mechanics cannot be derived, but begins from a set of postulates. These are
written here using Dirac notation:
(i) Complete information about the state of a particle is provided by the state function |i,
a vector in a Hilbert space.
When that
(ii) For every observable there exists a corresponding Hermitian operator .
observable is measured we will obtain one of the eigenvalues of .

(iii) If the particle is in state |i then a measurement of will give one of the eigenvalues
with probability P () |h|i|2 and leave the system in the eigenstate |i.
(iv) The expectation value of an observable in a state |i is hi = h||i.

(v) In the absence of a measurement, the time dependence of the state function is given by
H|i
= i~ |i.
t
25
(4.1)
26
LECTURE 4. REVIEW OF SINGLE-PARTICLE QUANTUM MECHANICS
In single-particle quantum mechanics, the hamiltonian has the form

2
= p
+ U (
r)
H
2m
(4.2)
(Later on, the general many-body hamiltonian will be expanded

=
H
X p
X
2i
1X
+
U (
ri ) +
V (
ri
rj ) + three-body terms + ...
2m
2 i6=j
i
i
(4.3)
Along with the added complexity of interactions between the particles, the number of particles
will in general not be fixed.)
In quantum mechanics we often work in the position representation (or r-rep). More formally,
this is the basis set formed by the eigenstates of the position operator
r.
r|r0 i = r0 |r0 i
(4.4)
This satisfies the necessary requirements of a basis set:

it spans the Hilbert space
Z
dr|rihr| = 1
completeness
(4.5)
orthonormality
(4.6)
and it forms an orthonormal set

hr|r0 i = (r r0 ).
This is a perfectly good way of doing single-particle quantum mechanics. We can take any
abstract state |i, and project it onto the position basis:
|i hr|i = (r),
(4.7)
showing that the wavefunction is the probability amplitude of finding a particle at a given
point. In the position basis the hamiltonian takes the form of the Schrodinger equation
~2 2
p
2
+ U (
r)
+ U (r),
H=
2m
2m
(4.8)
where r is now just a coordinate, not an operator.

But this is not the only way of representing a statefunction and the hamiltonian. We
can equally well work in the momentum representation, where the statefunctions (k) are
Fourier transforms of the Schrodinger wavefunctions (r). The basis functions |ki are the
plane waves
1
hr|ki = eikr .
(4.9)
V
4.1. SINGLE-PARTICLE QUANTUM MECHANICS
27
Because we are working with a discrete set of allowed wavevectors in a finite volume V , the
conditions for completeness and orthonormality take a slightly different form:
X
|kihk| = 1
completeness
(4.10)
k
hk|k0 i = k,k0 .
orthonormality
(4.11)
We can also choose to work in the natural representation of the Hamiltonian the energy
basis. The basis states |i are the energy eigenstates of the hamiltonian.
H|i
= E |i.
(4.12)
For this basis, we have

X
|ih| = 1
completeness
(4.13)
h|0 i = ,0 .
orthonormality
Any state in the Hilbert space can be expanded in terms of the set {|i}:
X
X
|i =
|ih|i =
c |i, c = h|i.
(4.14)
(4.15)
This can be projected onto the coordinate basis hr| to give:

X
c (r), where (r) hr|i.
(r) =
(4.16)
Operators can be expressed in terms of their matrix elements V0 h|V |0 i:

!
!
X
X
V =
|0 ih0 | V
|00 ih00 |
0
(4.17)
00
V0 00 |0 ih00 |.
(4.18)
0 00
The operator |0 ih00 | gives zero when it acts on any state |i except when = 00 it
then gives |0 i. In other words |0 ih00 | removes or annihilates a particle from state |00 i and
puts it into or creates state |0 i. We can also define an empty or vacuum state |0i, that is
normalized but contains no particles. We can then write
|0 ih00 | = |0 ih0|0ih00 |
= (|0 ih0|) (|0ih00 |)
(4.19)
(4.20)
where we now have explicit expressions for the creation operator c0 |0 ih0| and the
annihilation operator c00 |0ih00 |. Using these, the original operator V becomes
X
V =
V0 00 c0 c00 .
(4.21)
0 00
This way of representing operators comes into its own when we work with many-particle
systems in that case it is the only feasible approach.
28

V = 1/2 k x2
|4>
|3>
|2>
|1>
|0>
Figure 4.1: Energy eigenstates of the harmonic oscillator.
4.2
The harmonic oscillator
Any system fluctuating by a small amount near a configuration of stable equilibrium can be
described by a collection of oscillators, which can be decoupled by making a transformation to
the systems normal coordinates. (The dynamics of a collection of noninteracting oscillators
is no more complicated than that of a single oscillator, so the problem we look at here is
very relevant to many-particle systems.) In one dimension the hamiltonian and Schrodinger
equation are
1
p2
+ m 2 x2
2m 2
H|i = E|i.
=
H
(4.22)
(4.23)
In the coordinate basis this becomes

~2 2 1
2 2
+ m x (x) = E(x),
2m
2
(4.24)
which has solution

mx2
n (x) = A(n) exp
2~

r

Hn

m
1
x , En = n +
~.
~
2
(4.25)
4.2. THE HARMONIC OSCILLATOR
29
Here A(n) is a normalization constant that depends on n and Hn (y) are the Hermite
polynomials:
H0 (y)
H1 (y)
H2 (y)
H3 (y)
Hn+1 (y)
=
=
=
=
=
1
2y
4y 2 2
8y 3 12y
2yHn (y) 2nHn1 (y).
(4.26)
(4.27)
(4.28)
(4.29)
(4.30)
As we stated at the beginning, all we can know about a quantum system is the statistical
distribution of the eigenvalues of our measurement operators, which we obtain by evaluating
matrix elements. In the coordinate basis, this requires us to form inner products by sandwiching a differential operator between two wavefunctions and integrating, something that
rapidly becomes tedious. There must be a better way!
Fortunately there is, using a method due to Dirac. With this technique we can not only find
the energy spectrum, but evaluate the matrix elements of any operator, as long as it can be
expressed as a function of x and p. All we need is the canonical commutation relation
[
x, p] = i~.
(4.31)
Lets introduce the operator

r
a=
m
x + i
2~
1
p,
2m~
(4.32)
and its adjoint
a =
m
x i
2~
1
p.
2m~
(4.33)
Now evaluate the commutation relation [a, a ]. This has the form
[A + iB, A iB] = [A, iB] + [iB, A] = 2i[A, B]
(4.34)
Therefore
r
r
m
1
[
x, p]
[a, a ] = 2i
2~ 2m~
2i
= i~
2~
= 1.
(4.35)
(4.36)
(4.37)
Next, write down a a:

a a = (A iB)(A + iB)
= A2 + B 2 + i[A, B]

1 m 2 2
1 2
1
=
x +
p
~
2
2m
2
H
1
=
.
~ 2
(4.38)
(4.39)
(4.40)
(4.41)
30
Therefore
=
H
1
a a+
2

(4.42)
~.
(One interesting observation apparent from this derivation is that the extra term ~/2
the zero point energy of the oscillator comes from the noncommuting nature of x and p.)
We want to solve
= |i.
H|i
(4.43)
Scale the hamiltonian to get a dimensionless operator:

H
1
0
H
=
H
= a a+
.
~
2
(4.44)
Now evaluate the commutators with a and a :

0 ] = [a, a a + 1 ] = [a, a a] = [a, a ]a = a,
[a, H
2
(4.45)
0 ] = a .
[a , H
(4.46)
and similarly
0 they generate others. To see this,
a and a are useful because given an eigenstate of H
assume |i is a eigenstate. What is the energy of a|i?

0 (a|i) = aH
0 [a, H
0 ] |i
H
(4.47)

0 a |i
= aH
(4.48)
= ( 1)a|i.
(4.49)
a|i is an eigenstate with energy ( 1). Similarly, a |i is a eigenstate with energy ( + 1).
a is a creation or raising operator, and a an annihilation or lowering operator.
It can easily be shown that the eigenvalues of the harmonic oscillator are nonnegative (this
is because the hamiltonian is quadratic in both the hermitian operators x and p), so there
must be a lowest eigenstate |0 i. Acting on |0 i with the lowering operator a must therefore
give zero.
a|0 i = 0
(4.50)
Operating on this with a must also give zero:
a a|0 i = 0

1
0

|0 i = 0
H
2
0 |0 i = 1 |0 i 1 |0i.
H
2
2
(4.51)
(4.52)
(4.53)
The ground state energy is therefore 0 = 12 ~.

The excited states can be obtained from the ground state by repeated application of a .
|ni (a )n |0i.
(4.54)
4.2. THE HARMONIC OSCILLATOR
31
The excited states form an evenly spaced ladder of levels, so n = (n + 1/2)~. (There must
be only one family of levels, because there is no degeneracy in one dimension.)
Lets now determine the normalization constant. Assume that |n 1i is normalized and
work out the normalization factor for |ni.
a|ni
hn|a a|ni
0 1 |ni
hn|H
2
2
so |cn | = n
= cn |n 1i,
(hn|a = hn 1|cn )
= hn 1|n 1i|cn |2 = |cn |2
1
= hn|n|ni
(n = (n + )~)
2
i
cn = ne ,
(4.55)
(4.56)
(4.57)
(4.58)
where we usually set the phase to zero. This and a similar derivation for a give us the
two important equations
a|ni =
n|n 1i,
(4.59)
a |ni =
n + 1|n + 1i.
(4.60)
Using these two equations we can show that

a a|ni = a n|n 1i = n n|ni = n|ni.
(4.61)
In other words, n
= a a is the number operator, which when acting on an eigenstate gives
the number of quanta. This is very useful.
Equations 4.59 and 4.60 are also useful for evaluating matrix elements, and therefore physical
observables.
hn0 |a|ni =
nhn0 |n 1i = n n0 ,n1
(4.62)
0
0
hn |a |ni =
n + 1hn |n 1i = n + 1 n0 ,n+1
(4.63)
These equations can be used to find any physical observable that is a function of x and p,
as these can be written, in turn, in terms of a and a :
r
~
x =
(a + a )
(4.64)
2m
r
m~
p = i
(a a).
(4.65)
2
Finally, the nth excited state, properly normalized, is generated by
a
a
a
(a )n
|ni = |n 1i =
|n 2i = ... = |0i.
n
n n1
n!
A general feature of this approach is that the
1/2
0
~
H
0
..
.
(4.66)
hamiltonian is diagonal in the energy basis.
0
0 ...
3/2 0
(4.67)
0 5/2
32
This can also be the case in a many-particle system. If we can diagonalize the many-particle
hamiltonian, that is put it in the form
X
X
=
H
i ai ai + const =
i n
i + const,
(4.68)
i
then we have solved the problem. The total energy is then the sum of the energy of the
individual oscillators, which are independent and are the true quasiparticles of the system.
Mean field theory is all about making approximate factorizations of the interaction terms in
order that the hamiltonian can be transformed to a basis in which it is diagonal.
Lecture 5
Many-particle quantum systems
References: Introductions to second quantization can be found in many books, including Chapter 2 of
Taylor and Heinonen [7], Many-Particle Physics, by G. Mahan [8] and Quantum Theory of Many Particle
Systems, by Fetter and Walecka [3].
5.1
Quantum mechanics of many-particle systems
This lecture contains an introduction to second quantization, an essential tool for manyparticle quantum mechanics. What is important to remember is that second-quantized
notation is used everywhere in the description of many particle quantum systems, and not
just by people who carry out calculations. It is therefore important that theorists and
experimentalists alike be familiar with it.
What happens in the many-particle problem (N 1, usually N 1020 ) if we try to work
in the coordinate representation? In principle we can still do quantum mechanics this way.
We can write down the many-particle wavefunction (r1 , 1 ; ...; rN , N ; t), which is now a
function of 4N + 1 variables. (3N coordinates, N spins, and a time variable.) The following
step would be to write down the Schrodinger equation
r (r1 , 1 ; ...; rN , N ; t) = i~ (r1 , 1 ; ...; rN , N ; t),
H
t
(5.1)
~2 2 X
1X
i +
U (
ri ) +
V (
ri
rj ) + ...
2m
2
i
i6=j
(5.2)
where
r =
H
X
i
Forget for the moment that such an equation would be impossible to write down, let alone
solve. Our next step might be to expand the wavefunction in a convenient basis set, built
for instance from the one-particle complete basis { (r)}, in terms of which any function in
the single-particle Hilbert space can be expanded:
f (r) =
c (r).
(5.3)
33
34
LECTURE 5. MANY-PARTICLE QUANTUM SYSTEMS
In principle, the many-particle wavefunction can be expanded in a set of products of the

single-particle basis functions
X
(r1 , ..., rN , t) =
c1 ...N (t)1 (r1 )...N (rN ).
(5.4)
1 ...N
Provided the original single-particle basis is orthonormal, we now have a complete and orthonormal basis for the N -particle Hilbert space: {1 ...N (r1 , ..., rN )} = {1 (r1 )...N (rN )}.
But, in the case of a system of electrons, we are dealing with fermions. The many-particle
wavefunction must therefore be antisymmetric under the interchange of the coordinates of
any pair of particles. As a result, we need to work in a much smaller subspace of the original
N -particle Hilbert space that contains only properly antisymmetrized wavefunctions.
1 X
(1)P 1 (rP1 )...N (rPN ),

1 ...N (r1 , ..., rN ) A
(r
,
...,
r
)
=
N
1 ...N 1
N! P
(5.5)
where P runs over all possible permuations of (1, 2, ..., N ). This can be written compactly
as a Slater determinant:

(r1 ) . . . (r1 )
1
N

1

..
..
(r
,
...,
r
)
=
A
(5.6)

N
.
.
1 ...N 1

N!
1 (rN ) . . . N (rN )
Each Slater determinant has N ! terms. We now have a way of expanding any proper fermionic
wavefunction:
X
c1 ...N (t)A
(5.7)
(r1 , ..., rN , t) =
1 ...N (r1 , ..., rN ).
1 ...N
We showed in the previous lecture on single particle quantum mechanics that complete
information about the state of a quantum system can be obtained by computing matrix
elements. How difficult will this task be in the N -particle case? In our hamiltonian we have
two types of operators:
Single particle operators:
A =
N
X
Ai N terms
(5.8)
i=1
Two particle operators:

N
X
ij N (N 1) terms
=1
B
B
2 i6=j=1
2
(5.9)
A general matrix element will have the following form:

Z
X Z
X
h|O|i = dr1
. . . drN
(r1 , 1 ; . . . ; rN , N ; t)O(r
1 , 1 ; . . . ; rN , N ; t) (5.10)
1
5.2. SECOND QUANTIZATION
35
In the best possible case, our wavefunction will be a single Slater determinant. Then

N
(5.11)
h|O|i (N integrals + N spin sums ) N ! N (N 1) N !
2
This is clearly impossible to carry out, even in the simplest case. Fortunately, these difficulties are due entirely to the fact that we insisted on working in the coordinate representation.
In what follows we will see that all these problems go away when we use second quantization
and work in the number representation.
5.2
Second quantization
In the previous section we showed that wavefunctions become extremely complicated when
we work with large numbers of identical interacting particles and the task of evaluating
matrix elements between them is essentially impossible. Interactions, and the requirements
of the Pauli exclusion principle, introduce strong correlations between the positions of the
particles.1 In the presence of these correlations, it is no longer possible to say which singleparticle states are occupied, independently of the motion of the rest of the particles in the
system. However, we can always use the single-particle states to form a basis set for the
many-particle Hilbert space the set of antisymmetrized product functions:
1 X
(1)P 1 (rP1 )...N (rPN ).

(5.12)
A
(r
,
...,
r
)
=
1
N
1 ...N
N! P
These states clearly have the proper symmetry under particle exchange. However, we showed
that we cannot work with these Slater determinants explicitly they are impossible to conceive of using for a system of N 1020 particles. Also, the Schrodinger wavefunction
contains a feature that makes no sense at all we label the particles as though they were
distinguishable, and then promptly remove that distinguishability by antisymmetrizing the
wavefunction. It is the process of antisymmetrizing that introduces all the algebraic complexity. Taking a hint from the single-particle quantum harmonic oscillator, we look for a
different representation that focuses on operators instead of coordinate wavefunctions. We
now introduce the occupation number representation, which never labels the indistinguishable particles, and has the added virtue that it treats states with different total numbers of
particles on exactly the same footing.
5.2.1
Occupation number representation
Since the particles are identical, all we need to know is which single-particle states are
occupied and which are empty.
First step: Choose the single particle states |i (r). These must be eigenstates of a
separable (i.e. noninteracting) hamiltonian. For example:
1
Hence the name strongly correlated electrons, given to this general area of research. It is important
to note that correlation 6= interaction. Identical particles are correlated by virtue of the Pauli exclusion
principle, even in the absence of interaction.
36

Eigenstates of momentum and spin: |i |ki
Eigenstates of position (and spin): |i |ri, hr|r0 0 i = (r r0 ),0
Atomic-like orbitals centred on a particular atom in the crystal. (The only difference from true atomic orbitals is that they must have been made orthogonal to
the orbitals centred on the other lattice sites. We will discuss this more when we
come to the tight-binding model.): |i |ri i
Second step: Order the states by index . For example, if is the energy, then order
the states by increasing single-particle energy: E1 < E2 < ... < E < ... It doesnt
matter what ordering scheme we use all physical observables we calculate will be
independent of the ordering scheme as long as we are consistent. This must include
the ordering scheme for the spin labels as well.
Third step: Use abstract occupation-number vectors |n1 , n2 , ..., n , ...i as the basis vectors of the many-particle Hilbert space. (i.e. state 1 has n1 particles, state 2 has n2
particles, ... and so on.) For fermions, n = 0, 1. For bosons, n = 0, 1, 2, ...
Example: |0, 1, 0, 0, 1, 0, 1, 0, 0, ...i represents a state with
and 7 . This is equivalent to the Slater determinant

(a)
1 7
|0, 1, 0, 0, 1, 0, 1, 0, 0, ...i 5 (a)
3! (a)
2
identical fermions in states 2 , 5

7 (b) 7 (c)
5 (b) 5 (c) .
2 (b) 2 (c)
(5.13)
The rows of the determinant are written in reverse order. The reason for doing this will become clear below when we compare the Schrodinger and occupation number representations.
A very compact way of ensuring that our states have the proper fermion antisymmetry under
particle exchange is to use the JordanWigner algebra. For each state |i, define a creation
operator c and an annihilation operator c . These satisfy the anticommutation relations:
o
n
= c c0 + c0 c = ,0 ,
(5.14)
c , c0
n
o
c , c0
= 0,
(5.15)
n
o
c , c0
= 0.
(5.16)
It follows from this that:
2
(c )2 = c = 0
(Pauli principle)

2
c c
= c c c c = c 1 c c c = c c
(5.17)
(5.18)
Let n
= c c . Therefore n
2 = n
, so n
must have eigenvalues 0 and 1, as expected for
fermions.
We also need to define phase factors. Dropping the index , let
c |0i
c |1i
c|0i
c|1i
=
=
=
=
|1i
0
0
|0i.
(5.19)
(5.20)
(5.21)
(5.22)
37
A general antisymmetric basis state in the occupation number representation can then be
written:
(5.23)
|n1 , n2 , ..., n , ...i = (c1 )n1 (c2 )n2 ...(c )n ...|0i,
where |0i is the vacuum state or empty state.
Because the c anticommute, order is important!
5.2.2
Representation of states in second quantization
Here are some examples of many particle states in second quantized notation:
Filled Fermi sea:
|FSi =
ck |0i.
(5.24)
|k|<kF ,
BardeenCooperSchrieffer superconducting state:

Y

uk + vk ck ck |0i.
|BCSi =
(5.25)
This demonstrates that in the occupation number representation we can easily work
with states of mixed particle number, something we can not conveniently do in the
Schrodinger representation.
Occupation number representation vs. Slater determinants:
Let |2, 5, 7i = c2 c5 c7 |0i be the state we wrote down before:

7 (a) 7 (b) 7 (c)

1
|2, 5, 7i 5 (a) 5 (b) 5 (c) .
3! (a) (b) (c)
2
2
2
(5.26)
c1 acting on |2, 5, 7i is clearly zero, because state 1 is unoccupied.

c1 c2 c5 c7 |0i = (1)3 c2 c5 c7 c1 |0i = 0.
(5.27)
(The phase factor (1)3 comes from moving c1 through the rest of the operators.) Now
look at the effect of c5 on the same state:
c5 c2 c5 c7 |0i = (1)c2 c5 c5 c7 |0i

= (1)c2 1 c5 c5 c7 |0i
= (1)c2 c7 |0i.
(5.28)
(5.29)
(5.30)
Lets look at the same operation carried out on the Slater determinant. First we have
to bubble the row corresponding to the state we want to destroy to the bottom of the
determinant.

7 (a) 7 (b) 7 (c)
7 (a) 7 (b) 7 (c)
(1)

1
(5.31)
|2, 5, 7i 5 (a) 5 (b) 5 (c) = 2 (a) 2 (b) 2 (c) .
3! (a) (b) (c)
3! (a) (b) (c)
2
2
2
5
5
5
38

(Swapping rows in the determinant introduces a minus sign each time.) The bottom
row and right column can then be removed:

(1) 7 (a) 7 (b)
|2, 7i =
.
(5.32)
2! 2 (a) 2 (b)
General states:
In general, the annihilation operator c acting on a state |n1 , n2 , ..., n , ...i removes a
particle and gives:
c |n1 , n2 , ..., n , ...i = (1)S n |n1 , n2 , ..., n 1, ...i,
(5.33)
P1
where S =
i=1 ni is the number of states that come before in the ordering.
Likewise, we can show that when the creation operator adds a particle we get:
c |n1 , n2 , ..., n , ...i = (1)S (1 n )|n1 , n2 , ..., n + 1, ...i.
(5.34)
For example, the number operator n

= c c :
c c |n1 , n2 , ..., n , ...i =
=
=
2
2n n =
=
5.2.3
(1)S n c |n1 , n2 , ..., n 1, ...i

(5.35)
S
S
(1) (1) n (1 (n 1))|n1 , n2 , ..., n , ...i (5.36)
(2n n2 )|n1 , n2 , ..., n , ...i
(5.37)
1, n = 1
(5.38)
0, n = 0.
(5.39)
Representation of operators in second quantization
One and two particle operators are represented in the following ways in second quantization:
One particle operators:
U
N
X
U (ri )
(first quantization)
(5.40)
i=1
h|U |0 ic c0 ,
(second quantization)
(5.41)
where
h|U | i =
0
XZ
dr (r)U (r)0 (r).
(5.42)
Two particle operators:

V
N
1 X
V (ri , rj )
(first quantization)
=
2 i6=j=1
1 X
h|V |0 0 ic c c 0 c0 ,
(second quantization)
2 0 0
(5.43)
(5.44)

where
h|V |0 0 i =
39
XZ
Z
dr
dr0 (r) (r0 )V (r, r0 )0 (r) 0 (r0 ).
(5.45)
Note carefully the order of the electron operators.
5.2.4
Field operators
Now introduce the field operators:

(r) =
(r)
=
(r)c
(5.46)
(r)c
(5.47)
where the functions (r) form an orthonormal set. Using the anticommutation relations
for c and c , it is straightforward to show that
n
o
(r),
(r0 )
= (r r0 )
(5.48)
n
o
0)
(r),
(r
= 0
(5.49)
n
o
(r), (r0 )
= 0.
(5.50)
For the most commonly encountered case, where the single particle basis |i is the set of
momentum eigenstates of spin projection , we have
1 X ikr
e
ck
(r) =
V k
1 X ikr
(r) =
e ck .
V k
(5.51)
(5.52)
In terms of these the one- and two-particle operators become

XZ
U (r)
dr (r)U (r) (r)
(5.53)
1X
V (r, r0 )
2 0
Z
dr
dr0 (r) 0 (r0 )V (r, r0 )0 (r0 ) (r),
(5.54)
where the order of the operators is very important. (For one thing, this ordering prevents
self interactions.) What we see is that the second quantized operators look very similar to
expectation values in Schrodinger quantum mechanics, with the state and its conjugate
replaced by the operators and . The localized operators are what we get if we quantize
the Schrodinger field hence the name second quantization, as the eigenvalues of particle
number are now integers.
40
5.2.5
Examples of second quantized operators
Kinetic energy

N
X
XZ
p2i
~2 2
T =
T =
(r)
dr (r)
2m
2m
i=1
(5.55)
Density operator
n(r) =
N
X
(r ri ) n
(r) =
XZ
dr0 (r0 )(r r0 ) (r0 ) =
i=1
(r) (r) (5.56)
Total number of particles

Z
XZ
X
N = dr n
(r) =
dr (r) (r) =
c c
(5.57)
Spin operator
~=
S
N
X
i=1
X
~X
~i = ~
~i
S
2 i=1
2 ,0
dr (r)~,0 0 (r),
where ~ is the vector of Pauli matrices

0 1
0 i
1 0
~ = (x , y , z ) , x =
, y =
, z =
.
1 0
i 0
0 1
(5.58)
(5.59)
In particular,
~
Sz =
2
o ~Z
n
dr (r) (r) (r) (r) =

dr {
n (r) n
(r)} ,
2
(5.60)
as expected.
Hamiltonian

2
Z Z
XZ
~
1X
H=
dr (r)
+ U (r) (r)+
dr dr0 (r) 0 (r0 )V (rr0 )0 (r0 ) (r)
2m
2 0
(5.61)
Note that the second quantized operators have the same form regardless of the number of
particles, which is very convenient for many particle problems where we are often interested
in systems where the total number of particles is fixed only on average. The number of
particles is contained in the wavefunctions, which we have already shown are very flexible in
this regard and are even capable of having mixed particle number.
Lecture 6
Applications of second quantization
6.1
The tight-binding model
A common starting point for the discussion of electrons in solids is the tight-binding model.
(We will come back to the physics of this model in more detail later in the course, but for now
it serves as a good example.) Here we focus attention on a set of atomic orbitals arranged
on the sites of a lattice, with each orbital able to hold one electron of either spin. We have
localized creation operators ci that create an electron of spin projection at the site i. At
the typical densities found in solids, the atomic orbitals have substantial overlap with their
neighbours, resulting in a finite amplitude for the electron to tunnel, or hop, from one site
to the next. The typical arrangement is shown below, for a simple square lattice of side a.
i
j
Figure 6.1: An electron hopping from site j to site i on a simple square lattice of side a.
The time evolution depicted in the figure would be driven by a term in the hamiltonian of
the form tci cj , where t is the overlap between orbitals on neighbouring sites i and j. Note
that spin is conserved in this process. Including all such terms results in the hamiltonian
X
= t
H
ci cj ,
(6.1)
hi,ji,
where the brackets hi, ji denote a sum over all sites and nearest neighbour combinations of i
41
42
LECTURE 6. APPLICATIONS OF SECOND QUANTIZATION
and j. With periodic boundary conditions, this sum guarantees the hamiltonian is hermitian,
as it must be.
We now want to manipulate the hamiltonian into diagonal form that is, we want to find
the noninteracting eigenmodes and their energies. We begin by noting that the intersite
hopping and the spatial periodicity of the problem should result in running-wave solutions.
We look for these by transforming into momentum space. Suppressing the spin index, we
define creation and annihilation operators for electrons of wavevector k:
1 X ikri
e ci
(6.2)
ck =
N ri
1 X ikri
ck =
e
ci .
(6.3)
N ri
The inverse transform is defined:
1 X ikri
ci =
e
ck .
N k
(6.4)
We now substitute into the original hamiltonian.

X
= t
H
ci cj
(6.5)
hi,ji
X 1 X
1 X iqrj
= t
eikri ck
e
cq
N k
N q
hi,ji
(6.6)
A convenient way to do the nearest neighbour sum is to define a set of vectors such that
rj = ri + . For the 2D square lattice {a
x, a
y }, where x and y are unit vectors.
XXXX
= t
ei(kq)ri eiq ck cq
H
(6.7)
N i k q
The sum over the phase factors involving ri oscillates rapidly and vanishes unless k = q:
X
ei(kq)ri = N k,q .
(6.8)
ri
into diagonal form:

We use this to perform two of the summations and put H
XXX
= t
H
k,q eiq ck cq
= t
XX
(6.9)
eik ck ck .
(6.10)
The sum over we write out, and call k :

X
k t
eik
(6.11)
= 2t (cos(kx a) + cos(ky a)) .
(6.12)
Finally,
=
H
k n
k,
n
k = ck ck .
(6.13)
6.2. THE JELLIUM MODEL
6.2
43
The jellium model
As another good example, we now consider the model problem of N electrons interacting with
a fixed uniform background of positive charge, (hence jellium.) We will initially assume the
Coulomb interaction is screened, with a Yukawa-type form. The hamiltonian of the problem
can be broken into three parts:
=H
el + H
back + H
el-back .
H
(6.14)
Only the electrons have any interesting dynamics the background charge is just there to
maintain overall electrical neutrality.
el =
H
N
N
X
e2 1 X e|ri rj |
p2i
+
2m 40 2 i6=j=1 |ri rj |
i=1
(6.15)
1 is the electrostatic screening length, needed here as a convergence factor in the integrals.
We also have:
Z
Z
2
0 |rr0 |
e
1
0 n(r)n(r )e
Hback =
dr dr
,
(6.16)
40 2
|r r0 |
where n(r) is the density of positive charges = N/V = constant, from overall charge neutrality. The interaction between the electrons and the positive background is given by
N Z
e|rri |
e2 X
dr n(r)
.
(6.17)
Hel-back =
40 i=1
|r ri |
By making the change of variables = r r0 , we can immediately evaluate the energy of the
positive background.
Z
Z
0 |rr0 |
e2 1
0 n(r)n(r )e
dr dr
(6.18)
Hback =
40 2
|r r0 |
2 2
Z
Z
N
e
e 1
=
dr d3
(6.19)
V
40 2
2 2
Z
N
e 1
=
V 4
d e
(6.20)
V
40 2
0
N 2 e2 1
=
.
(6.21)
V 20 2
We can also evaluate the attractive potential between electrons and the background
N Z
e2 X
e|rri |
Hel-back =
dr n(r)
(6.22)
40 i=1
|r ri |
N Z
e2 N X
e
d3
=
(6.23)
40 V i=1
e2 N
1
=
N 4 2
40 V
2
2
e N 1
=
,
0 V 2
(6.24)
(6.25)
44
where we have taken advantage of translational invariance. The jellium hamiltonian can
then be written
2
2
=H
el e N 1 .
(6.26)
H
20 V 2
Since this is a translationally invariant problem, we should use the |ki basis.
X
T
hk0 0 |T |kick0 0 ck ,
(6.27)
k,k0 0
where

0
~2 2 eikr
eik r
,0
hk |T |ki =
dr
2m
V
V
Z
~2 k 2 1
0
= ,0
dr ei(kk )r
2m V
~2 k 2
k,k0 .
= ,0
2m
Z
0 0
(6.28)
(6.29)
(6.30)
The kinetic energy is therefore diagonal in wavevector

T =
X ~2 k 2
k
2m
ck ck .
(6.31)
Using the rule for two-particle operators, we can write the electronelectron interaction in
terms of the plane wave states.
1 X
V
2 k ,k
1 1
2 2
hk1 1 , k2 2 |V |k3 3 , k4 4 ick1 1 ck2 2 ck4 4 ck3 3 ,
(6.32)
k3 3 ,k4 4
where
0
eik3 r eik4 r
eik1 r eik2 r
V (r r0 )1 ,3 2 ,4 (6.33)
hk1 1 , k2 2 |V |k3 3 , k4 4 i = dr dr
V
V
V
V
Z
Z
2
|rr0 |
e
0 i(k3 k1 )r i(k4 k2 )r0 e
dr
dr
e
e
.(6.34)
= 1 ,3 2 ,4
40 V 2
|r r0 |
Z
Let = r r0 r0 = r .
e
.
(6.35)
The first integral is a momentum-conserving delta function, and the second is the Fourier
transform of the Yukawa potential with respect to the momentum transfer, so
e2
hk1 1 , k2 2 |V |k3 3 , k4 4 i = 1 ,3 2 ,4
40 V 2
hk1 1 , k2 2 |V |k3 3 , k4 4 i = 1 ,3 2 ,4
dr e
i(k3 k1 +k4 k2 )r
d3 ei(k4 k2 )
e2
4
k1 +k2 ,k3 +k4
.
40 V
|k4 k2 |2 + 2
(6.36)
6.2. THE JELLIUM MODEL
45
We introduce q = k4 k2 and redefine the momenta in terms of it:

k1
k2
k3
k4
=
=
=
=
k+q
k0 q
k
k0 ,
(6.37)
(6.38)
(6.39)
(6.40)
so that the momentum-conserving delta function will automatically be satisfied. Then

V =
e2 X X 4
c
c 0
0 ck0 0 ck .
80 V kk0 q 0 q 2 + 2 k+q, k q,
We treat the q = 0 term separately:

ck ck0 0 ck0 0 ck = ck ck0 0 ck ck0 0
h
i
0
0
= ck k,k , ck ck0 0 ck0 0
= n
k n
k0 0 k,k0 ,0 n
k .
(6.41)
(6.42)
(6.43)
Therefore
e2 X X 4
(
nk n
k0 0 k,k0 ,0 n
k )
80 V kk0 0 2

e2 1 N 2 N
=
.
20 2 V
V
V (q = 0) =
(6.44)
(6.45)
This cancels the constant we already had, provided 1 L, where V = L3 . Since the
energy no longer depends on the screening length 1 , we can set to zero, and the jellium
model can finally be written
=
H
X ~2 k 2
k
2m
ck ck +
e2 X X X 1
c
c 0
0 ck0 0 ck .
20 V kk0 q6=0 0 q 2 k+q, k q,
(6.46)
46
Lecture 7
The HartreeFock approximation
References: The HartreeFock approximation originated in atomic physics, but is just as easy to understand
in the context of electrons in solids. It is discussed in most solidstate textbooks.
7.1
A model two-electron system.
A very good example of the physics of interacting electrons is provided by a simple model
system of an atom or molecule with two single-particle orbitals and two electrons. Let the
orthogonal single particle orbitals be 1 (r) and 2 (r) and assume, to begin with, that these
single-particle orbitals are unchanged by the interaction. An important simplification arises
because the Coulomb interaction is independent of the spin of the particles. The operators
for total spin S and spin projection Sz will therefore commute with the hamiltonian, implying
that the two-electron wavefunctions will factorize into separate spatial and spin parts, and
that s and sz will be good quantum numbers for the two-electron states.1 There are four
possible spin states:
Triplet
S=1
1
2
Singlet
S=0
1
2
| i
(| i + | i)
| i
Sz = 1
Sz = 0
Sz = 1
(7.1)
(| i | i)
Sz = 0
(7.2)
The notation | i means spin up for electron one and spin down for electron two. The
singlet state is odd under particle exchange, and the triplet states are even. As a result, the
singlet state must be paired with an even spatial wavefunction, and the triplet state with a
spatially odd wavefunction, in order that the total wavefunction have overall antisymmetry
under exchange of particle coordinates. Since we must construct our states from only two
1
This would not be the case if there were a spinorbit term L.S in the hamiltonian. The states would
then be eigenstates of total angular momentum J and projection Jz .
47
48
LECTURE 7. THE HARTREEFOCK APPROXIMATION
single-particle states, the only possibilities are:

1
T (r1 , r2 ) = (1 (r1 )2 (r2 ) 2 (r1 )1 (r2 ))
2
1
S (r1 , r2 ) = (1 (r1 )2 (r2 ) + 2 (r1 )1 (r2 ))
2
(7.3)
(7.4)
The subscripts T and S label triplet and singlet wavefunctions respectively.

The requirement of antisymmetry under particle exchange introduces an important difference
between the singlet and triplet wavefunctions. The electrons in the triplet state keep further
apart than they would if they had been independent, and the electrons in the singlet state
stay closer together. We therefore expect the triplet state to have a lower Coulomb energy
than the singlet, which we can shown explicitly by evaluating the expectation value of the
hamiltonian. When we do this we find that
hHiS,T = E1 + E2 + EHartree Eexchange ,
(7.5)
where the +/ signs are for singlet and triplet respectively. E1 and E2 are the single particle
energies. The last two terms come from the matrix element of the Coulomb interaction. The
first term is the Hartree energy, and is just the interaction energy between the charge densities
of the single particle states.
Z
Z
e2
|2 (r)|2
(7.6)
EHartree = dr dr0 |1 (r0 )|2
40 |r r0 |
The second term has no classical analogue. It is called the exchange energy.
Z
Z
e2
Eexchange = dr dr0 2 (r)1 (r0 )
1 (r)2 (r0 )
40 |r r0 |
(7.7)
Despite the fact that the Coulomb interaction is independent of the spin of the electrons, we
end up with a spin-dependent term in the energy due solely to the requirement of antisymmetry in the wavefunction. This is the origin of magnetism in solids.
7.2
The HartreeFock approximation
It is generally impossible to find the true N -particle ground state, so we need to come
up with an approximation scheme. One way is to use a variational approach. We choose
a simpler, approximate form for the many-electron wavefunction , and then optimize it
so that it minimizes h|H|i, the total energy, subject to the constraints imposed on the
wavefunction by its approximate form.
In the HartreeFock method, we work with the simplest possible many-body wavefunction
for fermions a single Slater determinant. Although this is a drastic approximation the
true wavefunction is a linear combination of many different Slater determinants it has the
virtue that it will allow us to carry out calculations.
7.2. THE HARTREEFOCK APPROXIMATION
49
Having decided to throw away all but a single Slater determinant, we are now faced with the
choice of which single-particle orbitals to construct it from. While it may seem obvious that
these should be the single-particle states with the lowest kinetic energy, this is often not the
best choice. We actually have the freedom to choose any basis set { (r)}, and we should
make the choice that minimizes h|H|i. 2
Solving a HartreeFock problem is a variational procedure, and the HartreeFock energy
will always be greater than the true ground-state energy. The usual approach is to use an
iterative method, repeating until a self-consistent solution is found. It is quite possible that
during this process stationary states of h|H|i will be found that do not give the minimum
HartreeFock energy. The procedure should therefore include a way of testing that the
solution is a global minimum of h|H|i. Unfortunately, these other stationary states have
little to do with the true excited states of the system. We will show below that the problem
can be cast into a set of HartreeFock equations, which have the form of coupled nonlocal,
nonlinear Schrodinger equations.
The easiest and most honest way to derive the HartreeFock equations is to use second
quantization. Assume that we already know which single-particle states minimize the total
energy, and that these are the first N states drawn from a complete, orthonormal basis {|i}.
The corresponding electron operators are {c } and {c }. The HartreeFock wavefunction
|HFi is the Slater determinant
|HFi = c1 c2 ...cN |0i.
(7.8)
1 and a two-body part H
2.
The hamiltonian, in general, will have a one-body part H
= H
1 + H
2
H
X
1 X
h|V |0 0 ic c c 0 c0
=
h|T + U |0 ic c0 +
2 0 0
0
(7.9)
(7.10)
The one-body energy is

1 |HFi =
hHF|H
h|T + U |0 ihHF|c c0 |HFi
(7.11)
h|T + U |0 i0
(7.12)
occupied 0
N
X
h|T + U |i.
(7.13)
=1
hHF|c c0 |HFi = 0 , if |i is occupied, because |HFi is a single Slater determinant.

The interaction term is
X
2 |HFi = 1
h|V |0 0 ihHF|c c c 0 c0 |HFi
(7.14)
hHF|H
2 0 0
2
We need to be very careful at this point that we dont overlook any possibilities. The states { (r)} need
not be the single-particle states with the lowest kinetic energy, and the resulting many-body wavefunction
need not have the full symmetry of the hamiltonian.
50
Initial guess for the single particle states |>
Compute VH, VE
Solve the Hartree-Fock equations

Find new single particle states |>
Is the solution self-consistent?
No
Yes
Done
Figure 7.1: The iterative self-consistency procedure for HartreeFock calculation.
There are two possibilities:

= 0 , = 0 :
hHF|c c c c |HFi = 1 |i, |i occupied
= 0 , = 0 :
hHF|c c c c |HFi = hHF|c c c c |HFi = 1 |i, |i occupied
(7.15)
(7.16)
(7.17)
(7.18)
The interaction term is therefore

N
o
1 X n
h|V |i h|V |i
hHF|H2 |HFi =
2 6==1
(7.19)
If = , c2 = 0. We dont need to worry about this explicitly, because the direct and
exchange terms will cancel. Writing the total energy in terms of the single particle orbitals,
we have
=
hHi
N Z
X
dr
(r)
=1

~2 2
+ U (r) (r)
2m
(7.20)
Z
N Z
1 X
+
dr dr0 (r) (r0 )V (r r0 ) [ (r) (r0 ) (r0 ) (r)] (7.21)
2 ,=1
7.3. HARTREEFOCK THEORY FOR JELLIUM
51
If |i = |HFi is the best single Slater determinant, then it will correspond to a minimum of
the total energy. Using a Lagrange multiplier E to enforce the normalization constraint, we
need to minimize h|H|i

Eh|i with respect to all the single particle orbitals (r):
i
h
h|
H|i
Eh|i
= 0.
(7.22)
(r)
This leads directly to the HartreeFock equations. For each , we have:

Z
~2 2
+ U (r) (r) + VH (r) (r) dr0 VE (r, r0 ) (r0 ) = E (r), where

2m
VH (r) =
VE (r) =
N Z
X
=1
N
X
dr0 V (r r0 )| (r0 )|2
V (r r0 ) (r0 ) (r)
(7.23)
Hartree potential
(7.24)
exchange potential
(7.25)
=1
These equations are solved iteratively.
7.3
HartreeFock theory for jellium
In some cases we can use symmetries of the hamiltonian to guess the correct single-particle
states { (r)}. For instance, if the hamiltonian doesnt depend explicitly on spin, we might
expect a paramagnetic state
|HFi = c1 c1 c2 c2 ...cN cN |0i.
2
(7.26)
However, this can be dangerous, as the lowest energy state can be a broken-symmetry state,
such as the ferromagnetic state
|FMi = c1 c2 ...cN |0i.
(7.27)
We now want to apply the HartreeFock method to the jellium model. From translational
symmetry, we can guess that
Y
|HFi =
ck |0i.
(7.28)
|k|<kF ,
From the last lecture, the jellium hamiltonian is

X ~2 k 2
e2 X X X 1
=
ck ck +
c
c
c 0 0c
H
2 k+q k0 q 0 k k
2m
2
V
q
0
0
0
k
kk q6=0
The kinetic energy is already diagonal in (k), so
X ~2 k 2
hHF|T|HFi =
hHF|ck ck |HFi
2m
k
X ~2 k 2
=
(kF |k|),
2m
k
(7.29)
(7.30)
(7.31)
52

F(x)
1
0.8
logarithmic
singularity
0.6
0.4
0.2
0.2
0.4
0.6
0.8
Figure 7.2: Plot of the function F (x) =
1.2
1
2
1.4
1x2
4x

.
ln 1+x
1x
where (x) is the unit step function.

In the interaction term there is only one possibility that will give a nonzero contribution to
hHF|V |HFi:
k + q = k0 q = k0 k and = 0 .
(7.32)
The direct term, q = 0, has already been used to balance the interaction of the electrons
with the positive background. This implies that k 6= k0 . We therefore have
1
e2 X X
hHF|ck0 ck ck0 ck |HFi
(7.33)
hHF|V |HFi =
0
2
20 V k6=k0 |k k |
i
h
e2 X X
1
0
0
(7.34)
=
hHF|c
c
c
k,k
k k ck |HFi
k0
20 V k6=k0 |k k0 |2
=
e2 X X
1
hHF|
nk0 n
k |HFi
20 V k6=k0 |k k0 |2
= 2
e2 X
20 V
|k|<kF
X
|k0 |<kF
1
|k k0 |2
(7.35)
(7.36)
Convert one of the sums to an integral:

Z 1
Z kF
X e2 V
k 0 2 dk 0
hHF|V |HFi =
2
d(cos
)
0 V (2)3
k 2 + k 0 2 2kk 0 cos
1
0
|k|<k
(7.37)
Evaluating this integral allows us to write the single particle energy (k) as

~2 k 2
e2
k
(k) =
2 kF F
,
2m
2 0
kF
where

1 1 x2 1 + x
F (x) = +
ln
.
2
4x
1 x
(7.38)
(7.39)
7.3. HARTREEFOCK THEORY FOR JELLIUM
53
/F
2
kinetic energy
0.5
total energy
1.5
k/kF
-1
-2
Figure 7.3: Plots of the single particle energy (k) with and without the exchange energy.
The exchange term substantially lowers the energy and increases the bandwidth. Neither
the increased bandwidth nor the singular form of the energy dispersion are supported by
experiments such as photoemission spectroscopy, electrical transport and thermodynamics.
In the HartreeFock approximation, the one-electron levels of the interacting system are still
plane waves, but their energy is lowered by an exchange interaction that acts only between
electrons of the same spin projection. If the single particle energies are summed over all
occupied states, we get the total energy of the N electron system. This can be shown to be

3 e2 kF
3
(7.40)
Etotal = N F
5
16 2 0
The energy dispersion (k) has a logarithmic singularity in the slope at k = kF . This leads
to a depression of the density of states at the Fermi level to zero, called a Coulomb gap. For
electron systems at metallic densities, this behaviour is unphysical, with no experimental
evidence to support it. The origin of the problem can be traced back to the long-range
nature of the Coulomb interaction, which causes divergences in the interaction strength at
small momentum transfer. We will see in the next lecture that charge screening by the
electron gas changes the bare Coulomb interaction to a short-range repulsive potential. The
singularities in the theory then disappear.
54
Lecture 8
Screening and the random phase
approximation
References: The ThomasFermi theory of screening is discussed in most solid-state textbooks. This presentation of the random phase approximation follows Chapter 2 of Taylor and Heinonen [7].
8.1
Screening
Screening is one of the simplest and most important examples of electronelectron interaction. Imagine introducing a positive test charge, with charge density ext (r), into a free
electron gas, and holding it fixed in position. It will attract the nearby electrons, creating
an excess of negative charge in its vicinity, compensating its own charge. How effective is
this, and over what range does it occur?
Introduce two potentials: ext (r), due solely to the external charge, and tot (r), due to all the
charges in the metal, including the external charge. Both potentials obey Poissons equation:
ext (r)
,
0
tot (r)
.
2 tot (r) =
0
2 ext (r) =
(8.1)
(8.2)
Let tot (r) = ext (r) + ind (r), where ind (r), the induced charge density, is what we want
to calculate. ext (r) and tot (r) are related by the dielectric function r (r r0 ), which in a
homogeneous system is just a function of separation.
Z
ext
(r) = dr0 r (r r0 )tot (r0 )
(8.3)
In real space the situation is quite complex. The dielectric function r (r r0 ) is a nonlocal
response function, requiring a convolution integral. The situation becomes much simpler if
we work in reciprocal space. We define the Fourier transform
Z
fq dr eiqr f (r).
(8.4)
55
56
LECTURE 8. SCREENING AND THE RANDOM PHASE APPROXIMATION
After Fourier transformation Eq. 8.3 becomes an algebraic equation.

tot
ext
q = r (q)q
(8.5)
Now introduce the charge susceptibility q , which is defined by

tot
ind
q = q q .
(8.6)
In Fourier space, the Poisson equations become

ext
q
,
0
tot
q
=
.
0
=
q 2 ext
q
(8.7)
q 2 tot
q
(8.8)
Rearranging we get:
2
ext
ind
= q tot
tot
q
q = 0 q
q q
1
ext
tot
q = q
1 q /0 q 2
q
r (q) = 1
.
0 q 2
8.2
(8.9)
(8.10)
(8.11)
ThomasFermi theory
We can make a simple approximation to calculate the induced charge ind (r) from the potential tot (r), which will be accurate as long as tot (r) varies slowly in space that is, as
long as q kF . We assume that the effect of the total potential is to shift all the single
electron energies by etot (r). This is completely equivalent to a local shift in the chemical
potential
(r) = + etot (r).
(8.12)
The chemical potential determines the electron density, with all single particle states filled
to the chemical potential at zero temperature. A local shift in the chemical potential has
the effect:
n(r) n(r) + n(r),
(8.13)
where
n(r) =
dn
dn
(r) =
e tot (r).
d
d
(8.14)
The induced charge is

ind (r) = e n(r)
dn
= e2 tot (r).
d
(8.15)
(8.16)
8.2. THOMASFERMI THEORY
57
(r)
tot(r)
ext(r)
n(r)
Figure 8.1: The response of the electron gas to an external charge.
dn/d is just the density of states at the Fermi level D(F ).

ind (r) = e2 D(F )tot (r)
q = e2 D(F ),
(8.17)
(8.18)
independent of q. Therefore, the q-dependent dielectric function is

e2
D(F )
0 q 2
k2
= 1 + 20 ,
q
2
e
D(F ).
=
0
r (q) = 1 +
k02
(8.19)
(8.20)
(8.21)
When the external charge is a point charge

Q
40 r
Q
=
0 q 2
1 ext
=
r (q) q
Q 1
=
.
0 q 2 + k02
ext (r) =
(8.22)
ext
q
(8.23)
tot
q
(8.24)
(8.25)
When Fourier transformed back to real space, this gives a screened, short-ranged, Yukawatype potential:
Q k0 r
tot (r) =
e
.
(8.26)
40 r
k0 is typically of the order of kF . At metallic densities the Coulomb interaction is therefore
strongly screened for distances greater than 1
A.
58
8.3
The density operator
In the following, spin does not play a role in the interactions, so the spin index will be
suppressed. Were we to consider a magnetic system, spin could be included and the same
approach used to discuss spin density waves.
We saw in Lecture 5 that we can define fermion field operators in terms of momentum space
operators
1 X ikr
(r) =
e
ck
(8.27)
V k
1 X ikr
(r) =
e ck
(8.28)
V k
and that these can be used to measure the particle density at point r
(r) n
(r) = (r) (r).
(8.29)
The density operator is defined to be proportional to the Fourier transform of the particle
density.
Z
1
eiqr (r)dr
(8.30)
q
V
1 X
=
c ck+q .
(8.31)
V k k
The normalization is chosen so that 0 gives the average particle density. The adjoint operq , q0 ] = 0.1
ator is q = q . For the electron gas, the density operators commute: [
The density operators are useful because we can always express the electronelectron interaction in terms of them. In Lecture 6 we derived the jellium hamiltonian. With spin indices
suppressed this is
X
e2 X X 1
k ck ck +
H=
ck+q ck0 q ck0 ck ,
(8.32)
2
20 V kk0 q6=0 q
k
where k = ~2 k 2 /2m is the kinetic energy. Using the density operators the jellium hamiltonian can be rewritten[7]
X ~2 k 2

e2 X 1
=
ck ck +
V 2 q q N ,
(8.33)
H
2
2m
20 V q6=0 q
k
with N the total particle number. In general, the interaction term of any hamiltonian will
be diagonal in the Fourier components of the particle density. Only in rare circumstances,
however, will density fluctuations of well-defined wavenumber also diagonalize the kinetic
energy. We will return to this point in the context of spincharge separation, which occurs
in one-dimensional metals. In that case both the kinetic and potential energy are diagonal
in the basis of spin and charge density waves.
1
In Lecture 25 we will study the LuttingerTomonaga model of spincharge separation in a onedimensional metal. There the density operators do not always commute. In that case, the noncommutation
arises from the somewhat artificial assumption that the one-dimensional energy band consists of occupied
states extending down to infinite negative energy.
8.4. THE RANDOM PHASE APPROXIMATION
8.4
59
The random phase approximation
In the noninteracting case, the excited states of the electron gas are particlehole excitations
about the Fermi surface. We would like to know what the excited states of the interacting
system are. We assume they exist and that they are created by the operator b .
We start with the many-body system in its ground state |i. The ground state energy 0 is
given by
H|i
= 0 |i.
(8.34)
If b creates an excitation, then
|i = (0 + b )b |i
Hb
(8.35)
b H)|i
(Hb
= b b |i.
(8.36)
or
If this holds in general (not just for the ground state) then
b ] = b b .
[H,
(8.37)
This is the algebra for a bosonic raising operator, which we saw earlier in the context of the
harmonic oscillator.
What is b ? A first guess might be that
b = cp+q cp .
(8.38)
This takes an electron from state |pi and places it into state |p + qi. For the noninteracting
hamiltonian
X
0 =
H
k ck ck
(8.39)
k
this choice works. In that case

0 , cp+q cp ] = (p+q p )cp+q cp .
[H
(8.40)
The situation changes somewhat when we include the Coulomb interaction. At large momentum transfers the kinetic energy dominates the Coulomb energy, and particlehole excitations are still good approximate excited states. However, at small q the interaction term
becomes too important to ignore. We then have to try a different approach, by summing
the particlehole operator cp+q cp over all p. This is just the density operator
X
(8.41)
q =
cp+q cp
p
Now when we evaluate the commutator of q with the hamiltonian, the interaction term
makes no contribution because density operators commute. The commutator is just the sum
over all momenta of Eq. 8.40.
X
] =
[H,
(p+q p )cp+q cp .
(8.42)
q
p
60
It is still not clear we are on the right track, even approximately. We are looking for something
of the form
] ~ .
[H,
(8.43)
q
q
If indeed that is approximately what we have, then
[H,
]] (~)2 .
[H,
q
q
(8.44)
The double commutator is evaluated in Taylor and Heinonen, with the final result that, for
the jellium model,

2
V X
~2 q q0
1 X ~2
(2p q + q ) cp+q cp +
V q0
(
q0 q q0 q0 qq0 ),
[H, [H, q ]] =
V p 2m
2 q0 6=0
m
(8.45)
where Vq e2 /0 V q 2 are the matrix elements of the Coulomb potential.
All the physics is contained in this expression. We are primarily interested in small q, as this
is where the particlehole excitations cease to be good eigenstates. The first term goes to
zero like q 2 so is unimportant in the long wavelength limit. In the second term, one Fourier
component of the particle density stands out from the rest. This is the zeroth component, 0 ,
which is just the average density of particles. Therefore terms containing 0 will dominate
the sum. Because q0 = 0 is omitted from the sum (this term was used to cancel the energy
of the positive background in the jellium model) 0 only appears when q0 = q. Omitting
the rest of the terms is called the random phase approximation or RPA. We are left with
e2 ~2 q 2
(
0 q + q 0 )
20 q 2 m
~2 e2
=
0 q
0 m
= (~)2 q
[H,
]]
[H,
q
(8.46)
(8.47)
(8.48)
The frequency of the charge density excitations is

2 =
e2 0
,
0 m
(8.49)
which is just the classical plasma frequency p .

There is another way of looking at what we have just done. In the equation of motion
method we make use of the fact that the time dependence of an operator is generated by
the hamiltonian. We then have that
i~

H].
O = [O,
t
(8.50)
What we have shown above is that, at long wavelengths

2
+ p2 q = 0.
t2 q
(8.51)
That is, charge fluctuations of definite wavenumber are oscillator-like solutions to the model.
8.5. COLLECTIVE EXCITATIONS OF THE ELECTRON GAS
8.5
61
Collective excitations of the electron gas
The relevant excitations at long wavelengths are collective motions of the electron gas, called
plasmons. We can include them in an energymomentum diagram along with electronhole
excitations, which occupy the hatched region. The plasmons become heavily damped in that
region.
Figure 8.2: Excitations of the electron gas, from Mahan[8].
62
Lecture 9
Scattering and periodic structures
In the last few lectures we have concentrated on systems of interacting electrons and have
ignored the crystalline structure of real solids. We will now take the opposite approach and
focus on the effect of a periodic potential on the electronic structure. For the time being we
will ignore the Coulomb interaction, which will make the problem entirely tractable. In real
solids we will very often get away with doing this, as in many metals the electronelectron
interaction energy is smaller than we would calculate for a bare Coulomb interaction, due
to the phenomenon of screening. Later in the course we will see another reason for treating
the electrons as weakly interacting particles Landaus Fermi liquid theory which shows
that in many systems there is a one-to-one mapping of the electrons of a noninteracting
system onto the weakly interacting quasiparticles of the full many-body hamiltonian.
The hamiltonian of the crystal, in the absence of electronelectron interactions, is:
=
H
N
X
p2i
+ U (ri ),
2m
i=1
(9.1)
where U (ri ) is a one body potential with the full periodicity of the crystal lattice. We
immediately notice that this hamiltonian is separable, which allows the N electron problem
to be recast in terms on N completely independent one-electron problems. We saw in
Lecture 7 that for any Slater determinant the expectation value of the one-body part of
the hamilonian is just the sum of N single-particle energies, despite the strong correlations
between particle positions that are built into the Slater determinant. As a result, fermion
correlation in the many-body wave function only affects the interaction terms, which we are
now going to ignore. This means that, as far as the one-body terms go, the problem of
N electrons really does split up into N separate single-particle problems, all of which are
identical. At this level, fermion correlations only come into the problem through the Pauli
exclusion principle, by determining which single particles levels are occupied and which are
empty.
63
64
LECTURE 9. SCATTERING AND PERIODIC STRUCTURES
9.1
The Born approximation
Before treating electrons moving in a periodic potential, it is useful to look at the problem of
a wave scattering from a distributed system. We will consider the problem of electron waves,
but the same approach could be taken for the scattering of light, sound, neutrons, etc. All
that would be required is a different form of the potential. Here we consider the case of a
quantum particle scattering weakly from a potential V (r). The Schrodinger equation is:

~2 2
+ V (r) (r) = E (r).
2m
This can be rewritten:

(2 + k 2 )(r) =
where k =
2m
V (r)(r),
~2
(9.2)
(9.3)
p
2mE/~2 . Let the incident wave be A exp(iki r). It is a solution of
(2 + k 2 )(r) = 0.
(9.4)
We can write a formal solution to Eq. 9.3 as

Z
2m
iki r
(r) = Ae
+ dr0 G(r r0 ) 2 V (r0 )(r0 ),
~
(9.5)
where G(r) is the Greens function of Eq. 9.3. That is

(2 + k 2 )G(r) = 3 (r).
(9.6)
Although this is formally a solution, it contains (r) on both sides. It does, however, provide
a useful way of obtaining a perturbative solution to Eq. 9.3 by iteration. This procedure is
called the Born approximation.
It turns out that G(r) has the form of a spherical wave,
G(r) =
eikr
,
4r
(9.7)
which can be seen by substituting into Eq. 9.6 and using

1
2
= 4 3 (r).
r
(9.8)
(It is a good exercise to verify this result if you do so, use the spherical coordinate
expressions for div, grad and 2 = .)
Using this we obtain
(r) = Ae
iki r
2~2
dr0
eik|rr |
V (r0 )(r0 ).
|r r0 |
(9.9)
9.2. PERIODIC STRUCTURES
65
1
2 2
r2 2r r0 + r0
1

r0 r0 2 2
(
r is a unit vector)
= r 1 2
r + 2
r
r

r0
r 1
r
as r
r
|r r0 | =
(9.10)
(9.11)
(9.12)
We need to retain both these terms in the exponent, but only the first in the denominator:
0
0
exp ikr(1
r rr )
eik|rr |
(9.13)
|r r0 |
r
1 ikr ikf r0
=
e e
,
(9.14)
r
where kf = k
r is the outgoing wavevector.
So
Z
meikr
0
iki r
dr0 eikf r V (r0 )(r0 ).
(r) Ae
2
2~ r
(9.15)
For weak scattering, the wavefunction in the sample is comprised mainly of the incoming
wave. So, to first order in the potential, we can substitute the incoming wave into the
integral.
Z
A m eikr
0
iki r
dr0 ei(ki kf )r V (r0 ).
(r) = Ae
(9.16)
2
2~ r
That is, the scattering amplitude is proportional to the Fourier transform of the potential
with respect to the momentum transfer q = ki kf .
Z
f (, ) dr eiqr V (r).
(9.17)
9.2
Periodic structures
In solid state physics we are interested in taking the Fourier transform of periodic functions,
either to calculate diffraction conditions, in which case the periodic function is the electron
density or spin density, or to find out which plane wave states are mixed when we switch on
the periodic potential.
9.2.1
Convolution as a means of replication
The calculation of Fourier transforms of periodic functions is greatly simplified if we introduce

the idea of convolution. The convolution of f1 (r) and f2 (r) is
Z
F (r) = f1 (r) f2 (r) dr0 f1 (r0 )f2 (r r0 ).
(9.18)
66
We will always be interested in the case where one of the functions is a set of -functions.
To see why, let f2 (r) = (r R).
Z
F (r) = f1 (r) f2 (r) dr0 f1 (r0 )((r R) r0 )
(9.19)
= f1 (r R)
(9.20)
Convolution of f (r) with a -function replicates f (r) at a different position. We now have
a way of representing arbitrary periodic functions: we make a new function, which is finite
only in the vicinity of one of the lattice points (i.e., within one unit cell of the lattice) and
convolve it with a set of -functions centred at each of the lattice points, thereby tiling the
function periodically over the whole volume of the crystal.
9.2.2
The convolution theorem
We often want to calculate the Fourier transform of a convolution:

Z
G(q) = dr eiqr F (r),
(9.21)
where F (r) = f1 (r) f2 (r).

Z
G(q) =
dr e
iqr
dr0 f1 (r0 )f2 (r r0 )
(9.22)
Let r00 = r r0 .
Z
iq.(r00 +r0 )
dr0 f1 (r0 )f2 (r00 )

Z
Z
0
00 iqr00
00
=
dr e
f2 (r ) dr0 eiqr f1 (r0 )
G(q) =
00
dr e
(9.23)
(9.24)
In other words, the transform of a convolution = the product of the transforms.

A similar result can be derived for the transform of a product it is the convolution of the
transforms. (You should prove this as an exercise.)
9.3
The reciprocal lattice
A Bravais lattice is defined by a set of three fundamental (or primitive) translation vectors
a1 , a2 and a3 . If we choose as the origin one of our lattice points, then the set of lattice
points are the vectors
R = n1 a1 + n2 a2 + n3 a3 ,
(9.25)
where ni are integers. The most convenient unit cell to use is the WignerSeitz cell, the
smallest volume enclosed by the intersection of the perpendicular bisecting planes of the
lattice vectors. A function with the same periodicity of the lattice has the property
f (r + Ri ) = f (r),
lattice vectors Ri .
(9.26)
9.3. THE RECIPROCAL LATTICE
67
It can therefore be written

f (r) = f0 (r)
(r Ri ),
(9.27)
where f0 (r) = f (r) within the WignerSeitz cell and is zero everywhere else.
The Fourier transform g(q) is then the product
Z
Z
X
0
iqr
(r0 Ri )
g(q) =
dr e
f0 (r) dr0 eiqr
(9.28)
= g0 (q)
iqRi
(9.29)
g0 (q) is called the structure factor. In the summation we are adding together terms with
different phases. These will cancel (add to zero) unless the Bragg condition is satisfied:
q Ri = 2m,
(9.30)
for all the Ri in the lattice, where m is an integer. The special values of q that satisfy this
condition lie on a lattice, which is called the reciprocal lattice. (It is a lattice, because if we
find any two vectors that satisfy Eq. 9.30, then their sum also satisfies Eq. 9.30.)
The primitive vectors of the reciprocal lattice are given by
b1 = 2
a2 a3
a1 a2 a3
and cyclic permutations.
(9.31)
68
Lecture 10
The nearly free electron model
We saw in the last lecture that scattering from
a periodic structure results in Bragg reflection.
The scattering amplitude, as a function of the
momentum transfer q = k k0 , is proportional to
the Fourier transform of the scattering potential,
and the Fourier transform of a periodic structure
is finite only at special values of q. These reflections form a lattice, called the reciprocal lattice.
Vectors in the reciprocal lattice are labelled G.
The lattice spacing is determined by the periodicity of the scattering potential, and the strength
of the individual reflections is determined by the
details of the potential or density within a single
unit cell of the scatterer. In particular, when the
primitive unit cell contains more than one atom,
the crystal structure consists of a Bravais lattice
+ a basis, and we expect the structure factor (the
Fourier transform of the basis) to cancel some of
the reflections completely in some instances.
The conditions for Bragg reflection are:
/2G
k
G
k-G
/2G
k
k - 1/2G
Figure 10.1: Bragg scattering.
energy conservation: k 2 = k 0 2
conservation of crystal momentum: k =
k0 + G, where G is a reciprocal lattice vector.
Together, these conditions imply
|G|
.
(10.1)
2
That is, the projection of k onto G lies halfway along G. The locus of points satisfying this
condition therefore form a set of planes Bragg planes which cut the reciprocal lattice
vectors perpendicularly through their midpoints. These planes divide k-space into zones,
=
kG
69
70
LECTURE 10. THE NEARLY FREE ELECTRON MODEL
called Brillouin zones. The first Brillouin zone is the WignerSeitz cell of the reciprocal
lattice and is the set of all points in k-space closer to G = 0 than any other reciprocal lattice
vector.
10.1
Blochs theorem
In a crystal, the potential of the ion cores is periodic it has discrete translational symmetry:
U (r + R) = U (r),
(10.2)
where R is any vector in the real-space lattice. As a result, the hamiltonian commutes with
the translation operator TR , which has the effect
TR (r) = (r + R).
(10.3)
We can define TR in terms of the generator of translations, the momentum P:
TR = eiPR/~
TR
= e
iPR/~
(10.4)
(10.5)
= 0, TR and H
must have common eigenfunctions, but with different
Because [TR , H]
eigenvalues. Therefore, any energy eigenstate |i must also be an eigenstate of TR .
TR |i = eiPR/~ |i cR |i
(10.6)
We define the eigenvalue of translation to be cR . Now

hr|TR = hr + R|,
(10.7)
hr|TR |i = hr + R|i = cR hr|i

(r + R) = cR (r).
(10.8)
(10.9)
so that
Now operate on the plane wave state |ki:

hk|TR = eikR hk|.
(10.10)
hk|TR |i = eikR hk|i = cR hk|i,
(10.11)
Therefore
so either hk|i = 0 or cR = eikR . In other words, the energy eigenstates |i that have
finite overlap with the plane wave state |ki can be labeled by their Bloch wavevector k, and
have eigenvalue eikR when acted on by the translation operator TR . There are infinitely
many different eigenstates with the same eigenvalue under translation, as k is only defined
to within a reciprocal lattice vector G, and eiGR = 1 . To distinguish between them, we
need to introduce a new quantum number, the band index n. However, because k and k + G
are equivalent, we can specify a unique and complete set of labels by restricting ourselves to
a single Brillouin zone. In the following, we will use the convention followed in Ashcroft and
Mermin [4], where q is an arbitrary wavevector, and k = q + G is a wavevector in the first
Brillouin zone.
10.2. FREE ELECTRON IN 1D AS A BLOCH WAVE
71
/ (h22/2ma2)
10
8
6
4
2
3/a
2/a
/a
/a
2/a
3/a
Figure 10.2: One dimensional energy dispersion in the extended zone scheme.
10.2
Free electron in 1D as a Bloch wave
In the limit where the periodic potential vanishes (U (r) 0), we must recover free electrons
with wavefunction q (r) eiqr . These can be viewed as a special case of Blochs theorem, if
we remember what our reciprocal lattice vectors G were before we switched off the potential.
This will serve to demonstrate the connection between the band index n and the reciprocal
lattice vectors.
q (r) eiqr
= eikr eiGr
(10.12)
(10.13)
= eikr ein( a )r
n,k (r)
(10.14)
(10.15)
(In higher dimensions it is not possible to define such a direct mapping between reciprocal
lattice vectors and the band index, but the same principle applies). If we plot the energy
dispersion (q) = ~2 q 2 /2m as a function of q, we get the extended zone scheme shown in
Fig. 10.2. If we plot the dispersion as a function of k, we have the reduced zone scheme,
where the energy bands (k, G) = ~2 (k G)2 /2m are folded back into a single zone, as shown
in Fig. 10.3. A third possibility is to use the repeated zone scheme, good for demonstrating
the periodicity of the energy bands, but then we will over-count the states.
72
/ (h22/2ma2)
10
/a
/a
Figure 10.3: One dimensional energy dispersion in the reduced zone scheme.
10.3. NEARLY FREE ELECTRONS
10.3
73
Nearly free electrons
We can use the periodicity of the ionic potential to expand U (r) in a set of discrete Fourier
components at the reciprocal lattice vectors G.
X
U (r) =
UG eiGr
(10.16)
G
U (r + R) =
UG eiGr eiGR
(10.17)
since eiGR = 1.
= U (r),
10.3.1
(10.18)
Properties of UG
U (r) is real:
U (r) = U (r)
X
X
iGr
UG eiGr =
UG
e
G
(10.19)
(10.20)
UG
eiGr
(10.21)
UG = UG
.
(10.22)
If the crystal has inversion symmetry:

X
U (r) = U (r)
X
UG eiGr =
UG eiGr
(10.23)
(10.24)
UG eiGr
(10.25)
UG = UG .
(10.26)
While the ionic potential is always real, crystals do not always have inversion symmetry. If
a crystal does, we can make the Fourier components of the potential real by choosing the
origin r = 0 to be a centre of inversion symmetry.
What are the UG ?
X
U (r) =
UG eiGr
(10.27)
G
iG0 r
dr U (r)e
cell
X
G
Z
UG
dr ei(GG )r
(10.28)
cell
UG Vcell G,G0
(10.29)
UG
0 V
= UG
ZN
N
=
dr U (r)eiGr ,
V cell
(10.30)
(10.31)
74
where N is the number of unit cells in the crystal and V is the volume of the crystal.
10.4
The Schr
odinger equation in momentum space
We can now write the Schrodinger equation

~2 2
+ U (r) (r) = E(r)

2m
(10.32)
in momentum space, for a periodic potential. Lets first Fourier-expand the wavefunction:
X
(r) =
cq eiqr ,
(10.33)
q
remembering that q is an arbitrary wavevector. Substituting this into the Schrodinger

equation we get
X
2 2
X
X
~q
iqr
cq eiqr
UG eiGr = 0.
(10.34)
E +
cq e
2m
q
q
G
We want to concentrate on each Fourier component separately, so rearrange and group
together terms with common plane-wave components:
2 2
XX
X
~q
iqr
cq e
E +
cq UG ei(q+G)r = 0.
(10.35)
2m
q
q
G
Let q0 = q + G, and use the fact that the sums over q and G run to infinity:
2 2
XX
X
~q
0
iqr
cq e
E +
cq0 G UG eiq r = 0.
2m
q
G
q0
But q0 is just an index of summation, so we are free to relabel it q0 q:
(
)

2 2
X
X
~
q
eiqr
E cq +
cqG UG = 0.
2m
q
G
(10.36)
(10.37)
The plane waves form an orthogonal set, so each term in the sum must separately be zero:
2 2

X
~q
E cq +
cqG UG = 0.
(10.38)
2m
G
We usually work in the reduced zone scheme, with q = k K, where K is the reciprocal
lattice vector that maps q into the first Brillouin zone.
2

X
~ (k K)2
E ckK +
UG ckKG = 0,
(10.39)
2m
G
10.5. THE PERIODIC POTENTIAL AS A WEAK PERTURBATION
75
or, if we redefine G G K,

2
X
~ (k K)2
E ckK +
UGK ckG = 0.
2m
G
(10.40)
The original problem separates into N independent problems, one for each allowed value of
k in the first Brillouin zone. Each problem has an infinite set of solutions constructed from
plane waves of wavevector k, and wavevectors differing from k by a reciprocal lattice vector.
X
k (r) =
ckG ei(kG)r
(10.41)
G
States of this form are Bloch functions:

k (r + R) =
ckG ei(kG)r eikR eiGR
G
ikR
= e
10.5
(10.42)
k (r).
(10.43)
The periodic potential as a weak perturbation
We now imagine switching on the periodic potential as a weak perturbation. To zeroth order,
our solutions are just free electron plane waves. All the UG are zero and we can write

2
~ (k K)2
E ckK = 0.
(10.44)
2m
For a given k and K, only one coefficient is nonzero, ckK , and E =
We get one solution for each wavevector k and each band K.
10.5.1
~2
(k
2m
K)2 0kK .
The nondegenerate case
If, for some fixed wavevector k and a band corresponding to a particular reciprocal lattice
vector K1 ,
|0kK1 0kK | U, K 6= K1 ,
(10.45)
we can use nondegenerate perturbation theory. We want to solve
X

UGK1 ckG = 0.
0kK1 E ckK1 +
(10.46)
To first order, set ckG = ckK1 G,K1 .

0kK1 E ckK1 + U0 ckK1 = 0
(10.47)
The energies are just shifted by the average potential U0 . We will set U0 = 0, without
any loss of generality. Now calculate the shift in the ckK to first order, again assuming
ckG = ckK1 G,K1 in the sum.
X

0kK 0kK1 ckK +
UGK ckK1 G,K1 = 0
(10.48)
G6=K
0kK
0kK1
ckK + UK1 K ckK1 = 0

(10.49)
76
Therefore
ckK =
UK1 K
ckK1
0
kK1 0kK
+ O(U 2 ).
(10.50)
We can now substitute in the new coefficients to the original equation to obtain the shift in
energy to second order:
X

E 0kK1 ckK1 =
UGK1 ckG
(10.51)
G6=K1
X UGK UK G
1
1
ckK1
0
0

kG
kK1
G6=K
(10.52)
|UGK1 |2
ckK1 .
0kK1 0kG
(10.53)
|UGK1 |2
.
0kK1 0kG
(10.54)
X
G6=K1
The energy of the Bloch states, to second order, is

kK1 = 0kK1 +
X
G6=K1
This shows that the perturbed energy levels repel each other. (If 0kG > 0kK1 , then the
contribution to the shift is negative, and vice versa.)
Lecture 11
The nearly free electron model and
tight binding
11.1
Degenerate electrons in a periodic potential
We will always have points in k-space where free electron bands from two or more different
reciprocal lattice vectors come close in energy. The situation is sketched in Fig. 11.1. We
then have no choice but to consider all free electron bands on the same footing and solve the
full Master equation for the bands concerned:
X

0kK E ckK +
UGK ckG = 0.
(11.1)
G
To make the problem easier, we usually just focus on the near-degenerate states, ignoring
bands that are further off in energy. (The correct approach is to carry out a consistency
check to make sure that the shifts in energy that result from the mixing of bands are
smaller than the separation in energy of any neglected bands.)
Figure 11.1: The shaded region shows the range of k-space where degenerate perturbation
theory must be used. (From Ashcroft and Mermin[4].)
We start by considering a simple example in one dimension that of two bands mixing at
the zone boundary.
77
78 LECTURE 11. THE NEARLY FREE ELECTRON MODEL AND TIGHT BINDING
2|U2/a|
/2K = /a
Figure 11.2: The Fourier component of the periodic potential U 2 opens an energy gap at
a
the Bragg plane equal to twice its magnitude.
are degenerate. We have

At the point k = a , the bands associated with K = 0 and K = 2
a
!

0k E
U 2
c
k
a
=0
(11.2)
ck 2
U 2 0k 2 E
a
This has a nontrivial solution when

0k
2

0

E k 2 E U 2 = 0.
(11.3)
That is, when

1
E=
2
(
0k + 0k 2
a
Right at the zone boundary, k =
r
0k 0k 2
2
,
a
2

+ 4 U 2
a
(0k
)
.
(11.4)
0k 2 )
a

so E = U 2 .
a
a
0
the energies are equal

=

That is, we open up an energy gap of magnitude 2 U 2 . This is sketched in Fig. 11.2.
a
If the potential is attractive, U 2 < 0, the wavefunctions are
a

cos
x
,
a
a

x
+
sin
.
a
a
(11.5)
(11.6)
The modulus squared of these wavefunctions gives the real-space charge densities of the
states, which are plotted in Fig. 11.3. The results are physically appealing in the lower
energy state, the electrons are attracted to the ion cores, and vice versa for the high energy
state. At the zone boundary, Bragg reflection makes the states equal mixtures of left- and
11.1. DEGENERATE ELECTRONS IN A PERIODIC POTENTIAL
79
|+(x)|2
Ions
|-(x)|2
-2a
-a
2a
Figure 11.3: Charge densities of the zone-boundary states
and +
right-moving waves, resulting in standing waves. This is a general property of solutions

at the zone boundary. We will see later that these states have zero velocity and carry no
current. This is an important difference from free electrons. Away from the zone boundary,
the states quickly become much more plane-wave like, have a more uniform charge density,
and have finite velocity and carry currents. Figure 11.4 shows the scheme for constructing
energy bands in a one dimensional periodic potential.
In three dimensions we must consider the most general case. All the action still takes place
at Bragg planes, although now it is possible to have more than two free electrons bands
intersecting at the same point, as we can see in Fig. 11.5 for the face-centred cubic structure.
For instance, we could have four near-degenerate bands, resulting from four reciprocal lattice
vectors K1 , K2 , K3 and K4 . If we write out the nonzero terms from Eq. 11.1, we get the
following linear system.
0kK1 E UK2 K1
UK3 K1
UK4 K1
ckK1
0
UK1 K2
kK2 E UK3 K2
UK4 K2 ckK2
UK1 K3
UK2 K3
0kK3 E UK4 K3 ckK3
UK1 K4
UK2 K4
UK3 K4
0kK4 E
ckK4
=0
(11.7)
This is a Hermitian matrix, because UG = UG

, and the (real) energy eigenvalues are found
by setting the determinant equal to zero.
In two and three dimensions, the periodic potential opens an energy gap all along the Bragg
plane. This is illustrated in Fig. 11.6, which shows a free electron Fermi circle intersecting
the edge of the first Brillouin zone.
Figure 11.4: Construction of energy bands in a one-dimensional periodic potential. (a) The
parabolic free-electron dispersion. (b) A second free-electron parabola is drawn, shifted by
the reciprocal lattice vector K. (c) The degeneracy of the two parabolas at k = K/2 is split
by the Fourier components of the potential UK and UK . The bands repel and an energy gap
is opened. (d) The portions of (c) corresponding to the original free-electron parabola. (e)
The effect of all Bragg planes on the free electron parabola. This is known as the extended
zone scheme. (f) The same energy levels in the reduced zone scheme. (g) The energy levels
in the repeated zone scheme. (From Ashcroft and Mermin[4].)
11.2. THE TIGHT BINDING METHOD
81
Figure 11.5: Free electron bands of the FCC structure. (From Ashcroft and Mermin[4].)
11.2
The tight binding method
So far we have treated the periodic potential of the crystal lattice as a weak perturbation
to otherwise free electrons. We now begin from the opposite point of view, by starting from
a collection of N widely separated neutral atoms and bringing these together to form the
crystal. Initially, all the electrons will be in highly localized atomic orbitals, and the band
structure will be trivial a set of flat bands at the energies of the atomic levels, which will
each be N -fold degenerate. However, the orbitals will eventually start to have significant
overlap as the atoms approach one another. At this point, the atomic wavefunctions will
cease to be good approximations to the energy eigenstates. The tight-binding approximation
works in this limit, where the overlap between orbitals on different atoms is small and the
resulting eigenstates have strong atomic character.
Many people, most famously Philip Anderson[9], have been dismissive of the tight-binding
method. While there are many more powerful techniques available for ab-initio calculations
of electronic structure, the tight-binding method has many advantages of its own. These
include:
allowing the description, in an intuitive way, of energy bands and bonds in a wide
variety of periodic systems.
having a direct connection to the chemistry of the material, so that the effects of the
shape and symmetry of the atomic orbitals can readily be seen.
Figure 11.6: (a) Free electron Fermi circle cutting a Bragg plane at k = K/2. (b) Deformation
of the free electron Fermi surface near the Bragg plane. The necking out of the Fermi surface
to touch the Bragg plane will always occur. Note that the Fermi surface intersects the Bragg
plane perpendicular to it. (From Ashcroft and Mermin[4].)
easy modification to permit the description of incommensurate systems and disordered

systems.
allowing a local description of transport phenomena. (When considered locally, the
electric potential is finite and easy to treat.)
being the natural framework in which to introduce correlation effects, as these are
usually the result of short-range forces.
providing excellent parameterizations of the electronic structure of a solid, when the
overlap integrals are treated as phenomenological parameters to be taken from more
detailed calculations, or from fits to experimental data.
These last two points bear more comment. In most interesting materials currently being
studied, even a qualitative description of the electronic behaviour eludes a first-principles
calculation. We rely on model building to incorporate the essential physics, and tightbinding models provide a simple and transparent parameterization of the band-structure, to
which interaction terms can readily be added. Tight-binding should be the technique of first
resort for everyone except perhaps the professional band theorist.
11.2.1
Introduction to tight binding
Before getting into the formalism, it is good to start with a physical picture of the tightbinding method. Figure 11.7 shows a schematic model of a one-dimensional metal as a
collection of potential wells, which need not be all the same depth, although they will be
in a crystalline solid (or at least alternate in a regular pattern). Wells of random depth
would correspond to a highly disordered solid. Figure 11.7 also shows an electron, almost
83
(r)
Potential
Figure 11.7: A model of a one-dimensional metal.
trapped in one of the wells. The tight-binding approach begins by considering the atomic
eigenstates, which are localized in individual wells, but, realizing that such states are no
longer eigenstates when the wells are brought together, allows for a finite probability for the
electron to leak into a neighbouring well. The rate at which it does determines the energy
dispersion of electrons propagating through the extended structure. The depth of the wells
in Fig. 11.7 doesnt really indicate the magnitude of the potential, but rather the energies of
the atomic bound states. Therefore, the one-dimensional potential could represent a chain
of atoms stuck together. In a random potential, electrons can become trapped in one place.
To find out how electrons move through such a system, we suppose we know the individual
atomic binding energies. We then introduce a set of states {|ii}, where |ii is a state localized
at the ith atom. In order to make the mathematics as simple as possible, we choose the
set {|ii} to be orthonormal. Such a choice is always possible by construction, although
how localized the states |ii are depends on the extent to which the original atomic states
overlapped with their neighbours to begin with. The procedure is to use GrammSchmidt
orthogonalization, starting from the original atomic eigenstates |i i. Lets concentrate on
the state at the origin, |0 i, and its nearest neighbours |1 i and |1 i. We modifiy |0 i by
subtracting off the parts that arent orthogonal to the states on neighbouring sites.
|0 i |0 i |1 ih1 |0 i |1 ih1 |0 i
(11.8)
This can be extended over all the atoms in the chain, to get the orthonormalized functions
|i i:
!
X
|i i = A |i i
|j ihj |i i ,
(11.9)
j6=i
where A is the new normalization constant. The orthogonalized states are call Wannier
orbitals, and are important in the formal development of the tight-binding method. The
procedure is illustrated in Fig. 11.8. It works best when the original atomic states dont
overlap too strongly, in which case the Wannier functions are very similar to the original
atomic orbitals, and are well localized. If the overlap between neighbouring states becomes
too strong, the Wannier states start to become quite spread out. Another thing to note is
0.8
0.6
0.4
(a)
0.2
-4
-6
-2
0.8
0.6
0.4
(b)
0.2
-4
-6
-2
0.8
0.6
0.4
(c)
0.2
-6
-4
-2
0.8
0.6
0.4
(d)
0.2
-6
-4
-2
1
0.75
(e)
0.5
0.25
-6
-4
-2
-0.25
-0.5
1
0.75
(f)
0.5
0.25
-6
-4
-2
-0.25
-0.5
Figure 11.8: The process of orthogonalizing atomic orbitals. a) An atomic orbital (x) =
A exp(x2 ), centered on the origin. b) (x) is clearly not orthogonal to its neighbours.
c) The orbitals after GrammSchmidt orthogonalization. d) A comparison of the orbitals
before and after orthogonalizing. e) When the lattice sites get closer together, the original
atomic orbitals overlap more strongly and it becomes difficult to keep the orthogonalized
orbitals well localized. f) The results of orthogonalizing closely spaced orbitals.
85
that the Wannier states are neither perfect eigenfunctions of the isolated potential wells, nor
eigenfunctions of the infinite collection of wells.
As a shorthand, let ci be the electron creation operator for the state |i i. An approximate
hamiltonian for an electron in the collection of potential wells is
X
tb =
H
Ui ci ci ,
(11.10)
i
where Ui is the energy of the bound state at site i. It is a good thing that this is just
an approximate hamiltonian, because it doesnt do anything. An electron starting out in
a state |j i would just sit there forever. What is missing is the fact that the tails of the
wavefunctions extend out into neighbouring wells, giving the electron a finite amplitude to
leak or tunnel into an adjacent site. If we call this amplitude t, then we can allow for its
effect by adding terms like tc1 c0 to the hamiltonian. (We also have to add the adjoint,
t c0 c1 , to make the hamiltonian hermitian.) Doing this for all the sites, and considering
only nearest neighbours, we have the full tight-binding model in one dimension.
o X
X n
Ui ci ci .
(11.11)
Htb =
t ci ci+1 + ci+1 ci +
i
In the simplest case, in which all the Ui are the same (= U0 ), we can solve the tight-binding
model by taking the Fourier transform of the Wannier orbitals, as we have already seen:
1 X ikri
e ci .
ck =
N i
(11.12)
In that case the solution is

=
H
k n
k,
n
k = ck ck ,
(11.13)
where
k = 2t cos(ka) + U0 .
(11.14)
Lecture 12
The tight-binding approximation
Lets put the tight-binding method on a more rigorous footing. Imagine we have a periodic
atom , each with a set of discrete levels
lattice of identical atoms, with atomic hamiltonians H
with wavefunctions n (r) and energies En . Our eigenstates must obey Blochs theorem, so
lets take a linear combination of atomic orbitals as our ansatz for the eigenstate of the full
crystal Hamiltonian:
1 X ikR
|ki = nk (r) =
e n (r R),
(12.1)
N R
where R are the lattice vectors and N is the number of cells in the crystal. Specializing to
the case of a single orbital per lattice site, we can now calculate the energy of this state to
first order in perturbation theory:
1 X ik.(Ri Rj )
h(r Ri )|H|(r
Rj )i
e
N R ,R
i
j
Z
X
ikR
=
e
dr (r R)H(r).
E(k) = hk|H|ki
=
(12.2)
(12.3)
The wavefunctions are weakly overlapping, so we keep only the terms where the orbitals are
either on the same site, or on nearest neighbour sites connected by the vector . The onsite
H
atom in the vicinity of the
term gives a contribution close to the atomic energy, since H
origin:
Z
0 = dr (r)H(r)
En .
(12.4)
The overlap term between neighbouring orbitals is called the hopping integral:
Z
t = dr (r )H(r).
(12.5)
As a result, the band energy is:

E(k) = 0 t
eik .
(12.6)
87
88
LECTURE 12. THE TIGHT-BINDING APPROXIMATION
For a cubic lattice of spacing a, which has six nearest neighbours, the dispersion relation is
E(k) = 0 2t[cos(kx a) + cos(ky a) + cos(kz a)].
(12.7)
The bandwidth is 12t. Bandwidth is an important parameter, as it sets the scale of the kinetic
energy of the electrons in the solid. The more atomic-like the structure is, the narrower the
band, and the less electron kinetic energy. In narrow-band metals the potential energy
is proportionally more important, and is why many narrow band systems have interesting
magnetic properties. The tight binding energy dispersion also allows us to say something
about the effective mass of the electrons. The top and bottom of the band are parabolic,
and the effective mass m is defined:
1 2 E(k)
m = 2
~ ki2
1
=
~2
.
2ta2
(12.8)
We will later see that the effective mass defines the response of the Bloch electrons to external
fields. As a rule, the narrower the band, the heavier the mass.
12.1
Degenerate tight-binding theory
The calculation we have just seen is too simple to capture the physics of many real metals.
We often need to form trial Bloch states from more than one type of atomic orbital, as
two or more atomic orbitals can be degenerate with one other. Even in the absence of
strict degeneracy, tunneling of electrons between adjacent sites adds dispersion to the energy
spectrum, giving a finite bandwidth equal to the number of neighbours twice the hopping
integral t. Any other atomic level that falls within or even close to this energy range must
be included in the trial wavefunction, unless it is prevented from mixing by symmetry.
Fortunately the general case is not much more difficult to set up. For each atomic orbital
i (r), we construct a Bloch sum of wavevector k:
1 X ikR
e |i (r R)i.
|ki i =
N R
(12.9)
Our trial wavefunction for the degenerate case is then the linear combination:
|k i =
ci (k)|ki i,
(12.10)
where the coefficients ci (k) are to be determined as part of the eigenvalue problem. Act on
this state with the hamiltonian.
k i = E(k)hk |k i
hk |H|
X
kj i = E(k)
ci (k)cj (k)hki |H|
ci (k)cj (k)hki |kj i
i,j
i,j
(12.11)
(12.12)
12.1. DEGENERATE TIGHT-BINDING THEORY
89
Call the matrix elements of the crystal hamiltonian Mij (k):

kj i
Mij (k) = hki |H|
X
1
0
j (r R0 )i
=
eik.(RR ) hi (r R)|H|
N R,R0
X
j (r R)i.
=
eikR hi (r)|H|
(12.13)
(12.14)
(12.15)
The overlap matrix elements Sij (k) = hki |kj i are approximately diagonal in the case of
well localized orbitals. In fact, if the orbitals we began with were Wannier orbitals, this
would be exactly the case Sij (k) = ij . From now on we will make that assumption. The
problem can be written as the matrix equation:
M11 (k) E(k)

M1N (k)
c1 (k)
..
..
..
(12.16)
= 0.
.
.
.
MN 1 (k)
MN N (k) E(k)
cN (k)
We set the determinant to zero to get the energy eigenvalues and the coefficients ci (k) of the
eigenstates.
It is common to express the crystal potential as a sum of spherically symmetric atomic-like
potentials Va (r R) centred at the lattice positions.
2
X
= p +
Va (r R)
H
2m
R
Then
Mij (k) =
ikR
i (r)
(12.17)

p2
0
+ Va (r) + V (r) j (r R)dr,
2m
(12.18)
(12.19)
where
V 0 (r) =
Va (r R).
R6=0
atom = p2 /2m + Va (r) with energy Ei ,

If we use the fact that i (r) is an eigenfunction of H
then
Z
X
ikR
Mij (k) = Ei ij +
e
i (r)V 0 (r)j (r R)dr.
(12.20)
R
The R = 0 term gives the crystal field integral

Z
Iij = i (r)V 0 (r)j (r)dr.
(12.21)
If V 0 (r) is almost constant near r = 0, then Iij is a constant diagonal matrix and contributes
a rigid energy shift of the entire band structure but does not influence the dispersion curves.
For this reason it is often neglected. For the R 6= 0 terms, we usually limit the sum to
a small number of neighbouring sites. (A more accurate model might require next-nearest
90
neighbours, and so on.) We also neglect three-center integrals in Mij (k), and limit the
calculation to two-centre integrals, which can be tabulated in terms of a small number of
independent parameters. (All the quantum chemistry and orbital symmetries are contained
in the two-centre integrals these are explained and tabulated in Figs. 12.1 and 12.2.)
Putting all this together we have
Z
X
ikR
Mij (k) Ei ij +
(12.22)
e
i (r)Va (r R)j (r R)dr.
R
Finally, if the unit cell contains more than one atom, which in general may be different, we
need to include Bloch sums centred at each of the atomic sites.
1 X ikR
e |i (r R d)i.
(12.23)
|kid i =
N R
Note that it is not necessary to include d in the phase factor, as we have a phase degree of
freedom in the wavefunction anzatz, thanks to the coefficients cid (k).
X
|k i =
cid (k)|kid i
(12.24)
id
In the following examples we will only consider crystals with a monatomic basis, but the
extension to the multi-atom case is straightforward to implement.
In summary, the approximations made in the tight-binding method are:
to assume we are working with orthogonal Wannier orbitals, not the eigenstates of the
well-separated atoms. In practice, for well-localized orbitals, the differences are small.
we ignore integrals of the form
Z
Iij =
i (r)V 0 (r)j (r)dr,
(12.25)
where
V 0 (r) =
Va (r R).
(12.26)
R6=0
0
V (r) is only finite away from the origin, where i (r) should be rapidly becoming small.
we ignore three centre integrals
Z
i (r)Va (r R1 )j (r R2 )dr,
R1 6= R2 ,
(12.27)
as these are typically small.

We usually take the point of view that the tight-binding model is a phenomenological parameterization of experimental results or a more accurate calculation, in which case these
approximations do not matter. The great benefit of the tight-binding method is its simplicity, and the transparency with which we can see the effects of symmetry and chemical
structure.

0
91
-1
-1
-2
-2
-3
-3
-4
-4
E(k)/eV
Figure 12.1: s-like band in a face-centred cubic crystal. = (0, 0, 0), X = ( 2

, 0, 0), L =
a
( a , a , a ). Es = 1 eV, V (ss) = 0.2 eV.
12.1.1
Example 1: s-like band in a face-centred cubic crystal
We now use the tight-binding method to calculate the energy dispersion of an s-like band in
a face-centred cubic crystal. We assume there are no orbitals that are near-degenerate with
the atomic s orbitals s (r).
We begin by forming a single Bloch sum
1 X ikR
|ks i =
e |s (r R)i.
(12.28)
N R
The energy dispersion is given by the expectation value of the hamiltonian in this state.
ks i
hks |H|
hks |ks i
Z
X
ikR
s (r)Va (r R)s (r R)dr,
Es +
e
E(k) =
(12.29)
(12.30)
where the sum is restricted to the 12 nearest neighbours, R = a2 (1, 1, 0), a2 (0, 1, 1), a2 (1, 0, 1).
This involves a two-centre integral between s states, with Va (r) spherically symmetric. Looking this up in Fig. 12.1 or 12.2, we see that there is no dependence on bond angle. All 12
integrals will be the same (nearest neighbour distance is a constant) and will be denoted
V (ss). All that remains is to evaluate the phase factors, which we will call F (k).
X
F (k) =
eikR
(12.31)
R
92
This consists of three similar parts, for xy, yz and xz.

X
X
eiky a/2
Fxy (k) =
eikx a/2
(12.32)
= 4 cos
kx a
ky a
cos
.
2
2
(12.33)
F (k) = Fxy (k) + Fyz (k) + Fxz (k)

kx a
ky a
ky a
kz a
kx a
kz a
= 4 cos
cos
+ cos
cos
+ cos
cos
.
2
2
2
2
2
2
(12.34)
(12.35)
The energy dispersion, plotted in Fig. 12.1, is:

E(k) = Es + V (ss)F (k).
12.1.2
(12.36)
Example 2: p-like bands in a face-centred cubic crystal
We now use the tight-binding method to calculate the dispersion of p-like bands in an FCC
crystal. The atomic p orbitals are threefold degenerate, so we need to use 3 Bloch sums.
1 X ikR
e |i (r R)i,
|ki i =
N R
i = x, y, z
According to our prescription, we need to set up a secular equation:

Mxx (k) E(k)
Mxy (k)
Mxz (k)

M
(k)
M
(k)
E(k)
Myz (k)
yy
xy

Mzz (k) E(k)
Myz (k)
Mxz (k)
where
Mij (k) = Ei ij +
ikR
(12.37)

= 0,

(12.38)
i (r)Va (r R)j (r R)dr.
(12.39)
The calculation is greatly simplified by the fact that there are only two independent matrix
elements, Mxx (k) and Mxy (k), with the rest obtained by cyclic permutation of the indices.
The overlap integrals of p-orbitals have nontrivial angle dependence, expressed in terms of
the direction cosines `i cos i , where i is the angle between the lattice vector R and the
i axis. (i = x, y, z.) Let us first make a table of the direction cosines for the face-centred
cubic structure.
R
cos x
cos y
cos2 x
sin2 x
cos x cos y
a
(1, 1, 0)
2
12
12
1
2
1
2
12
a
(0, 1, 1)
2
0
12
0
1
0
a
(1, 0, 1)
2
12
0
1
2
1
2
0
93
-0.25
-0.25
-0.5
-0.5
-0.75
-0.75
-1
-1
-1.25
-1.25
-1.5
-1.5
-1.75
-1.75
-2
-2
E(k)/eV
, 0, 0), L =
Figure 12.2: p bands in a face-centred cubic crystal. = (0, 0, 0), X = ( 2
a

( a , a , a ). Ep = 1 eV, V (pp) = 0.2 eV and V (pp) = 0.02 eV.
Mxx (k) = Ep +
ikR
x (r)Va (r R)x (r R)dr.
(12.40)
x (r)Va (r R)x (r R)dr = `2x V (pp) + (1 `2x )V (pp)

= cos2 x V (pp) + sin2 x V (pp)
(12.41)
(12.42)
Taking the direction cosines from the table and evaluating the phase factors in a similar
way to Example 1, we have.

ky a
kx a
kz a
kz a
kx a
ky a
cos
+ cos
cos
cos
Mxx (k) = Ep +2 (V (pp) + V (pp)) cos
+4V (pp) cos
2
2
2
2
2
2
(12.43)
Similarly,
Z
X
ikR
Mxy (k) =
e
x (r)Va (r R)y (r R)dr.
(12.44)
R
x (r)Va (r R)y (r R)dr = `x `y (V (pp) V (pp))

= cos x cos y [V (pp) V (pp)]
(12.45)
(12.46)
Paying careful attention to signs in the phase factor, we get:

Mxy (k) = 2 [V (pp) V (pp)] sin
kx a
ky a
sin
.
2
2
(12.47)
94
We use cyclic permutation to find the other matrix elements, and then solve the eigensystem
numerically, as a function of k. The resulting band structure has been plotted along two
symmetry directions in Fig. 12.2. We can see that Ep is just an additive offset, and the
qualitative behaviour is controlled by the ratio V (pp)/V (pp).
95
Table 12.1: Two centre integrals, from Grosso and Parravicini[10].
96
Table 12.2: The definitive table of two-centre integrals[11]. l, m and n are the direction
cosines for the x, y, and z axes respectively.
Lecture 13
Energy bands and electronic structure
So far we have used two different approaches to calculate the properties of electrons in crystalline solids. In the first method we started with free electrons, which have plane-wave
eigenstates, and then introduced the periodic potential of the ion cores as a weak perturbation. This approach focussed explicitly on how the symmetry of the solid modifies the
one-electron Schrodinger equation. In the tight-binding method we began at the opposite
extreme, considering electron tunneling between atoms as a perturbation to the highly localized atomic eigenstates of a set of well-separated atoms. In this lecture we review what we
have done so far and then focus on the particular problem of understanding why some materials are metals, while others are semiconductors or insulators. We will be able to address
this issue using a simple geometric recipe for constructing energy bands and Fermi surfaces.
13.1
Review of the nearly free electron model
The main results for a single electron moving in a periodic potential are summarized below
and generalized for two- and three-dimensional problems.
A periodic potential in real space can be decomposed into a set of discrete Fourier
components. These are finite only at special wavevectors G. The vectors G form a
lattice in reciprocal space.
X
U (r) =
UG eiGr
(13.1)
G
Every reciprocal lattice vector G has a corresponding Bragg plane, defined to be its
= |G|/2.
perpendicular bisector. That is, k G
Along the Bragg plane defined by G, the free electron energies k and kG are degenerate:
~2 (k G)2
~2 k 2
=
.
(13.2)
2m
2m
As a result, states near these planes are strongly mixed by the Fourier components of
the potential UG and UG , and an energy gap in k-space is opened at the Bragg plane.
The energy gap is proportional to |UG |.
97
98
LECTURE 13. ENERGY BANDS AND ELECTRONIC STRUCTURE
/2G
k
G
k-G
/2G
k
k - 1/2G
Figure 13.1: Every reciprocal lattice vector G defines a Bragg plane.
(a)
(b)
Figure 13.2: (a) The opening of an energy gap at a Bragg plane in one dimension. (b)
Constant energy contours for a two-dimensional electron gas with a one dimensional periodic
potential. (From Taylor and Heinonen[7].)
The Bragg planes break reciprocal space up into zones. The first Brillouin zone is the
set of points in k-space that can be reached without crossing any Bragg planes. This
is the WignerSeitz cell of the reciprocal lattice. The nth Brillouin zone is defined as
the set of points that can be reached from the origin by crossing n 1 Bragg planes,
but no fewer. The Brillouin zones of the square lattice are shown in Fig. 13.3.
Each Brillouin zone contains one state, of each spin, for every unit cell in the real-space
lattice. As a result, if the crystal contains N primitive cells in real space, each Brillouin
zone will be able to hold 2N electrons.
Each Brillouin zone contains one branch, or band, of the energy dispersion k .
All higher-order Brillouin zones can be mapped back into the first Brillouin zone by
translating them by reciprocal lattice vectors and, when this procedure is carried out,
each Brillouin zone will exactly fill the first Brillouin zone. This is called the reduced
zone scheme. The mapping procedure is shown in Fig. 13.3.
13.1. REVIEW OF THE NEARLY FREE ELECTRON MODEL

5
99
5
3
1
2
3
5
6
3
4
3
4
3
5
6
3
1
2
1st zone
3rd zone
3
2nd zone
Figure 13.3: Brillouin zones of the two-dimensional square lattice. Each Brillouin zone in
the extended zone scheme can be mapped back to precisely fill the WignerSeitz cell of the
reciprocal lattice in the reduced zone scheme.
Each zone is a primitive cell of the reciprocal lattice, so there exists a simple procedure
for constructing the different branches of the Fermi surface in the reduced zone scheme.
1. Draw the free electron sphere in the extended zone scheme. The radius of the
sphere is the Fermi wavevector kF , determined by the density of electrons n.
2. Deform the sphere slightly near the Bragg planes. The effect of the periodic potential is to open gaps at the Bragg planes, requiring the constant energy surfaces
to intersect Bragg planes at right angles. In the limit of weak potentials this step
can be skipped.
3. Take the portion of the sphere lying in the nth zone and translate it by reciprocal
lattice vectors back into the first zone.
4. The resulting surface will be continuous and is a branch, or sheet, of the Fermi
surface.
100

5. The effect of a weak potential is to round the sharp corners of the Fermi surface
sheets.
6. Stronger potentials can cause small pieces of the Fermi surface to disappear. These
can be electron-like or hole-like, as defined below.
3
1
2
3rd zone
1st zone
2nd zone
3rd zone
Figure 13.4: The Fermi surface of a square lattice of tetravalent ions. The first Brillouin
zone is completely filled. The second Brillouin zone is over half full and contains a pocket
of empty states surrounding the zone centre. The third Brillouin zone is only partly filled
and consists of four small pieces near the zone corners. A redrawn third zone, centred on
the point (/a, /a), consists of a single, connected pocket of electron states.
13.2
Free electron Fermi surfaces in 2D
As an example, we consider a tetravalent metal with a simple square lattice of side a in two
dimensions. There are four electrons per primitive cell so, allowing for spin degeneracy, the
area of the Fermi surface will precisely fill two Brillouin zones.
2
2
8
2
2
= kF kF =
(13.3)
a
a
The Fermi surface is sketched in the extended zone scheme in Fig. 13.4. Pieces of the Fermi
surface lying in higher-order zones are mapped back into the first Brillouin zone. The first
zone is completely filled and as a result is electrically inert. The second zone is largely filled,
but has a small pocket of empty states in the centre. The third zone is only partly filled its
area corresponds precisely to the missing area in the second zone. The pieces of the Fermi
13.3. ELECTRONS AND HOLES
101
surface are located in the corners of the Brillouin zone, and appear not to be connected.
However, there is nothing to say that when we map the Fermi surface pieces we have to map
them into a zone centred on the origin of k-space. If we were to view the 3rd zone in the
repeated zone scheme we would immediately see a better way to represent this piece of the
Fermi surface. We can choose a new zone, of the same area and shape as the first Brillouin
zone, centred on the zone corner. With this choice, the 3rd zone Fermi surface is continuous
and has a shape called a rosette.
2nd zone
3rd zone
Figure 13.5: Second zone hole pocket and third zone electron pocket for the square lattice.
Fermi surface sheets are constant energy surfaces. The gradient of the energy is perpendicular
to the Fermi surface, and points from filled to empty states.
Now consider the action of a weak periodic potential on the Fermi surface. This will open
small energy gaps at the Bragg planes and cause the sharp corners of the Fermi surface pieces
in the second and third zones to be rounded, as shown in Fig. 13.5.
A simple way of constructing the different Fermi surface pieces is to use the Harrison construction, shown in Fig. 13.6. This is a series of intersecting spheres of radius kF , each
centred on a different point in the reciprocal lattice. The surfaces of the intersecting spheres
define the different Fermi surface sheets.
13.3
Electrons and holes
We have seen above that there are two distinct types of Fermi surface sheets those that
close around filled states and those that close around empty states. There is a third kind as
well open Fermi surface sheets, which do not close within the Brillouin zone. A surface
that closes around empty states is called a hole surface. In this case the gradient of the energy
points into the surface. Surfaces that close around filled states are called electron surfaces.
When we come to discuss electrical transport, we will see that hole surfaces respond to
applied fields as though they contain a small density of positively charged particles. Open
Fermi surfaces have mixed character.
102
Figure 13.6: The Harrison construction in three dimensions.
13.4
Metals, semimetals, insulators and semiconductors
We are now in a position to see why some materials are metals and some are insulators.
Depending on the number of electrons in the unit cell, and the size of the energy gaps
opened along the Bragg planes by the periodic potential, it is possible to have situations in
which all the bands (all the Brillouin zones) in a solid are either completely filled or empty.
A filled Brillouin zone is electrically inert there are no low energy excited states to make
transitions into, so the electron assembly cannot respond to low frequency fields by carrying
a current. It is therefore an insulator. The different types of solid are outlined below and
are sketched in Fig. 13.7.
Metals. These are solids with at least one partially filled band. This can occur because
there is an odd number of electrons per unit cell, making it impossible to completely
fill all occupied bands, or, when there is an even number of electrons per cell, because
the energy gaps are small enough that there are several partially occupied bands. The
latter case is called a compensated metal. It must be pointed out that this prescription
does not always work there are solids, such as NiO, with an odd number of electrons
per unit cell, that form Mott insulating states due to Coulomb repulsion between the
electrons. The Mott insulator is one of the best examples of the breakdown of the
independent electron approximation.
Insulators. To the extent that one-electron band structure provides a good description
of the states, these are solids with an even number of electrons per primitive cell,
13.4. METALS, SEMIMETALS, INSULATORS AND SEMICONDUCTORS
103
Energy
Density of States
Insulator
Metal
Semimetal
Semiconductor
Figure 13.7: A schematic view of the density of states of various types of electronic solid.
and band gaps large enough that every Brillouin zone is either completely filled or
completely empty.
Semiconductors. These are small-gap insulators, in which the energy gap is low
enough (typically 1 2 eV) that a small but finite proportion of the electrons are
thermally excited from filled to empty bands, creating a low density of mobile charge
carriers.
Semimetals. These are compensated metals, with an even number of electrons per
unit cell, that verge on being insulators. That is, they have a very small density
of holes in an otherwise filled band, and the same density of electrons in the next,
almost empty, Brillouin zone. An example is bismuth metal. Carrier densities are
typically 3 to 4 orders of magnitude lower than in metals, with Fermi wavelengths that
are correspondingly larger. This makes these materials of interest for studying the
classical to quantum crossover that occurs when the thermal de Broglie wavelength
becomes of the order of the interparticle spacing.
We close this lecture by looking at electronic structure from the tight-binding viewpoint.
It is useful to imagine what would happen if the atoms of a solid were brought together in
a controlled way, so that the lattice spacing a was a parameter which could be varied. At
large lattice spacings there would be very little overlap and the electronic structure would
be identical to that of the isolated atoms, although each atomic level would have an N -fold
degeneracy. On reducing the lattice spacing, the atomic levels would broaden into bands.
104
Figure 13.8: (a) For large lattice spacing a the eigenstates are discrete atomic levels. As
the lattice spacing is reduced the atomic levels broaden into bands. (b) Monovalent metals
have half-filled bands and are metallic. (c) Divalent atoms have a filled band at large lattice
spacings and are insulating. At smaller lattice spacings, band overlap leads to the formation
of a compensated metal. (From Taylor and Heinonen[7].)
Fig. 13.8 illustrates this for monovalent atoms, which have a half-filled band and are usually
metallic as a result, and for divalent atoms, which form insulators when the bandwidth is
small (at large a) but become metallic when the bands overlap at smaller lattice spacings.
Lecture 14
Electronic structure calculations
Nearly free electrons and tight binding are not accurate methods of electronic structure calculation, but both are good for illustrating the basic principles. They are commonly used
to provide simple parameterisations of energy bands, with the parameters determined by
more accurate, first-principles calculations or by comparison with experiment. The next
two lectures will look at some of the more accurate techniques used for calculating electronics structure, and point out other considerations, such as relativistic effects, that must be
included in real calculations.
14.1
Orthogonalized plane waves and pseudopotentials
Experiments such as de Haasvan Alphen spectroscopy reveal the Fermi surface of gold to be
roughly spherical. Taken with other experiments such as heat capacity, we can view a piece
of gold as a nearly empty box containing one electron per atom. But the atomic number
of gold is 79. The other 78 electrons seem somehow to just crowd around the nucleus and
screen its charge from the outside. The problem of how to treat these other electrons, and the
much-reduced core potential they leave behind, was solved by Philips and Kleinman in 1959,
when they introduced the concept of pseudopotentials. Pseudopotentials do two things: they
show how the real Schrodinger equation of a solid can be mapped on to a much simpler one,
providing a justification of the nearly free electron model; and they substantially improve
computational techniques, allowing the band structure of very complicated materials with
many electrons to be calculated using smooth potentials and far fewer basis states.
14.1.1
Example: the need for pseudopotentials
Imaging using a brute force approach to solve the Schrodinger equation for silver in the
nearly free electron approximation
X

0kK E ckK +
UGK ckG = 0.
(14.1)
G
How many plane wave states would be needed to represent the valence electrons, which are
drawn from atomic 5s states? The 5s state has 4 nodes, in a distance of about 0.5
A. This
105
106
LECTURE 14. ELECTRONIC STRUCTURE CALCULATIONS
implies that k 2/ = 2/0.25

A 24
A1 . The lattice constant of silver is a = 4
A, so
the smallest reciprocal lattice vector is G0 = 4/a 3
A1 . In order to Fourier expand the
5s state, we need Fourier components ranging from 8G0 ...8G0 , in all three directions. This
is a total of 173 5000 plane wave states!
By introducing pseudopotentials, we will get pseuodwavefunctions with far fewer nodes.
Away from the ion core these can be chosen to be the same as the real 5s valence states.
The result is that we will need a much smaller basis set of plane waves.
14.2
Orthogonalized plane waves
While not particularly useful in band-structure calculations, orthogonalized plane waves

provide a clear illustration of idea of the pseudopotential method. The approximation relies
on our being able to divide the electrons into two groups: core electrons and conduction
electrons. The core electrons are localized around particular atomic sites, and we assume
we know their wavefunctions |c i. The basic idea is that a pure plane wave is not a very
good approximation to the conduction electron wavefunction because it is not orthogonal to
the core states. As it makes its way past each ion core, the wavefunction of the conduction
electrons must wiggle rapidly in order not to overlap with any of the electrons in the core.
However, we know that plane waves must be reasonably good solutions away from the ion
cores, because they do a good job of describing the properties of many solids. Realizing
this, we introduce new basis states that retain plane-wave-like characteristics away from the
ion cores, but have been made orthogonal to the core states using the GrammSchmidt
procedure.
X
|c ihc |ki,
(14.2)
|kps i = |ki
c
where ps stands for pseudo k-state, and the sum is over all occupied core levels |c i. Now
write the Schrodinger equation in the |kps i basis.

p2
+ U |kps i
2m
)
2
(
X
p
=
+ U
|ki
|c ihc |ki
2m
c
!
2

X
p
=
|ki + U
(c )|c ihc | |ki
2m
c
2

p
=
+ Ups |ki,
2m
)|kps i =
(H
(14.3)
(14.4)
(14.5)
(14.6)
where we have used the fact that

p2
+ U
2m

|c i = c |c i
(14.7)
14.2. ORTHOGONALIZED PLANE WAVES
107
ps(r)
(r)
Ups(r)
U(r)
Figure 14.1: The true potential U (r) has a wavefunction (r) for the valence electrons that
oscillates rapidly near the core. The pseudopotential Ups (r) has a wavefunction ps (r) that
is smooth near the core but approximates the true wavefunction far from the core region.
to define the pseudopotential

Ups = U
(c )|c ihc |.
(14.8)
The final result is that the full Schrodinger equation in the pseudo plane-wave basis maps
onto a much less singular Schrodinger equation in a pure plane-wave basis.
)|kps i = (H
ps )|ki.
(H
(14.9)
The pseudopotential is useful because it justifies working with a small number of plane waves
in the nearly free electron model. Ups is smooth, so its Fourier components are small except
for the first few reciprocal lattice vectors. A minor disadvantage is that the pseudopotential
in nonlocal but, to a good approximation, Ups can be replaced in calculations by a local
potential. It also depends on the unknown eigenenergy , requiring a self-consistent solution.
In actual electronic structure calculations, each atomic potential is replaced by a model pseudopotential that has the same scattering amplitude for valence electrons as the real potential.
This is shown schematically in Fig. 14.1. The real- and pseudopotentials are identical outside the core, so the radial parts of the wavefunction are proportional. A norm-conserving
pseudopotential results in pseudowavefunctions that are identical to the real wavefunctions
outside the core, corresponding to the same charge density. This constraint is sometimes
relaxed in calculations in favour of a so-called ultrasoft pseudopotential. Pseudopotentials
and wavefunctions for silver are shown in Fig. 14.2.
108
Figure 14.2: Real and pseudo potentials (top) and wavefunctions (bottom) for the 5s, 5p
and 4d states of silver. (From Marder[5].)
14.3
Relativistic effects
We will now look at one of the effects that are important in accurate electronic structure
calculations relativistic corrections. At first sight it seems as though relativistic corrections
would not be significant in solids. The Fermi energy of a metal (the energy difference between
the highest and lowest filled conduction band states) is usually just a few electron volts, a
very small fraction of the 0.5 MeV rest mass energy of the electron. But for electrons
moving in the deep nuclear potentials of heavy ions, relativistic effects can be substantial.
More importantly, relativistic effects can lift some of the degeneracies that occur at high
symmetry points in k-space.
We have been describing the quantum behaviour of electrons in solids by using the Schrodinger
equation and putting the electron spin in by hand. Electrons are actually described by the
14.3. RELATIVISTIC EFFECTS
109
Dirac equation
|i = c p
+ mc2 |i,
(14.10)
t
where |i is a four-component spinor. In the nonrelativistic limit the Dirac equation can
be split into separate equations for the electron and positron. The hamiltonian, which now
acts on a two-component electron wavefunction, is
i~
p
4
2
~
~2
= p
+ V (r)
H
+
~
[V
(r)
]
+
2 V (r) + ...
2m
8m3 c2 4m2 c2
8m2 c2
(14.11)
We will focus on the second correction to the Schrodinger equation, the spinorbit term
~
~ [V (r) p
],
4m2 c2
(14.12)
which is a measure of the coupling of the electrons magnetic moment to the magnetic field
produced by its orbital motion.1 Of all the the relativistic effects, the spinorbit coupling
produces the most observable effects, not because it is the largest in magnitude, but because
it does not have the same symmetry as the periodic potential. As a result, it can lift
degeneracies, in some cases causing large changes in Fermi surface topology. These effects
are particularly important in hexagonal-closest-packed metals, in which the crystal structure
is not a Bravais lattice, but a lattice convolved with a basis of two identical atoms within
the unit cell. The Fourier transform of the real-space potential has a structure factor that
cancels some of the reflections exactly, resulting in degeneracies along the missing Bragg
planes. The spinorbit interaction does not have the same symmetry and is able to lift
these degeneracies. These effects are less important in the light elements but become more
important the heavier the nuclei are.
We will illustrate these effects with a simple example from Section 4.5 of Taylor and Heinonen[7].
The spinorbit correction is the only term in the hamiltonian that explicitly depends on the spin of the
electron. However, it is not the origin of magnetism in solids. We have already seen that the Pauli exclusion principle, coupled with the spin-independent Coulomb repulsion, results in a spin-dependent exchange
potential. The exchange interaction is always much larger than the spinorbit coupling.
110
Lecture 15
Density functional theory
In the course so far we have taken two approaches to calculating and understanding the
properties of electrons in solids. We initially focussed on electrons in a uniform system,
and looked at the effect of interactions between the electrons. This was a hopelessly difficult
problem to solve exactly and required approximate methods to make any headway at all. We
then discarded the interactions and considered the problem of electrons moving in a periodic
one-body potential, a difficult problem in its own right but one that could in principle
be solved exactly. In real materials both effects are important. How do we include them
in electronic structure calculations in any sort of tractable way? For materials in which
correlation effects are not too strong, the answer is to use density functional theory.
15.1
The HohenbergKohn theorem
Hohenberg and Kohn observed that, as far as calculation of the ground state energy goes,
the electron density n(r) contains, in principle, all the information of the many-body wavefunction (r1 , 1 ; ...; rN , N , t). That this is true is quite astonishing. The many body wavefunction of an N -particle system is a function of 3N + 1 variables and N spin coordinates.
The density, on the other hand, is just a function of 3 space variables (and time). Not only
does n(r) determine the ground state energy, but many other important physical properties
as well. These include all the linear response functions, the spectrum of excited states, and
most transport properties.
Hohenberg and Kohn showed that if we know the ground state density n(r), we can deduce
from it the external potential Vext (r) in which the electrons move, up to an overall constant.
This is very important, because there are only two ways in which distinct many-electron
problems can differ:
in the external potential Vext (r). (i.e. the nuclear potentials)
and in the number of electrons
Z
N=
111
n(r)dr.
(15.1)
112
LECTURE 15. DENSITY FUNCTIONAL THEORY
According to Hohenberg and Kohn, both of these are determined purely by the electron
density. In the case of the total number of electrons this is plain to see. That n(r) also
determines Vext (r) is far from clear.
15.1.1
Proof of the HohenbergKohn theorem
(This proof is appropriate for nondegenerate ground states. Other proofs are possible for
the more general case.) We suppose that the theorem is false. Therefore there exist two
external potentials V1 (r) and V2 (r) that result in the same ground-state density n(r). Call
1 and H
2 , and let the normalized ground-state wavefunctions be 1 and
the hamiltonians H
2 . Here
1 = T + V + V1 and H
2 = T + V + V2 .
H
(15.2)
The kinetic energy T and the two-body electronelectron interaction V are the same for all
systems of interacting electrons.
From the RayleighRitz variational theorem,
1 |1 i < h2 |H
1 |2 i,
1 = h1 |H
(15.3)
1 and the states are nondegenerate.

because 1 is the only wavefunction that minimises H
Then
2 |2 i + h2 |H
1 H
2 |2 i
1 < h2 |H
= 2 + h2 |V1 V2 |2 i
(15.4)
(15.5)
1 and H
2 differ only in the external potential. The expectation value of the onebecause H
body potential can be expressed directly in terms of the ground-state density n(r). Therefore
Z
1 < 2 + n(r) (V1 (r) V2 (r)) dr.
(15.6)
But we can switch indices and find that
Z
2 < 1 + n(r) (V2 (r) V1 (r)) dr.
(15.7)
Adding the two inequalities, we have

1 + 2 < 2 + 1 ,
(15.8)
which is a contradiction. As a result, the external potential corresponding to n(r) must be

unique. In other words, the external potential is a functional of the density:
Vext = Vext [n(r)].
(15.9)
The ground state wavefunction is a functional of the external potential Vext , and therefore
so is the energy E[Vext ], the kinetic energy T [Vext ] and the interaction energy V [Vext ]. But
15.2. APPLICATION OF THE HOHENBERGKOHN THEOREM
113
since Vext is a functional of the density n(r), all of these quantities are functionals of the
ground-state density, including the ground-state wavefunction.
We now come to the second HohenbergKohn theorem, or density functional theorem. This
states that the ground-state density n0 (r) minimizes the energy functional
Z
E[n(r); Vext ] = T [n(r)] + V [n(r)] + n(r)Vext (r)dr.
(15.10)
15.1.2
Proof of the second HohenbergKohn theorem
Start with the wrong density n0 (r). This corresponds to a different external potential and a
0 , with ground state 0 . Therefore
different hamiltonian, H
0 i = E[n0 (r)] > h|H|i
h 0 |H|
= E[n0 (r)].
15.2
(15.11)
Application of the HohenbergKohn theorem
The HohenbergKohn result has important implications for the many-body problem. We
define the HohenbergKohn functional FHK [n(r)]:
FHK [n(r)] = T [n(r)] + V [n(r)], so that
Z
E[n(r); Vext ] = FHK [n(r)] + n(r)Vext (r)dr.
(15.12)
(15.13)
FHK is independent of Vext , and is therefore a unique functional, the same for all interacting
N -electron systems. In principle if we knew FHK we could solve all many-body problems in
terms of their density. In practice FHK is not known, and never will be known. People have
developed various approximations to it over the years, but do not have a single functional
that works for all types of materials.
15.3
The KohnSham equations
The HohenbergKohn theorems show that the ground state density n0 (r) on its own uniquely
determines the energy and ground-state properties of an interacting many-body system.
However, it doesnt give us any way of calculating n0 (r). The KohnSham procedure is one
possible way of carrying out the calculation. The first density functional theory calculations
were made in this way, and it remains appealing to us for the physical insight it gives.
We want to minimize the energy as a function of the density n(r). A convenient way to
proceed is to decompose n(r) in to a sum of fictitious independent orbital contributions
n(r) =
N
X
i (r)i (r)
(15.14)
i=1
where the i (r) are orthonormal. It is very important to note that these are not the wavefunctions of the interacting many-body hamiltonian. However, this form for the density is
114
exactly what we would find for a noninteracting system, in which the many-body wavefunction is a Slater determinant of the N lowest-lying single-particle orbitals.
The HohenbergKohn theorem guarantees that such a noninteracting system exists. That
is, there is a noninteracting system whose ground-state density n0 (r) = n(r) and, by the
HohenbergKohn theorem, n0 (r) uniquely determines the external potential Vs in the noninteracting hamiltonian.
We start with this noninteracting system. Its hamiltonian is
s = T + Vs
H
(15.15)
By the HohenbergKohn theorem there exists a unique energy functional

Z
Es [n] = Ts + Vs (r)n(r)dr.
(15.16)
Note that, while the kinetic energy operator is the same for interacting and noninteracting
systems, the kinetic energy functional for the noninteracting system, Ts [n], will be different
from that of interacting systems T [n] due to the effects of electron correlation. Actually,
unlike the interacting case, we can write down Ts [n]:
Ts [n] =
N
X
i=1
hi|
~2 2
|ii,
2m
(15.17)
because there are no correlations in the wavefunction beyond those of Pauli exclusion.
Since this is a noninteracting system we can easily determine the ground state density. We
solve the Schrodinger equation for the single particle orbitals

~2 2
+ Vs (r) i (r) = i i (r)
(15.18)
2m
and use Eq. 15.14 to construct the ground state density from the N lowest lying levels.
We are actually interested in a system of N interacting electrons in an external potential
Vext (r). We look for a potential Vs (r) for the noninteracting system such that the groundstate density of the noninteracting system is the same as that of the interacting system.
We start by taking the energy functional of the interacting system and trying to cast it into
a noninteracting form.
Z
E[n] = T [n] + V [n] + n(r)Vext (r)dr
(15.19)

ZZ
e2 1
n(r)n(r0 )
0
= Ts [n] + (T [n] Ts [n]) + V [n]
drdr
(15.20)
40 2
|r r0 |
ZZ
Z
n(r)n(r0 )
e2 1
0
+
drdr + n(r)Vext (r)dr
(15.21)
40 2
|r r0 |
ZZ
Z
e2 1
n(r)n(r0 )
0
= Ts [n] +
drdr + n(r)Vext (r)dr + Exc [n(r)] (15.22)
40 2
|r r0 |
15.4. THE LOCAL DENSITY APPROXIMATION
115
This looks much simpler. We have the kinetic energy of the noninteracting system, Ts [n], a
Hartree-like interaction term, an external potential, and an exchangecorrelation energy

ZZ
n(r)n(r0 )
e2 1
0
(15.23)
drdr
Exc [n] = FHK [n] Ts [n] +
40 2
|r r0 |
that contains all our ignorance about electronelectron interactions beyond the Hartree term.
Taking the functional derivative E[n]/n(r), we see that we have what appears to be independent electrons moving in an external potential
Z
e2
n(r0 )
Vs (r) =
dr0 + Vext (r) + Vxc [n(r)]
(15.24)
40 |r r0 |
where
Exc [n]
.
(15.25)
n(r)
The only catch is that Vs (r) depends on the density n(r), requiring us to solve the single
particle Schrodinger equation interatively, until a self-consistent determination of n(r) is
achieved.
The advantages of the KohnSham approach is that it is formally exact, as long as we
know Vxc (r). Of course, in practice, we dont, but good approximations exist and in weakly
correlated materials, such as most metals and semiconductors, the effects of exchange and
correlation are small.
The KohnSham equations resemble self-consistent Hartree equations with an added exchange
correlation potential. They are much easier to solve than the HartreeFock equations we
saw in an earlier lecture, because the effective potential is the same for each orbital.
Finally, the energies i in the KohnSham equations are just a formal device. However, if
Vxc (r) is small, they are often a good approximation to the single particle energies.
Vxc [n(r)] =
15.4
The local density approximation
To use the KohnSham equations we need an approximation for the exchangecorrelation

potential Vxc (r). A common choice, used in many band-structure calculations, is the local
density approximation or LDA. In LDA, the nonlocal nature of Vxc (r) is ignored and the
exchange correlation energy written
Z
Exc [n] = xc [n]n(r)dr.
(15.26)
Various approximations for xc [n] exist, interpolating between limits that can be solved
exactly.
15.5
ThomasFermi as a density functional theory
We have already seen one example of a density functional theory the ThomasFermi
theory. We used this to find the charge response of an electron gas to an external potential.
116
We made the approximation that the external potential was in the long wavelength limit
where it simply caused a rigid shift of the single particle energies. We then used it to calculate
the charge density induced around a point-like object, which really was overstretching the
limits of its validity. Using the HartreeFock approximation in the jellium model, we can
construct an explicity density functional for the total energy E, as a sum of the following
terms:
kinetic energy
V
2/3 5/3
~2 3
n
3 2
2m 5
(15.27)
external potential
Z
Vext (r)n(r)dr
(15.28)
Coulomb energy
e2 1
40 2
n(r)n(r0 )
drdr0
|r r0 |
(15.29)
3
V
4
1/3 2
3
e
n4/3
40
(15.30)
exchange energy
(This is called the ThomasFermiDirac theory if we include the exchange term.)

We need to constrain the total number of particles to be N , which we do by introducing a
Lagrange multiplier , the chemical potential, defined to be
E
(15.31)
We use as a dial with which to set the electron density. Subject to this constraint, the
energy is minimized by taking the functional derivative with respect to n(r).
1/3 2
Z

~2
3
n(r0 )
e
e2
0
2 2/3 2/3
dr
n1/3 =
(15.32)
3
n + Vext (r) +
0
2m
40 |r r |
40
Unfortunately, the ThomasFermiDirac model is not very accurate.
15.6
What can be calculated with density functional

theory?
Density functional theory is a theory for the ground-state energy of an interacting electron
system. Quantities that depend on the ground state energy and density can be calculated
most accurately. These include:
the total energy and structural phase transitions. The total energy is calculated for a
variety of different crystal structures and lattice spacings, allowing the crystal structure
to be predicted at different densities.
15.6. WHAT CAN BE CALCULATED WITH DENSITY FUNCTIONAL THEORY? 117

surface reconstructions. The total energy of a surface can be calculated very accurately
to predict how it will differ structurally from the bulk.
phonon energy dispersions. Using the BornOppenheimer approximation (i.e. that
electrons move much faster than ion cores), so called frozen phonon calculations
directly obtain the energy cost of passing an elastic wave through a solid.
quantum chemistry. Properties of molecules such as bond length, electron density, vibrational frequencies and ionization energies can be calculated using LDA, or the local
spin density approximation (LSDA). Chemists also commonly use another approximation to Vxc [n] the generalized gradient approximation (GGA).
band structures. The single-particle energy eigenvalues in the KohnSham equations
can be interpreted as energy bands and, although this has no formal justification, it
works well in many materials.
linear response functions. It can be shown formally that linear response functions such
as the electrical conductivity are properties of the ground state. There exist variants
of density functional theory for calculating them. As we will see later in the course,
poles in linear response functions correspond to the excited states of the system.
Density functional theory has some notable failures, too. It is not able to calculate band-gap
energies in semiconductors and insulators, and breaks down entirely in correlated electron
systems, where the exchangecorrelation energy is large.
118
Lecture 16
The dynamics of Bloch electrons I
The most important way in which a crystalline solid differs from a box of free electrons
is in the existence of bands of allowed energies. The eigenstates of a periodic solid are
Bloch electrons. Like free electrons, Bloch electrons for the most part propagate through a
regular array of ion cores as though it were not there, although with modified energies that
we describe by an energy band structure. Given any crystal, we can now calculate these
energy bands, in principle quite accurately for the many materials in which the effects of
electronelectron correlation are weak.
Now, with a view to understanding and predicting the transport properties of solids, we would
like to develop a model for the dynamics of electrons in crystalline materials, in particular
their response to external fields. We will see that Bloch electrons can be understood with a
simple set of rules, which we call the semiclassical model of electron dynamics.
16.1
Energy bands and group velocity
The correct velocity to use for a Bloch electron is the group velocity
vnk =
1
k nk .
~
(16.1)
In order to show this, we need to simultaneously specify the position and wavevector of the
electron. This is the semiclassical approach, which can be made rigorous by setting up a
wavepacket, centred on r with width r, constructed from a range of wavevectors of width
k, centred on k as shown in Fig. 16.1. This will be subject to the constraint rk > 1.
The Bloch electron wavepacket has the following form
Z
W (r, k, t) = dk0 w(k0 k)k0 eik0 t/~ ,
(16.2)
where w(k0 k) is a function sharply peaked at the origin and
k (r) = eikr uk (r),
uk (r) = uk (r + R).
119
(16.3)
(16.4)
120
LECTURE 16. THE DYNAMICS OF BLOCH ELECTRONS I
lattice constant
spread of wave packet
wavelength of applied field
Figure 16.1: The hierarchy of length scales in a Bloch wavepacket.
dk0 w(k0 k)eik r uk0 (r)eik0 t/~

Z
0
ikrik t/~
= e
dk0 w(k0 k)ei(k k)r uk0 (r)ei(k0 k )t/~
W (r, k, t) =
(16.5)
(16.6)
Taylor expand the energy about k:

k0 = k + (k0 k) k k .
(16.7)
Let k00 = k0 k, then

ikrik t/~
W (r, k, t) = e
dk00 w(k00 )eik
00 (r
k k t/~)
uk+k00 (r)
eikrik t/~ F (r k k t/~).
(16.8)
(16.9)
The wavefronts move with phase velocity k /~k. The centre of the envelope function F
moves at the group velocity
1
r = k k .
(16.10)
~
This forms the basis of the semiclassical model, in which a classical treatment of the electron
dynamics allows us to obtain deep insights into how the electrons will behave in transport
and thermodynamic measurements. By constructing the wavepacket from Bloch functions we
have ensured that the electron will be able to propagate through the periodic lattice without
attenuation. The only scattering will be caused by defects in the periodicity, including
static defects such as vacancies and impurities, and dynamical defects such as the thermal
vibrations of the ions.
One subtlety of the semiclassical model is that the periodic potential varies on a scale small
compared to the size of the wavepacket. The semiclassical model is actually only partially
in the classical limit the response to external, long-wavelength fields is treated classically,
but the periodic field of the ions is treated quantum mechanically in the calculation of the
Bloch wavefunctions.
16.2. RULES OF THE SEMICLASSICAL MODEL
16.2
121
Rules of the semiclassical model
The semiclassical model predicts how the position r and wavevector k of each electron evolve
in the presence of externally applied electric and magnetic fields, in the absence of collisions.
This can be achieved based entirely on a knowledge of the bandstructure, n (k), with no
other information about the periodic potential of the ions necessary. The end result of this
process is that we can calculate the response of the electrons to applied fields or temperature
gradients. That is, we can predict the solids transport properties. Very importantly, the
procedure can be run backwards, to infer the form of n (k) by analyzing data from transport
experiments.
Given the functions n (k), the model associates a position r, a wavevector k, and a band
index n for each electron. The external electric and magnetic fields in general depend on
space and time.
E = E(r, t)
B = B(r, t)
(16.11)
(16.12)
The electron dynamics are described by a set of rules, which we will justify further below:
The band index n is a constant of the motion.
The time evolution of r and k is determined by the equations of motion
1
r = vn (k) = k n (k)
~

~k = e E(r, t) + vn (k) B(r, t) .
(16.13)
(16.14)
Wavevector is defined only to within an additive reciprocal lattice vector G. This

means that we cannot have two distinct electrons with the same band index n and
position r, whose wavevectors k and k0 differ by a reciprocal lattice vector G. As a
result, {n, r, k} and {n, r, k + G} are equivalent ways of describing the same electron
and therefore all distinct wavevectors lie within the first Brillouin zone.
In thermal equilibrium, the occupation number of the volume element dk of k-space,
working in unit volume and including a factor of 2 for spin, is the usual Fermi distribution:
dk/4 3
dk

.
(16.15)
f (n (k)) 3 =
4
exp (n (k) )/kB T + 1
122
Comments on the rules of semiclassical electron dynamics.

The external fields are not allowed to cause interband transitions. Each band therefore
contains a fixed number of electrons of a particular type.
Completely filled bands are inert. They do not respond to external fields and therefore
carry no current. As a result, we only need to consider partially filled bands i.e.
bands within a few kB T of the Fermi energy.
Crystal momentum is not momentum! Within each band, the equations of motion are
the same as for free electrons, but with ~2 k 2 /2m n (k). ~k is not the momentum
of a Bloch electron. While p equals the total force, ~k equals the force exerted by the
external fields, not by the periodic field of the lattice. We have already taken account
of the electrostatic fields of the lattice quantum mechanically, in deriving the Bloch
states.
16.3
The kP method
Before discussing the consequences and limits of validity of the semiclassical model, we make
a brief digression and introduce the kP method, which underlies the equations of motion of
Bloch electrons.
In a finite sample, there is a conceptual difficulty that arises from the fact that the allowed
wavevectors are a discrete set of points in k-space. At any one of these points the energy
eigenstates in the presence of a periodic potential are formed by combining plane waves that
have wavevector differing from the original k by a reciprocal lattice vector G. The energy
dispersion k is then a discrete set of points in k-space, not a set of continuous curves. But
we need continuous curves in order to calculate the semiclassical dynamics. In other words,
given the eigen-energies at some wavevector k, we need to be able to track continuously how
the energies evolve when we move to some nearby wavevector k + k. The approach we
take is to recast the original hamiltonian into a form that depends explicitly on k, and then
treat the shift in wavevector k as a small change to be handled in perturbation theory. By
setting up the problem in this way we get an expression for the energies at wavevector k + k
entirely in terms of the wavefunctions at the original wavevector k.
Bloch functions have the form
nk (r) = eikr unk (r),
(16.16)
where unk (r) has the full periodicity of the crystal lattice. If we substitute this into the
Schrodinger equation

~2 2
+ U (r) nk (r) = nk (r)

(16.17)
2m
it is straightforward to show that unk (r) obeys the equation
2

~
2
2
2ik + k + U (r) unk (r) = unk (r).
2m
(16.18)
16.3. THE KP METHOD
123
Because unk (r) is periodic, Eq. 16.18 can be solved in a single unit cell of the crystal.
We now have a hamiltonian that depends explicitly on k, so we are ready to carry out our
pertubation procedure. Before we start, we expect that the energy dispersion n (k) will be
Taylor expandable around the point k:
X n
n (k + k) = n (k) +
ki
ki +
1 X 2 n
ki kj + O(k)3 .
2 ij ki kj
(16.19)
The shift in wavevector, k k+k, can be treated as a perturbation term in the hamiltonian:
2
2
2
k + Vk .
k H
k+k = H
k + ~ k (i + k) + ~ k H
H
m
2m
(16.20)
We will make use of the result from time-independent perturbation theory:

En =
16.3.1
En0

X hn|V |n0 i2
+ hn|V |ni +
+ O(V )3 .
0 E0
E
n
n0
n0 6=n
(16.21)
First order terms:
Keep terms linear in k:

X n
i
ki
ki =
X
i
2
k n =
hunk |
~2
ki (i + k)i |unk i
m
~
hunk |(k i)|unk i
m
(16.22)
(16.23)
But
unk = eikr nk
(16.24)
(k i)eikr = ieikr ,
(16.25)
and
so
~
hnk | i~|nk i
m
~
=
hnk |P |nk i
m
= ~h
v i,
k n =
(16.26)
(16.27)
(16.28)
defining v P /m. This confirms what we earlier deduced that the average velocity is
the group velocity of the wavepacket.
124
16.3.2
Second order terms:
Now isolate the second order terms.

2

~2
~2
0
0
k
(k
i)
|u
ihu
|
k
(k
i)
|u
i
hu
|
X X nk m i
i nk
nk m
j
j nk
~ k
1 X n
ki kj =
+
2 ij ki kj
2m
n0 6=n
nk n0 k
ij
(16.29)
We can use the same trick as Eqs. 16.24 and 16.25 to recast this in terms of the original
Bloch functions nk .
~2 k 2 1
1 X 2 n
ki kj =
+
2 ij ki kj
2m 2
~
m
2 X X h | i~ k | 0 ih | i~ k | 0 i + c.c.
nk
i nk
nk
j nk
xi
xj
nk n0 k
n0 6=n ij
(16.30)
That is
2 n
~2
= ij +
ki kj
m
~
m
2 X
hnk |Pi |n0 k ihnk |Pj |n0 k i + c.c.
nk n0 k
n0 6=n
(16.31)
To see what the curvature of the energy dispersion has to do with the dynamics of Bloch
electrons, calculate the acceleration.
X hvi i dkj
1 X 2 n dkj
d
hvi i =
=
= ~ M1 k
dt
kj dt
~ j ki kj dt
j
(16.32)
where
M1

ij
1 2 n
~2 ki kj
(16.33)
1 X hnk |Pi |n0 k ihnk |Pj |n0 k i + c.c.

ij
+ 2
m m n0 6=n
nk n0 k
(16.34)
is the inverse effective mass tensor, and controls how Bloch electrons accelerate in response
to external fields. We can interpret the effective mass equation (Eq. 16.34) as saying that
the band mass arises from virtual transitions between bands. The closer the adjacent band,
the bigger the deviation from the free electron mass.
nearby band of higher energy negative contribution to 1/m
nearby band of lower energy positive contribution to 1/m
At the top of the band, the overall curvature is negative. These negative mass Bloch electrons
accelerate in the opposite direction to the Lorentz force. (Actually, the fact that we have an
effective mass tensor means that the acceleration does not need to be parallel to the force.)
The usual way to think of these negative-mass electrons is as positively charged holes.
16.4. CONSEQUENCES OF THE SEMICLASSICAL MODEL
16.4
125
Consequences of the semiclassical model
We now look at some of the consequences of the semiclassical model of electron dynamics.
For simplicity we work with a single band and a zero temperature Fermi distribution nk :
nk = 1,
nk = 0,
16.4.1
(k) < EF
(k) > EF .
(16.35)
(16.36)
Electrical current
The current density of a single electron in the state k will be evk /V , where V is the volume
of the system.
The total current density carried by the band will be
2 X
(e)nk vk
(with a factor of 2 for spin)
V k
Z
2 V
(e)nk vk dk
V (2)3
Z
dk 1
= e
k k ,
3
occupied 4 ~
j =
(16.37)
(16.38)
(16.39)
where the integral is over the occupied states. The current density is independent of sample
volume, as it should be. In equilibrium j = 0, as for every occupied state k there is an
occupied state k that makes an opposite contribution to the electrical current. In the
presence of external fields this balance can be broken, resulting in a finite current.
16.4.2
Thermal current
The flow of heat can be treated in a similar way. A state k carries an energy current
(k)vk /V . The total energy current density is
2 X
(k)nk vk
V k
Z
2 V
(k)nk vk dk
V (2)3
Z
1
dk 1
=
k (2k ).
3
2 occupied 4 ~
j =
(16.40)
(16.41)
(16.42)
As with the electrical current, j = 0 in equilibrium.
16.4.3
Filled bands
For a filled band, the integrals in Eqs. 16.39 and 16.42 are over an entire Brillouin zone
i.e. over whole unit cells of the reciprocal lattice. The integrals therefore vanish, by
126
the theorem that the integral over any primitive cell of the gradient of a periodic function
must vanish. Filled bands are therefore inert, and make no contribution to electrical or
thermal currents. This justifies our earlier assertion that we focus attention on partially
filled bands when calculating the dynamical properties of Bloch electrons and shows why
electronic transport plays no role in insulators, as insulators consist solely of completely filled
and completely empty bands.
16.4.4
Electrons and holes
The contribution of all the electrons in a given band to the current density is
Z
dk
v .
j = (e)
3 k
occupied 4
A completely filled band carries no current, so
Z
Z
Z
dk
dk
dk
vk =
vk +
v
0=
3
3
3 k
occupied 4
unoccupied 4
zone 4
We can therefore write
(16.43)
(16.44)
Z
j = (+e)
dk
v .
3 k
unoccupied 4
(16.45)
That is, the current carried by a band is the same as if the states occupied by electrons were
empty, and the unoccupied states were filled with fictitious particles of positive charge +e
called holes.
This can be very convenient instead of working with an almost filled band of electrons, we
can work with a small density of holes, for which the energy dispersion at the top of the band
will be almost perfectly parabolic. That is, we can use the effective-mass approximation. A
quick work of warning though do not think of a band as consisting of electrons and holes
at the same time!
16.5
Semiclassical motion in a uniform dc electric field
In a static, uniform electric field the semiclassical equation of motion is

~k = eE.
(16.46)
This can be integrated to get

k(t) = k(0)
eEt
.
~
(16.47)
That is, in a time t the wavevector of every electron changes by the same amount, eEt/~.
For a metal (a solid with a Fermi surface) this corresponds to a sideways displacement of
the Fermi sea, in the opposite direction to the electric field, that grows linearly in time. The
resulting current density also grows linearly in time. Such a situation is unsustainable and in
a real material scattering processes intervene to restrict the displacement of the Fermi surface
16.5. SEMICLASSICAL MOTION IN A UNIFORM DC ELECTRIC FIELD
127
e E/h
Figure 16.2: A uniform electric field shifts the Fermi surface in k-space at a constant rate.
Scattering processes limit the acceleration to a finite displacement.
to an amount k = eE /~, where is a characteristic relaxation time of the electrons.

Later in the course we will develop transport theories to study this situation in more detail.
For an insulator the situation is less intuitive. The electrons still in principle obey an acceleration equation, with wavevectors that increase linearly in time. However, in an insulator all
the occupied Brillouin zones are completely filled. We then have to examine what happens at
the edge of the Brillouin zone, at a Bragg plane. In the semiclassical model our wavevectors
are only defined modulo a reciprocal lattice vector G. As a result, when the electric field
causes the wavevector of an electron to cross a Bragg plane, it will be Bragg reflected back
to the other side of the Brillouin zone, where it will make the opposite contribution to the
current density.
Another way to see this is in the extended zone scheme, as shown in Fig. 2. There (k) its
a periodic function, as is v(k). If an electron could be accelerated for an extended period of
time without scattering, its velocity would be a periodic function of time:
v(k(t)) = v(k(0) eEt/~).
(16.48)
The resulting contribution to current would also be oscillatory in time. Effects of this sort
are called Bloch oscillations, and have been observed in very clean semiconductors and,
very recently, in laser-cooled atoms trapped in optical lattices.
128
(k)
v(k)
zone boundary
zone boundary
Figure 16.3: (k) and v(k) are periodic functions in the extended zone scheme.
Lecture 17
The dynamics of Bloch electrons II
We investigate the dynamics of Bloch electrons further by studying their motion in a uniform
magnetic field. Along with the simple case of the response to a uniform static electric field,
which determines the electrical resistance, the motion of Bloch electrons in a magnetic field
is perhaps the most important experimental arrangement, being responsible for most of the
experimental data we have on the structure of Fermi surfaces of metals. These experiments
have at the same time provided detailed tests of the theory of Bloch electrons and extensions
to it such as Landaus Fermi liquid theory. The agreement with theory is very satisfying and
the experiments themselves are beautiful, so it is well worth taking the time to study how
electrons in solids respond to magnetic fields.
17.1
Semiclassical motion in a uniform magnetic field
In a static, uniform magnetic field B, the equations of motion for Bloch electrons are:
1
k (k),
~
~k = (e)v(k) B
e
= k (k) B.
~
r v(k) =
(17.1)
(17.2)
(17.3)
The constants of the motion are the energy

d
dk
= k (k)
dt
dt

e
= 2 k (k) k (k) B
~

e
= 2 B. k (k) k (k)
~
= 0
129
(17.4)
(17.5)
(17.6)
(17.7)
130
LECTURE 17. THE DYNAMICS OF BLOCH ELECTRONS II
Figure 17.1: In an applied magnetic field, the electrons undergo cyclotron motion, in a
plane perpendicular to the field and along contours of constant energy. (From Ashcroft and
Mermin[4].)
and the projection of the wavevector along the field direction

e
B dk = B v B dt
~

e
= v B B dt
~
= 0.
(17.8)
(17.9)
(17.10)
The resulting motion is shown in Fig. 17.1. The trajectories lie in planes perpendicular to
the magnetic field, and follow contours of constant energy. In particular, an electron at F
will trace out an orbit on the Fermi surface.
It is useful to calculate the real-space motion r(t) corresponding to the k-space orbit. Let
rk be the projection of r along the field direction, and r be the component normal to B.
in the direction of the magnetic field:
Define a unit vector B
B)
rk = B(r
(17.11)
B)
r = r rk = r B(r
r B).
r = r B(
(17.12)
(17.13)
with the equation for the acceleration, Eq. 17.2, and using
Taking the vector product of B
the vector identity (A B C) = B(A C) C(A B), we have
~k = (e)B
r B
B

B
r ) |B|
= (e) r B(
= (e)|B| r .
(17.14)
(17.15)
(17.16)
17.1. SEMICLASSICAL MOTION IN A UNIFORM MAGNETIC FIELD
131
Figure 17.2: The k-space orbit, shown on the left, is rotated by 90 and scaled by ~/eB to
give the perpendicular component of the real-space orbit. (From Ashcroft and Mermin[4].)
If we integrate the last equation, we have

r (t) r (0) =

~
B k(t) k(0) .
e|B|
(17.17)
This shows that the projection of the real-space orbit onto a plane perpendicular to the
magnetic field is just the k-space orbit, rotated by 90 , and scaled by ~/eB. Figure 17.2
shows the idea. This is a very useful result when trying to visualize the effect of a magnetic
field on the electrons. The real-space motion of a Bloch electron along the magnetic field is
affected by the field, but not in a simple way. In general the velocity along the field direction
will be periodically modulated in time.
17.1.1
The cyclotron frequency
We now calculate the time taken to traverse a closed orbit in k-space. Let t2 t1 be the time
taken for the electron to go from k1 to k2 . This can be written
Z
t2
t = t2 t1 =
t1
Z k2
=
k1
dt
(17.18)
1
dk.
|k|
(17.19)
132
From Eq. 17.17 we know that the real-space and k-space trajectories are related.
eB
|r |
~
eB
=
|(k k ) |
~2
=
|k|
(17.20)
(17.21)
So the time taken to traverse the trajectory is

~2
t =
eB
k2
k1
1
dk.
|(k k ) |
(17.22)
Figure 17.3: Diagram showing the construction used to calculate the cyclotron period. (From
Ashcroft and Mermin[4].)
It turns out that Eq. 17.22 has a simple geometric interpretation. To see this, let (k)
be a vector in the plane of the orbit, perpendicular to the orbit at k and joining k to a
neighbouring orbit with energy + . We then have
= k k (k)
= |(k k ) |(k). (The vectors are parallel.)
(17.23)
(17.24)
As a result
|(k k ) |1 =
(k)

(17.25)
17.2. LIMITS OF VALIDITY OF THE SEMICLASSICAL MODEL
133
and
~2 1
t =
eB
k2
(k)dk.
(17.26)
k1
R k2
(k)dk is just the area between two neighbouring orbits with energy difference , which
we call A12 . Then
~2 A12
~2 A12
t2 t1 =
(17.27)
eB
eB
k1
in the limit 0. We are usually interested in the traversal time of closed orbits, in which
case k1 = k2 . Then t2 t1 = T , the cyclotron period, which will be a function of the energy
(usually the Fermi energy) and kz , the projection of the wavevector onto the field axis.
T (, kz ) =
~2
A(, kz ),
eB
(17.28)
where A(, kz ) is the cross sectional area of an orbit of energy and projection kz . We usually
focus on the cyclotron frequency c = 2/T and, in analogy to the free-electron result, define
a cyclotron mass m by
eB
c = .
(17.29)
m
The cyclotron mass is
m =
~2
A(, kz ).
2
(17.30)
Again we see that an important dynamical property of the Bloch electrons is determined by
the geometry of the constant energy surfaces, which we can extract from the band structure
n (k).
The cyclotron frequency is directly accessible in experiments. One typically applies a large
magnetic field and then looks for the cyclotron motion of the electrons to come into resonance
with an applied microwave-frequency field. There are several experimental geometries in
which the resonance condition corresponds to an enhanced absorption of microwaves by the
orbiting electrons. The width of the resonant absorption in frequency is 1/ that is,
inversely proportional to the relaxation time of the electrons. For this reason, high purity
samples and low temperatures are usually required to see a sharp resonance.
17.2
Limits of validity of the semiclassical model
We know that in the limit of vanishingly small periodic potential the semiclassical model
must break down. In this limit, the Bloch electron becomes a free electron, and free electrons
can accelerate without limit, breaking our requirement that the band index be a constant
of the motion. As a result, there must be some minimum strength of the periodic potential,
relative to the strength of the external fields, before the semiclassical model applies. It turns
out that approximate constraints can be obtained using simple arguments. The conditions
134
for the semiclassical model to apply are:

eEa
~c
2
gap (k)
F
2
gap (k)
,
F
(17.31)
(17.32)
where
constant, c = eB/m is the cyclotron frequency, and gap (k) =
a is the lattice

min n0 (k) n (k) is the minimum energy separation to the nearest band.
Equation 17.31 is never violated in a metal, but can be exceeded in insulators and homogeneous semiconductors. When electric breakdown occurs, it is called Zener tunneling between
bands.
Equation 17.32 is relatively easy to violate in a metal, and is called magnetic breakdown
(or breakthrough). When it occurs, electrons can jump across Bragg planes to follow a
free-electron-like trajectory.
Other conditions that must be satisfied in the semiclassical model are that the frequency of
the external fields be low compared to the energy gap, ~ gap (k), and that the wavelength
of the external fields be long compared to the lattice spacing, a.
We can use simple arguments to arrive at the conditions for electric and magnetic breakdown.
When U (r) is vanishly small, electric breakdown occurs whenever an electron crosses a Bragg
plane, as this causes it to make an interband transition. When U (r) is weak but finite, we
can estimate how large an electric field would be needed to cause breakdown by focussing
on electrons in the vicinity of a Bragg plane.
Near Bragg planes gap (k) has large curvature. A small spread in wavevector (an unavoidable
consequence of forming a wavepacket) causes a large spread in velocity.

2
v
1

k
(17.33)
v(k) = k
k
~ k 2
For the semiclassical picture to hold, the spread in velocity must be much smaller than the
Fermi velocity.
v vF
k
(17.34)
~vF
2
( /k 2 )
(17.35)
Since the potential is weak we can use the result derived for nearly free electrons near a
Bragg plane, sketched in Fig. 17.4.
In the vicinity of the Bragg plane, the energy dispersion is just the sum in quadrature of
the unperturbed free electron energy and the relevant Fourier component of the periodic
potential. (An identical expression results for the energy dispersion of a superconductor,
and is a handy form to remember.)
2
(k )2 = (0k )2 + UG
,
(17.36)
17.2. LIMITS OF VALIDITY OF THE SEMICLASSICAL MODEL
135
+(k)
0(k-G)
UG
UG
0(k)
-(k)
Figure 17.4: Plot of the energy dispersion near a Bragg plane. The Fourier component of
the potential UG mixes the free-electron curves and opens a gap in the spectrum. This has
2
been approximated by the form (k )2 = (0k )2 + UG
, which is a general form for energy
gaps.
where
0k = 0k 0G/2
G
~2 G
~2 G
(k )
k vF ~k.
2m
2
2m
(17.37)
Therefore
k =
2
UG
+ (0k )2
(17.38)
(0k )2
2UG
~2 vF2 (k)2
= UG +
.
2UG
UG +
(17.39)
(17.40)
We need the curvature of the energy dispersion in the vicinity of the Bragg plane (where it
is largest). This is
2 k
2 k
~2 vF2
=
=
.
(17.41)
k 2
(k)2
UG
We require that
k ~vF
UG
UG
gap
=
.
2
2
~ vF
~vF
~vF
(17.42)
This requires that

x
1
~vF

,
k
gap
(17.43)
136
or that
eEx
eE~vF
.
gap
(17.44)
When the uncertainty in potential, , becomes larger than the energy gap, the electron
can easily make a transition between bands. To prevent this from happening, we require
that gap . That is
eE~vF
gap
.
(17.45)
gap
Since the Fermi energy F ~vF /a, where a is the lattice spacing, the condition can be
rewritten
2
gap (k)
.
(17.46)
eEa
F
17.3
Magnetic breakdown
In the magnetic case, energy cannot be gained from the magnetic field, which we showed
above. In order for breakdown to occur, the electron must therefore jump from one band
to the next while conserving energy. The situation in which this can occur is depicted in
Fig. 17.5, and is common in many metals. To avoid magnetic breakdown, we require that the
(k)
+(k)
gap
-(k)
k
Figure 17.5: Plot of the energy dispersions required for magnetic breakdown. In this case,
the electron cannot take energy from the field, so it must pass horizontally from one band
to the other. In a magnetic field B, the characteristic spread of the wavepacket goes as
k B. At high enough fields k > k, and magnetic breakdown occurs.
spread in wavevector of our wavepacket, k, be much smaller than the k-space separation
between bands, k gap /~vF . We showed above that the semiclassical orbit in real space
is the same as the k-space orbit, but rotated by 90 and scaled by ~/eB. Therefore, if the
17.3. MAGNETIC BREAKDOWN
137
Figure 17.6: The figure on the left shows a free electron orbit, and the same orbit shifted by
a reciprocal lattice vector. Where the orbits cross the Bragg plane they are degenerate. In
the presence of a lattice potential the degeneracy is lifted and the k-space orbits disconnect
to form two new orbits. These are shown on the right. At low fields the electrons follow
the perturbed orbits. At high fields magnetic breakdown causes the electrons to follow the
original free electron orbits. (From Ziman[12].)
wavepacket has a width kx in the x direction in k-space, it will have a width y = kx ~/eB
in the y direction in real space. The wave nature of the packet requires that
ky y 1 ky kx
eB
.
~
(17.47)
If we assume the wavepacket is isotropic, we can estimate the size of the wavepacket in a
given magnetic field.
r
p
eB
.
(17.48)
k kx ky
~
To avoid magnetic breakdown, we require
r
gap
eB
k

.
(17.49)
~
~vF
2gap
eB
2 2
(17.50)
~
~ vF
2gap
~eB
21 2
(17.51)
m
mvF
2
2gap
~c
(17.52)
F
It turns out that this condition is quite easy to violate in a metal, in laboratory fields, and
must always be considered as a possibility when interpreting magnetotransport data taken
under high field.
138
Lecture 18
Quantum oscillatory phenomena
In this lecture we treat quantum mechanically the cyclotron motion of electrons in a high
magnetic field. The results are quite surprising at sufficiently low temperatures, in high
purity samples, all physical quantities oscillate periodically in inverse field. These effects
have been central to the development of our current understanding of electrons in solids.
18.1
Quantum mechanics of the orbital motion
The hamiltonian of a (nonrelativistic) charged particle in a magnetic field is

= 1 (
p eA)2 .
H
2m
(18.1)
A very important property of this Hamiltonian is gauge invariance it is invariant under a

simultaneous transformation of the potential
A A +
(18.2)
eie/~ .
(18.3)
and the wavefunction

In the following we will work in a particular gauge, the Coulomb gauge, in which A = 0,
although all physical quantities will of course be independent of this choice.
Let A = (0, Bx, 0), then
Ay
A = (0, 0,
) = (0, 0, B),
(18.4)
x
corresponding to a magnetic field in the z direction.
Substituting this into the hamiltonian gives the following Schrodinger equation:

~2 2
ieB 2
2
+(
x) + 2 (r) = (r).
(18.5)
2m x2
y
~
z
We expect the solution to have the form
(x, y, z) = exp [i(y + kz z)] u(x).
139
(18.6)
140
LECTURE 18. QUANTUM OSCILLATORY PHENOMENA
That is, we expect the motion along the field direction to be unmodified, we still expect
plane-wave-like behaviour in the y direction with wavenumber , but we will have to solve
for the detailed shape of the wavefunction in the x direction.
The next step is to substitute the trial solution into the Schrodinger equation in order to
find u(x) and . We get

ieB 2
~2 2
2
x) kz u(x) = u(x)
+ (i
2m x2
~
On rearranging this becomes

~2 2
1
2
2
+ mc (x x0 ) u(x) = 0 u(x),
2m x2 2
(18.7)
(18.8)
where
0 =
~2 kz2
,
2m
(18.9)
eB
, and
m
1 ~
~
=
.
=
eB
c m
c =
(18.10)
x0
(18.11)
That is, the problem decouples into the translational motion of a free particle along the z
direction and, in the plane perpendicular to the field, quantized harmonic motion, centred
on x0 and oscillating at the cyclotron frequency. We have already solved the problem of the
harmonic oscillator and can write down its energy spectrum directly.
1
0 = (n + )~c
2
1
~2 kz2
= (n + )~c +
.
2
2m
(18.12)
(18.13)
The eigenstates of quantized cycltron motion are called Landau levels and are central to the
understanding of all electronic phenomena in high magnetic fields, for example the quantum
Hall effects, and quantum oscillatory phenomena.
18.2
Degeneracy of the Landau levels
The significance of the oscillators position becomes apparent when we calculate the degeneracy of the Landau levels. In the presence of a magnetic field, how do we count states?
Previously we imposed the Bornvon Karmann periodic boundary conditions to a sample of
finite volume Lx Ly Lz by requiring that the wavefunction be single valued. This of course
continues to hold, requiring that kz be quantized in units of 2/Lz and, from our wavefunction ansatz, that be quantized in units of 2/Ly . But there is an additional restriction on
18.3. LANDAU LEVELS IN A PERIODIC POTENTIAL
141
it cannot just take any value. The centre of each cyclotron orbit in real space is related
to
1 ~
(18.14)
x0 =
c m
and must be somewhere within the sample, i.e. 0 x0 Lx , which implies that
0
mc
Lx
~
(18.15)
The number of allowed values of is the degeneracy p.

mc
Lx Ly
2~
e
BLx Ly
=
h
=
,
0
p =
(18.16)
(18.17)
(18.18)
where = BLx Ly is the magnetic flux through the sample and 0 = h/e is the quantum
of magnetic flux for a particle of charge e. Note that p counts the number of states for one
spin only.
We can now check to see if this correctly counts the number of levels in a two-dimensional
slice of k-space.
In the last lecture we showed that two-dimensional areas Ak in k-space can be related to the
cyclotron mass m .
2m
Ak
=

~2
2m
Ak =

~2
(18.19)
(18.20)
If we suppose that = ~c , the quantum of cyclotron frequency, the number of states

enclosed between adjacent cyclotron orbits in k-space will be
Lx Ly 2m
Lx Ly
A
=
~c
k
(2)2
(2)2 ~2
m c
=
Lx Ly
2~
= p.
(18.21)
(18.22)
(18.23)
We get the same result.
18.3
Landau levels in a periodic potential
The results we derived above were for free electrons of mass m . What happens when we
switch on the periodic potential of the ion cores? The potential will alter the shape of
the Fermi surface drastically in some cases but we still expect the electrons to trace
142
out closed orbits in k-space, in planes perpendicular to the magnetic field. What is the
quantization condition?
In the last lecture we showed that cyclotron frequency corresponded to geometric properties
of the constant-energy surfaces. Specifically, in the kz plane
h
,
T (n , kz )
~2 A(, kz )
.
T (n , kz ) =
eB

n+1 n = ~c =
where
(18.24)
(18.25)
(18.26)
Therefore
A(n , kz )
2eB
=

~
2eB
A(n+1 ) A(n ) =
,
~
2eB
A =
.
~
Adjacent cyclotron orbits in k-space differ by a fixed area, so the area enclosed by the nth
orbit is (n + )2eB/~, where is some (small) constant.
We could have arrived at this result a different way, by appealling to the BohrSommerfeld
quantization condition. This states that the integral of the momentum around closed, semiclassical orbits must be quantized in units of Plancks constant:
I
p dr = (n + )h,
(18.27)
(n+1 n )
where 0 1. For the case of free electrons, = 1/2. (BohrSommerfeld quantization

follows from the requirement that phase be quantized in units of 2, up to some additive
fraction of 2, which is equivalent to saying that the number of nodes in the wavefunction is a
good quantum number.) We will take the semiclassical motion to be in a plane perpendicular
to the magnetic field (which is along the z direction) and use our previous results for the
semiclassical trajectory.
dr =
I
~
dk z
eB
I
(18.28)
p dr = ~
k dr
I
~2
k (dk z)
=
eB
(18.29)
(18.30)
k (dk z) is just the area of k-space enclosed by the semiclassical orbit. Our quantization
condition is then
2eB
An =
(n + ),
(18.31)
~
where An is the area of k-space enclosed by the nth orbit.
18.4. VISUALIZING LANDAU QUANTIZATION
18.4
143
Visualizing Landau quantization
In zero field, our quantum states are a set of points in k-space, laid out on a three-dimensional
grid with a spacing inversely proportional to the size of the sample. When a strong field is
switched on along the z direction, kx and ky cease to be good quantum numbers. We now
visualize the allowed states as Landau tubes or rings, which have quantized cross sectional
area and energy spacing that grows in proportion to the applied field. In zero field each
k-state could hold one electron of each spin. For a macroscopic sample, the Landau levels
are highly degenerate, as shown above. Quantization along the field direction is unaffected.
kz
B=0
filled states
empty states
ky
kx
kz
ky
B =/ 0
kx
filled states
empty states
Figure 18.1: In the field-free case (top), the electronic eigenstates have well-defined crystal
momenta in a coarse-grained k-space. If a magnetic field Bz is applied, kx and ky cease to
be good quantum numbers, and the new states can be visualized as Landau tubes. (After
Christoph Bergemann[13].)
144
18.5
Quantum oscillations as a Fermi surface probe
The transition to Landau quantization in high magnetic fields has profound experimental
consequences, and leads to a number of effects that have the power to reveal in detail the
structure of the Fermi surface. For these effects to be observable, several rather stringent
experimental conditions must be satisfied. To begin with, Landau quantization, which stems
from the BohrSommerfeld requirement of single-valued wavefunctions, will only occur if the
electron can complete a k-space orbit coherently, with a small probability of scattering. This
requires that the mean time between collisions that randomize the phase of the electron
wavefunction, , be much greater than the cyclotron period: 1 c . The second condition
relates to the temperature. We know that the Fermi distribution changes from 1 to 0 in
an energy range of order kB T . In order that thermal smearing not wipe out the effect of
the Landau quantization, we require the Fermi distribution to be sharp on the scale of the
Landau level spacing. This requires that kB T ~c .
Fortunately, in many materials these conditions can be met, although very high magnetic
fields and temperatures much smaller than 1 K are often required. When these requirements
are satisfied, the effect of sweeping the magnetic field is quite dramatic. The spacing between
the Landau levels grows in proportion to magnetic field. As the field is swept, the detailed
structure of k-space and the degeneracy of the Landau levels change. The Fermi sea must
still hold N electrons so, as field increases, Landau tubes pop through the Fermi surface
and are emptied. The thermodynamic potential changes abruptly at this point, and a sharp
jump occurs in all thermal and transport properties. The oscillations show up most strongly
in the magnetization. This is called the de Haasvan Alphen effect and historically has been
very important in surveying the Fermi surfaces of metals. Properties that exhibit quantum
oscillations include the resistivity (the Shubnikovde Haas effect) and even the size of the
sample.
We now calculate the thermodynamic potential 0 (T, V, ), of a two-dimensional slice of
area Lx Ly , for a noninteracting metal in a strong magnetic field. We will work in the grand
canonical ensemble. Although we focus attention on a single slice through the Fermi surface,
this will give us great insight into the behaviour of a three-dimensional metal. While the
oscillatory contributions from different Fermi-surface slices will in general add out of phase,
the regions near extremal cross sections of the Fermi surface will add coherently and will
resemble what we calculate for a single slice.
0 (T, V, ) = kB T
ln 1 + e(n )
(18.32)
n=0
To demonstrate the effect we carry out the calculation in the zero temperature limit. If
n < ,

ln 1 + e(n ) ( n ) as .
(18.33)
On the other hand if n > ,

lim ln 1 + e(n ) = ln 1 = 0.
(18.34)
18.5. QUANTUM OSCILLATIONS AS A FERMI SURFACE PROBE
145
As a result,
0
0 (T = 0, V, ) =
n
X
(n ),
(18.35)
n=0
where the sum runs over all levels of energy less than the chemical potential . In a high
magnetic field the energy levels are Landau levels n = (n + 1/2)~c and these are p-fold
degenerate, where p = /0 . p can be made arbitrarily close to an integer by going to the
limit of large sample size. The number of Landau levels required to hold N electrons of one
spin will be N/p.
0

n
X
1
0 (T = 0, V, ) = p
(n + )~c .
2
n=0

=
N
p
(18.36)

1,
(18.37)
1
= (n0 + 1 + )~c .
2
(18.38)
The highest Landau level is only partly occupied, but makes no contribution to the thermodynamic potential. In any real situation we will be at a finite temperature, and will be able
to tune this partial occupancy by placing just below the highest filled Landau level.
0

n
X
1
1
0
(n + ) (n + 1 + ) ~c
0 (T = 0, V, ) = p
2
2
n=0
p~c 0
(n + 1)(n0 + 2)
2

e2
N
2 N
=
Lx Ly B
+1 .
4m
p
p
N 0
B0
Ak h
N
=
=
, B0 = 2
p
B
4 e
(18.39)
(18.40)
(18.41)
(18.42)
Ak is the k-space area of the two-dimensional slice. Putting this together, the thermodynamic
potential per unit area for one spin is

2

Ak h
0 (T = 0, V, )
e2
1
2 1
=
b
+ 1 , where b = B/B0 .
(18.43)
Lx Ly
4m 4 2 e
b
b
0 (T = 0, V, ) is plotted in Fig. 18.2 as a function of B. The function is periodic in 1/B,
which can be seen clearly in Fig. 18.3. Figure 18.4 shows de Haasvan Alphen data on the
layered oxide metal SrRu2 O4 , from experiments by Mackenzie and coworkers[14]. These data
have been used by Bergemann et al.[15] to constuct the Fermi surface shown in Fig. 18.5.
146
(arb. units)
0.2
0.4
0.6
0.8
1.2
B/B0
1.4
-1
-2
Figure 18.2: Thermodynamic potential plotted vs B in units of B0 = Ak 0 /8 2 . ((B)

b2 b1/bcb1 + 1/bc, b = B/B0 ).
(arb. units)
10
15
20
25
B0/B
-1
-2
Figure 18.3: Thermodynamic potential plotted vs 1/B, revealing that the cusps are evenly
spaced in inverse field.
18.5. QUANTUM OSCILLATIONS AS A FERMI SURFACE PROBE
147
0.03
15
16
Field (T)
17
18
0.00
10
DHvA Frequency (kT)
18.64 kT
6.09 kT
0.01
12.58 kT
12.88 kT
0.02
2.93 kT
Amplitude Spectrum (a.u.)
3.09 kT
0.04
15
20
Figure 18.4: Quantum oscillations of the magnetization in SrRu2 O4 , showing the Fourier
transform with respect to inverse field. (After Mackenzie et al.[14])
Figure 18.5: The Fermi surface of SrRu2 O4 inferred from the angle dependence of the de
Haasvan Alphen amplitudes. (After Bergemann et al.[15])
148
Lecture 19
Electronic structure of selected metals
In some materials, electron correlations effects are weak and the electronic structure is well
described by the nearly free-electron model. This occurs when the electron density is high,
for two reasons. First, the electrostatic screening length is short, so the screened potentials
of the ion cores are weak. Second, at high electron densities the kinetic energy is much
more important than the electronelectron interaction energy. We now make a brief survey
of the periodic table and look at metallic elements in which the electrons can be treated as
independent particles.
19.1
Construction of free-electron Fermi surfaces
We begin with a recapitulation of the construction of free-electron Fermi surfaces in two

dimensions.
19.1.1
Free-electron Fermi surfaces in two dimensions
The recipe for creating free electron Fermi surfaces in 2D is as follows:

Begin with the reciprocal lattice vectors G. Their perpendicular bisectors define the
Bragg planes, which in turn divide reciprocal space into Brillouin zones, as shown in
Fig. 19.1.
Draw a free-electron Fermi circle of radius kF corresponding to the desired electron
density n, as shown in Fig. 19.2a. The effects of a weak periodic potential can be
taken into account by curving the sections of arc to meet the Bragg planes at right
angles.
Filled zones are inert.
Pieces of the higher Brillouin zones are mapped back into the first Brillouin zone on
translation by reciprocal lattice vectors. This is shown in Figs. 19.2b and 19.2c for the
second and third zones respectively.
149
150
LECTURE 19. ELECTRONIC STRUCTURE OF SELECTED METALS
(A)
(B)
2
3
2
3
3
2
Figure 19.1: Bragg planes and Brillouin zones in two dimensions. (From M. P. Marder[5].)
The same result can be achieved using the Harrison construction, shown in Figs. 19.2d.
The Fermi surface pieces are intersections of circles of radius kF .
19.1.2
Free-electron Fermi surfaces in three dimensions
Similar constructions are used to obtain free-electron Fermi surfaces in three dimensions. In
this case the separate pieces are formed by the intersections of spheres. The convention is
to plot each Fermi-surface sheet separately. This is usually carried out in the reduced zone
scheme, as shown in Fig. 19.3 for the face-centred cubic structure.
Figure 19.4 shows the free-electron Fermi surfaces for the face-centred cubic structure, for
materials with one, two and three electrons per unit cell. Figure 19.5 does the same for the
body-centred cubic structure. Figure 19.6 shows the Fermi surfaces for the hexagonal closest
packed structure for two and four electrons per unit cell. In the hcp structure, in the absence
of spinorbit coupling, there is no first-order band gap along the (001) Bragg planes. For the
lighter elements, it is therefore customary to draw the Fermi surface in an enlarged Brillouin
zone with the (001) planes removed.
19.1. CONSTRUCTION OF FREE-ELECTRON FERMI SURFACES
(A)
(B)
(C)
(D)
151
Figure 19.2: Constructing the two dimensional Fermi surface. The free-electron circle (A)
extends into the second (B) and third (C) Brillouin zones. (D) The Harrison construction.
(From M. P. Marder[5].)
152
Brillouin zone
Extended zone scheme
Reduced zone scheme
Empty
Empty
First
Second
Third
Figure 19.3: Free-electron Fermi spheres for the face-centred cubic structure in the extended
(left) and reduced (right) zone scheme. The Fermi surface shown here holds three electrons
per unit cell. (From M. P. Marder[5].)
Brillouin
1 electron/cell
2 electrons/cell
3 electrons/cell
zone
First
Second
Third
Figure 19.4: Free electron Fermi surfaces for the face-centred cubic structure for one, two
and three electrons per unit cell. (From M. P. Marder[5].)
Brillouin
1 electron/cell
2 electrons/cell
153
3 electrons/cell
zone
First
Second
Third
Fourth
Figure 19.5: Free electron Fermi surfaces for the body-centred cubic structure for one, two
and three electrons per unit cell. (From M. P. Marder[5].)
Brillouin
2 electrons/cell
zone
4 electrons/cell
4 electrons/cell
with hcp extinction
First
Second
Third
Fourth
Figure 19.6: Fermi surfaces for the hexagonal closest-packed structure for one, two, three and
four electrons per unit cell, and with the (001) Bragg plane removed. (From M. P. Marder[5].)
154
Atomic name
Atomic number and symbol
S ILICON
Atomic weight (12 C=12)

Density in 1022 atoms cm
u 28 09
n 4 99
[Ne]3s2 3p2
14 Si
Ground state electron configuration
T 1683
1 105
a 5 43
Electrical resistivity in
3,
at 293K or at melting
-cm at 298 K

Lattice parameters
Alk
ali
Me
tals
Melting temperature in K
Crystal structure, either at 293 K, or at
melting if liquid at 293 K
Ia
IIa
L ITHIUM
u 6 94
n 4 63
3 Li
1s2 2s1
T 454
8 55
a 4 38
Metal
Insulator
Semi-metal
Semiconductor
B ERYLLIUM
4 Be u 9 01
n 12 36
1s2 2s2
40
T 1551
a 2 29
c 3 58
S ODIUM
M AGNESIUM
11 Na u 22 99
n 2 54
12 Mg u 24 31
n 4 31
[Ne]3s1
T 371
42
a 3 77
c 6 15
[Ne]3s2
T 922
4 45
a 3 21
c 5 21
Transition Metals
VIb
VIIb
IIIb
IVb
Vb
VANADIUM
u 50 94
23 V n 7 22
[Ar]3d 3 4s2
T 2160
24 8
a 3 02
VIIIb
P OTASSIUM
19 K u 39 10
n 1 33
[Ar]4s1
T 337
6 15
a 5 33
C ALCIUM
20 Ca u 40 08
n 2 33
[Ar]4s2
T 1112
3 43
a 5 59
S CANDIUM
u 44 96
21 Sc n 4 00
[Ar]3d 1 4s2
T 1814
61 0
a 3 31
c 5 27
T ITANIUM
u 47 88
22 Ti n 5 70
[Ar]3d 2 4s2
T 1933
42 0
a 2 95
c 4 68
RUBIDIUM
37 Rb u 85 47
n 1 08
[Kr]5s1
T 312
12 5
a 5 62
S TRONTIUM
38 Sr u 87 62
n 1 75
[Kr]5s2
T 1042
23 0
a 6 08
Y TTRIUM
u 88 91
39 Y n 3 03
[Kr]4d 1 5s2
T 1795
57 0
a 3 65
c 5 73
Z IRCONIUM
u 91 22
40 Zr n 4 30
[Kr]4d 2 5s2
T 2125
42 1
a 3 23
c 5 15
C ESIUM
BARIUM
L UTETIUM
H AFNIUM
TANTALUM
T UNGSTEN [W OLFRAM ] R HENIUM
O SMIUM
u 174 97
u 178 49
u 190 2
u 180 95
u 186 20
u 183 85
73 Ta n 5 54
75 Re n 6 80
76 Os n 7 15
74 W n 6 32
71 Lu n k3 39 72 Hf n 4 49
[Xe]4 f 14 5d 2 6s2
[Xe]4 f 14 5d 3 6s2
[Xe]4 f 14 5d 1 6s2
[Xe]4 f 14 5d 4 6s2
[Xe]4 f 14 5d 5 6s2
[Xe]4 f 14 5d 6 6s2
55 Cs u 132 91 56 Ba u 137 33
n 0 85
n 1 57
[Xe]6s1
T 302
20 0
a 6 14
[Xe]6s2
T 1002
50
a 5 03
n 1 33
[Rn]7s2
T 973
100
a 5 15
[Kr]4d 4 5s1
T 2741
12 5
a 3 30
[Kr]4d 5 5s1
T 2890
52
a 3 15
[Kr]4d 5 5s2
T 2445
22 6
a 2 74
c 4 40
[Ar]3d 7 4s2
T 1768
6 24
a 3 54
[Ar]3d 8 4s2
T 1726
6 84
a 3 52
RUTHENIUM
R HODIUM
PALLADIUM
u 101 07
u 102 91
u 106 42
45 Rh n 7 26
46 Pd n 6 80
[Kr]4d 7 5s1
[Kr]4d 8 5s1
[Kr]4d 10 5s0
T 2583
76
T 2239
4 51
T 1825
10 8
a 2 71
a 3 80
a 3 89
c 4 28
44 Ru n 7 37
I RIDIUM
P LATINUM
u 192 22
u 195 08
78 Pt n 6 62
n 7 07
[Xe]4 f 14 5d 7 6s2
[Xe]4 f 14 5d 10 6s0
T 2683
53
T 2045
10 6
a 3 84
a 3 92
77 Ir
T 3269
RUTHERFORDIUM
D UBNIUM
S EABORGIUM
B OHRIUM
H ASSIUM
M EITNERIUM
104 Rf
105 Db
106 Sg
107 Bh
108 Hs
109 Mt
T 3327
8 12
a 2 73
c 4 32
a 3 30

T 3453
19 3
a 2 76
c 4 46
T 2503
35 1
a 3 19
c 5 05
T 3680
5 65
a 3 17
12 45
43 Tc n 7 00
[Ar]3d 6 4s2
T 1808
9 71
a 2 87
T ECHNETIUM
u 98 91
42 Mo n 6 41
L AWRENCIUM
u 260
103 Lr n
[Rn]5 f 14 6d 1 7s2
M OLYBDENUM
u 95 94
41 Nb n 5 55
88 Ra u 226 03
N IOBIUM
u 92 91
R ADIUM
u 58 69
28 Ni n 9 13
N ICKEL
u 58 93
27 Co n 9 09
F RANCIUM
87 Fr u 223
n
[Rn]7s1
T 300
u 55 85
26 Fe n 8 48
C OBALT
I RON
M ANGANESE
u 54 94
25 Mn n 8 15
[Ar]3d 5 4s2
T 1517
185 0
a 8 91
T 1936
79 0
a 3 50
c 5 55
C HROMIUM
u 52 00
24 Cr n 8 32
[Ar]3d 5 4s1
T 2130
12 7
a 2 88

L ANTHANUM
C ERIUM
P RASEODYMIUM
N EODYMIUM
P ROMETHIUM
u 140 12
u 138 91
u 140 91
u 144 24
u 145
59 Pr n 2 89
58 Ce n 3 54
60 Nd n 2 93
61 Pm n 3 00
[Xe]4 f 2 5d 0 6s2
[Xe]4 f 3 5d 0 6s2
[Xe]4 f 4 5d 0 6s2
[Xe]4 f 5 5d 0 6s2
[Xe]5d 1 6s2
57 La n 2 67
Lanthanides
[Rare Earths]
T 1194
57
a 3 77
c 1 22
T 1072
73
a 4 85
Actinides
T 1294
64 0
a 3 66
c 11 80
T 1441
a
50
S AMARIUM
E UROPIUM
u 150 36
u 151 97
63 Eu n 2 08
[Xe]4 f 6 5d 0 6s2
[Xe]4 f 7 5d 0 6s2
62 Sm n 3 01
T 1350
94 0
a 9 00
23 13
T 1095
90 0
a 4 58
A CTINIUM
T HORIUM
P ROTACTINIUM
U RANIUM
u 227 03
u 232 04
u 238 03
u 231 04
90 Th n 3 04
91 Pa n 4 34
92 U n 4 79
[Rn]5 f 0 6d 2 7s2
[Rn]5 f 2 6d 1 7s2
[Rn]5 f 3 6d 1 7s2
[Rn]6d 1 7s2
89 Ac n 2 67
T 1204
68
a 3 67
c 11 83
N EPTUNIUM
P LUTONIUM
A MERICIUM
u 243
93 Np u 237 05 94 Pu u 244
n 5 14
n 4 89
95 Am n 3 39
[Rn]5 f 4 6d 1 7s2
[Rn]5 f 7 6d 0 7s2
[Rn]5 f 6 6d 0 7s2
T 914
146
T 1320
a 5 31
13 0
T 2023
a 5 08
17 7
T 2113
a 3 93
c 3 24
T 1406
30 8
a 2 85
b 5 86
c 4 95

T 913
122
a 4 72
b 4 89
c 6 66

a 6 18
b 4 82
c 10 96
101 48

68
T 1267
a 3 47
c 11 24
Figure 19.7: The periodic table showing crystal structures at room temperature. (From
M. P. Marder[5].)
fcc:
bcc:
rhombohedral:
tetragonal:
hcp:
cubic:
orthorhombic:
monoclinic:
155
H YDROGEN
H ELIUM
u 4 003
u 1 008
2 He n 3 11
n 4 54
2
1s
1
1s
T 14 01
At 2 K, 26 atm
a 3 77
a 3 53
c 6 16
c 4 24
1H
hexagonal:
diamond:
IIIa
IVa
B ORON
u 10 81
5B
n 13 03
1s2 2s2 2p1
T
2573

1 8 1012
a 8 74
c 5 06
Va
C ARBON
VIa
u 12 01
n 17 59
1s2 2s2 2p2
N ITROGEN
u 14 01
7N
n 4 43
1s2 2s2 2p3
T 3820
1019
a 3 57
T 63 29
a 5 64
6C
No
b
Ha
lo
g en
le G
ase
VIIa
VIIIa
u 16 00
n 7 53
1s2 2s2 2p4
F LUORINE
u 19 00
9F
n
1s2 2s2 2p5
T 54 8
a 6 83
T 53 5
a 6 67
O XYGEN
8O
1s2 2s2 2p6

u 20 18
n 4 30
10 Ne
T 24 5
a 4 45
N EON
tals
me
A LUMINUM
u 26 98
13 Al n 6 02
ble
S ILICON
15 P
T 1683
1 105
a 5 43
T 317
No
[Ne]3s2 3p1
T 934
Ib
IIb
2 65
a 4 05
P HOSPHORUS
u 30 97
n 3 54
2
[Ne]3s 3p3
u 28 09
n 4 99
[Ne]3s2 3p2
14 Si
1 1017
a 18 51
S ULFUR
u 32 07
n 3 89
2
[Ne]3s 3p4
16 S
T 386
Z INC
u 63 55
G ALLIUM
u 69 72
u 65 39
G ERMANIUM
u 72 61
A RSENIC
2 1023
T 172
a 10 46
b 12 87
c 24 49
C OPPER
C HLORINE
u 35 45
n 3 45
2
[Ne]3s 3p5
17 Cl
u 74 92
u 39 95
[Ne]3s2 3p6
T 83 8
a 5 31
a 6 24
b 4 48
c 8 26
S ELENIUM
u 78 96
A RGON
18 Ar n 2 50
B ROMINE
u 79 90
K RYPTON
u 83 80
29 Cu n 8 49
30 Zn n 6 56
31 Ga n 5 10
32 Ge n 4 41
33 As n 4 64
34 Se n 3 65
35 Br n 3 05
36 Kr n 2 03
[Ar]3d 10 4s1
T 1357
1 67
a 3 61
[Ar]3d 10 4s2
T 693
5 92
a 2 66
c 4 95
[Ar]3d 10 4s2 4p1
[Ar]3d 10 4s2 4p2
[Ar]3d 10 4s2 4p3
[Ar]3d 10 4s2 4p4
[Ar]3d 10 4s2 4p5
[Ar]3d 10 4s2 4p6
T 303
27
C ADMIUM
u 112 41
47 Ag u 107 87 48 Cd n 4 63
n 5 86
10
1
10
[Kr]4d 5s
[Kr]4d 5s2
T 1235
1 59
T 594
6 83
a 4 09
a 2 98
c 5 62
4 6 107
a 5 66
T 1090
26
a 4 13
54 10
T 490
1 106
a 4 37
c 4 96
T 266
T 429
8 37
a 3 23
c 4 94
T 505
11 0
a 5 83
c 3 18
T 904
81 Tl
n 4 07
[Xe]4 f 14 5d 10 6s2
T 1338
2 35
a 4 08
T 234
u 207 2
n 3 30
[Xe]4 f 14 5d 10 6s2 6p1
94 1
a 2 99
70 45
T 577
18 0
a 3 46
c 5 53
[Xe]4 f 14 5d 10 6s2 6p2
T 601
39 0
a 4 51
57 7
723
20 65
a 4 95
387
a 4 46
c 5 93
B ISMUTH
P OLONIUM
u 208 98
u 209
84 Po n 2 68
n 2 81
83 Bi
[Xe]4 f 14 5d 10 6s2 6p3
T 545
4 36 105
106 8
a 4 75
57 14
[Xe]4 f 14 5d 10 6s2 6p4
T 527
140
a 3 35
1 3 1015
a 7 26
b 4 79
c 9 79
T 161
a 6 19
A STATINE
u 210
85 At n
R ADON
u 222
86 Rn n
[Xe]4 f 14 5d 10 6s2 6p5
T 575
[Xe]4 f 14 5d 10 6s2 6p6
T 202
T HALLIUM
L EAD
u 204 38
82 Pb
n 3 49
M ERCURY
[Xe]4 f 14 5d 10 6s1
80 Hg u 100 59
u 196 97
a 5 72
T IN
G OLD
T 117
T ELLURIUM
I ODINE
X ENON
A NTIMONY
u 118 71
u 114 82
u 131 29
u 126 91
u 121 75
u 127 60
49 In n 3 83
52 Te n 2 94
53 I
54 Xe n 1 62
50 Sn n 3 71
51 Sb n 3 31
n 2 34
10
2
1
10
2
2
10
2
3
10
2
4
10
2
5
10
[Kr]4d 5s 5p
[Kr]4d 5s 5p
[Kr]4d 5s 5p
[Kr]4d 5s 5p
[Kr]4d 5s 5p
[Kr]4d 5s2 5p6
79 Au n 5 90
a 6 74
b 4 55
c 8 76
I NDIUM
S ILVER
T 1211
a 4 52
b 7 66
c 4 53
G ADOLINIUM
T ERBIUM
H OLMIUM
E RBIUM
T HULIUM
Y TTERBIUM
DYSPROSIUM
u 173 04
u 157 25
u 164 93
u 167 27
u 158 93
66 Dy u 162 50 67 Ho n 3 21
65 Tb n 3 12
68 Er n 3 26
69 Tm u 168 93 70 Yb n 2 42
n 3 17
n 3 32
[Xe]4 f 7 5d 1 6s2
[Xe]4 f 9 5d 0 6s2
[Xe]4 f 10 5d 0 6s2
[Xe]4 f 11 5d 0 6s2
[Xe]4 f 12 5d 0 6s2
[Xe]4 f 13 5d 0 6s2
[Xe]4 f 14 5d 0 6s2
64 Gd n 3 02
T 1586
134
a 3 64
T 1629
114
a 3 59
b 6 26
c 5 72
C URIUM
u 247
96 Cm n 3 24
[Rn]5 f 7 6d 1 7s2

T 1610
C ALIFORNIUM
u 251
98 Cf n
[Rn]5 f 10 6d 0 7s2

E INSTEINIUM
u 254
99 Es n
[Rn]5 f 11 6d 0 7s2

a
?
T 1747
87 0
a 3 58
c 5 62
T 1802
87
a 3 56
c 5 59
T 1818
79 0
a 3 54
c 5 55
29 0
T 1097
a 5 49
B ERKLIUM
u 247
97 Bk n 3 60
[Rn]5 f 9 6d 0 7s2
T 1685
57 0
a 3 59
c 5 65
F ERMIUM
u 257
100 Fm n
[Rn]5 f 12 6d 0 7s2

M ENDELEVIUM
u 258
101 Md n
[Rn]5 f 13 6d 0 7s2

N OBELIUM
u 259
102 No n
[Rn]5 f 14 6d 0 7s2
T
Figure 19.8: The periodic table showing crystal structures at room temperature. (From
M. P. Marder[5].)
156
19.2
The alkali metals
The alkali metals crystallize in the body-centred cubic structure, although lithium and
sodium undergo low-temperature structural phase transitions. The alkali atoms contribute
one outer electron to the conduction band, with the remaining electrons tightly bound in the
ion cores. The core electrons give rise to flat bands that can be ignored when calculating the
electronic structure and Fermi surface. With one electron per atom, the Fermi wavevector
is given by
2
kF3
=n= 3
(19.1)
2
3
a
where the factor of 2 is due to the fact that a is the side of the conventional cubic unit cell,
which holds two atoms. kF = 0.620(2/a), which is less than the distance from the origin
to the nearest Bragg plane, kmin = 0.707(2/a). The Fermi sphere is confined to the first
Brillouin zone. Figure 19.9 shows a pseudopotential band-structure for sodium. (No core
states are included.) The Fermi energy is the dashed line, and falls entirely within the first
band. The Fermi surface, shown in Fig. 19.10, is spherical to within 0.1%.
Figure 19.9: Band structure of sodium. (From D. A. Papaconstantopoulos[16].)

The effective masses m of the alkali atoms Li, Na, K, Rb and Cs are 1.33, 0.97, 0.86, 0.78 and
0.73 electron masses respectively, very close to the free electron value. We can understand
this progression from the second-order perturbation theory result
m
2 X |hn|P |n0 i|2
=
1
+
.
m
m n0 6=n En0 En00
(19.2)
19.3. THE NOBLE METALS
157
Figure 19.10: First Brillouin zone of the body-centred cubic structure, showing a monovalent
Fermi surface. (From Ashcroft and Mermin[4].)
Mixing with states higher in energy acts to increase the effect mass, and coupling to lower
energy states has the opposite effect. For Li there are no lower energy states, so the mass
must increase.
Figure 19.11: The Fermi surface of copper showing neck and belly extremal orbits on the
left, and the dog-bone orbit on the right. (From Ashcroft and Mermin[4].)
19.3
The noble metals
The noble metals are Cu, Ag and Au. The electronic structure of copper ([Ar]3d10 4s1 ) differs
from that of potassium ([Ar]4s1 ) by a filled d shell. The closed-shell argon configuration
158
Figure 19.12: Band structure of copper[17].
leads to filled inert bands in both Cu and K. In the case of potassium the extra electron is
accommodated by half filling a free-electron like band. In copper (and silver and gold) the
d electrons are not so tightly bound to the atom that they can be considered as part of the
core six bands are required to accommodate the eleven additional electrons. We expect
to find a broad s band and a narrow d band, and these bands overlap and hybridize. The
mixing can be seen in the band structure of copper shown in Fig. 19.12. The result of the
hybridization is to lower the energy of the s band near the L point in the Brillouin zone.
This has an important effect on the Fermi surface topology, which now necks out to touch
the edge of the Brilluoin zone. The open Fermi surface can be seen in Fig. 19.11.
19.4
Divalent metals
The alkaline earth metals (column two of the periodic table) are divalent. There are two
electrons in the outer shell, which form the conduction band. The Fermi surface must
therefore have the same volume as the first Brillouin zone. Since the materials are metals,
the Fermi surface occupies the first and second Brillouin zones and is now quite complicated.
The band structure of calcium is shown in Fig. 19.14.
Be, Mg, Zn and Cd crystallize in the hexagonal closest packed structure. Beryllium is the
lightest and has the weakest spinorbit coupling. It has the enlarged Brillouin zone shown
in Fig. 19.6 and the Fermi surface shown in Fig. 19.13.
19.4. DIVALENT METALS
159
Figure 19.13: Fermi surface of beryllium[18].
Figure 19.14: Band structure of calcium. (From D. A. Papaconstantopoulos[16].)
160
19.5
The trivalent and tetravalent metals
The simplest trivalent metal is aluminium. It crystallizes in the face centred cubic structure
and has the Fermi surface shown in Fig. 19.15. The simplest tetravalent metal, lead, also
crystallizes in the fcc structure, shown in Fig. 19.16.
Figure 19.15: Fermi surface of aluminium[19].
19.6. TRANSITION METALS
161
Figure 19.16: Free electron Fermi surfaces for the face-centred cubic structure, with the third
zone Fermi surface sheet of Pb shown on the right.
19.6
Transition metals
The transition metals cannot be described by the nearly free electron model due to strong
correlations in the flat, partially filled d bands. We will discuss these electron correlation
effects in the next lecture. A periodic table showing Fermi surfaces for the metallic elements
can be downloaded from http://www.phys.ufl.edu/fermisurface . These Fermi surfaces
were calculated from tight-binding parameterizations of more accurate band structure calculations.
162
Lecture 20
Strongly correlated electron systems
& semiconductors
In the last lecture we discussed the elemental metals that can be described by the nearly
free electron theory. In the materials in which it applies, the success of the theory is nearmiraculous, with many Fermi surfaces instantly recognizable as reconstructed pieces of a
free-electron sphere.
We begin this lecture by looking at a number of materials in which the independent electron
approximation breaks down. These are materials in which the energy of electronelectron
interaction is comparable to or greater than the kinetic energy1 . We call these materials
strongly correlated electron systems. The consequences of the more delicate balance between
kinetic and potential energy are to form magnetic states, or for a band-metal2 to become
an insulator.
20.1
Interactions and the Hubbard U
A discussion of strongly correlated electron systems requires a localized tight-binding description of the electronic structure. The kinetic energy is of order t, the nearest neighbour
overlap integral. The dominant term in the electronelectron repulsion comes from two
electrons occupying the same site. This is called the Hubbard U , where
Z Z
1
1
e2
dr dr0 |(r)|2 |(r0 )|2
.
(20.1)
U=
2
40 |r r0 |
Kinetic and potential terms work against each other. Imagine starting with a simple solid
of N sites that has one electron and one orbital per site. We form extended states by
1
By kinetic energy we mean the bandwidth of the electronic states, which is proportional to the overlap
integral t between neighbouring atoms. The kinetic energy is then measured from the bottom of the band
and does not include the contribution from the electrons motion in the nuclear potential.
2
A band metal is a material that independent electron band theory predicts to be a metal. In particular,
band theory predicts that any material with an odd number of electrons per unit cell should be a metal,
because it will be unable to completely fill all the occupied Brillouin zones in order to become an insulator.
163
164
LECTURE 20. STRONGLY CORRELATED SYSTEMS & SEMICONDUCTORS

D()
D()
LHB
UHB
Figure 20.1: The density of states D() is sketched for the case t U (left) and t U
(right). When the Hubbard U is strong enough, it splits the conduction band into upper
(UHB) and lower (LHB) Hubbard bands, driving a metalinsulator transition.
making linear combinations of the atomic orbitals, which lowers the kinetic energy by order
t. The potential energy increases by U , because the probability of double occupancy in
the extended state is 21 .3 If t U , the extended state will have the lower energy. In the
opposite limit, t U , it is energetically favourable to localize the electrons, because this
will make the probability of double occupancy zero. The resulting state is an insulator, with
an energy gap U for charge excitations. The transition from extended to localized states is
called the Mott transition. Figure 20.1 shows a schematic of the MottHubbard density of
states.
20.2
Measuring the Hubbard U

+e
+2e
+e
+2e
e2
initial kinetic energy
0 a0
I1
I2
1 2e2
initial kinetic energy
4 0 a0
Figure 20.2: An illustration of the ionization processes that occur when measuring the first
and second ionization potentials. The ionization energy is the Coloumb energy required to
separate the electron from the positive ion, minus the initial kinetic energy of the electron.
Imagine carrying out the following experiment, depicted in Fig 20.2. Take a neutral atom.
3
To calculate the probability of double occupancy, note that in the extended state the probability of any
one electron being at a particular site is 1/N . There are N ways to choose the first electron at a site but,
once it has been chosen, Pauli exclusion requires that the second electron have opposite spin. There are then
only N/2 ways of choosing the second electron.
20.3. 3D TRANSITION METALS
165
Then measure the energy required to excite a bound electron and move it to infinity, leaving
behind a singly charged positive ion. (This experiment is carried out using photo-electron
spectroscopy at x-ray wavelengths.) The excitation energy is the first ionization potential I1 ,
and is equal to the Coulomb energy required to separate an electron from the positive ion,
minus the initial kinetic energy of the electron. Now remove a second electron and move it to
infinite separation. This is the second ionization potential I2 , given by the energy required
to separate an electron from a doubly charged ion, minus the initial kinetic energy. Due
to the double charge on the ion, I2 is larger than I1 . In fact, neglecting details about the
kinetic energy, the difference I2 I1 is just the Coulomb energy of two electrons separated
by distance a0 .
We have seen this problem before in a different guise. Imagine a highly simplified model of
an atom, in which we have one orbital that can be at most doubly occupied.
X
atom = 0 +
H
1 n
+ U n
n
,
(20.2)
where n
is the number operator and is the spin projection. The energies for zero, single
and double occupancy are
E(0) = 0
E(1) = 0 + 1
E(2) = 0 + 21 + U
(20.3)
(20.4)
(20.5)
U = E(0) + E(2) 2E(1)

= E(2) E(1) E(1) E(0)
(20.6)
(20.7)
Rearranging, we see that
If we identify E(2) E(1) with I2 and E(1) E(0) with I1 , we see that the Hubbard U is
just the difference between the first and second ionization potentials. The quantum particles
in the hamiltonian above are really holes, which are the elementary excitations of charge
removal.
20.3
3d transition metals
The 3d transition metals range from Sc to Zn. They are characterized by the gradual filling
of the d shell, going from scandium ([Ar]3d1 4s2 ) to zinc ([Ar]3d10 4s2 ). The argon-like core is
highly localized and plays no role in determining the physical properties of the solid. The 4s
orbitals are filled before the 3d orbitals, because the 4s states have a larger amplitude at the
nucleus and therefore experience a higher effective charge. However, for Cr ([Ar]3d5 4s1 ) and
Cu ([Ar]3d10 4s1 ) the stability of a filled or half-filled d shell partially empties the s state.
The 4s electrons extend away from the atomic core, in order to maintain orthogonality with
the 1s, 2s and 3s electrons. The 3d electrons have no such need and are much more highly
localized. They therefore overlap very little with d electrons on neighbouring atoms and the
effects of Coulomb repulsion are of much greater importance relative to the bandwidth. The
166
predominant effect of Coulomb repulsion in the 3d elements is the ferromagnetic alignment

of spins on the same atom (Hunds rule). In principle, the Coulomb repulsion could also
force the d electrons to localize and the d band to split into as many as 10 separate Hubbard
bands. Instead, the effective Coulomb repulsion between the 3d electrons is reduced by the
screening effects of electrons in other bands, especially the 4s. To see how this works, lets
try to estimate U for the Cu2+ or Ni+ configurations, which have the electronic configuration
3d9 s0 .
U = I2 I1

= E(3d8 ) E(3d9 ) E(3d9 ) E(3d10 )

= E(3d10 ) + E(3d8 ) 2E(3d9 )
(20.8)
(20.9)
(20.10)
This is the energy of the transition

2(3d9 ) 3d10 + 3d8 .
(20.11)
This works out to be about 13.5 eV, most of which is the Coulomb cost of a doubly-charged
ion versus two singly charged ions. In a solid this is an overestimate, because the s electrons
can relax to compensate for the charging of the ions. We should really consider the transition
2(3d9 4s1 ) 3d10 4s0 + 3d8 4s2 ,
(20.12)
which has an energy of only 1.8 eV. In transition metal oxides, however, the transition metal
ion is in a M+ or M2+ state, the 4s state is empty and, as a result, interatomic screening is
absent. Materials such as NiO or V2 O3 are the archetypical MottHubbard insulators.
20.4
Semiconductor structures
The semiconducting elements Si and Ge have the diamond structure, shown in Fig. 20.3.
This is a face-centred cubic (fcc) lattice, except that there are two atoms per primitive cell.
The first is at a corner of the fcc lattice, and the second is located 41 the way along the
main diagonal. Carbon, and one form of tin (grey tin) also adopt the diamond structure.
In the case of C (diamond), the energy gap is very large, approximately 5.5 eV, and the
structure is an excellent electrical insulator. In the case of grey tin, conduction and valence
bands touch at the centre of the Brillouin zone, making the material a semi-metal, although
the average energy gap is small and positive. In addition, tin can take two different crystal
structures, depending on the temperature. This reflects the fact that the diamond structure
becomes increasingly energetically unfavourable as we go down the fourth column of the
periodic table, for reasons we will discuss below. (Pb is a metal, and forms in a close-packed
structure.)
In contrast to metals, semiconductors are covalently bonded, with only four nearest neighbours at the corners of a tetrahedron, rather than the twelve of a close-packed metal. Instead
of lowering its energy by forming a high-density metallic state, cohesion in semiconducting
materials comes from directed bonding. In fact, we can think of a semiconductor crystal as
a giant molecule. This is borne out by detailed electronic structure calculations, which show
20.5. SEMICONDUCTOR CHEMISTRY
167
Figure 20.3: The diamond structure. (From Phillips[20].)
the valence charge concentrated along the bond directions. A number of binary compounds
with eight valence electrons per atom are also formed in tetrahedrally coordinated structures. These include the IIIV materials InSb and GaAs. Here the group III and group V
elements sit on separate, interpenetrating fcc lattices, in an arrangement called the zincblende
structure. If you look carefully at Fig. 20.3 you will notice that such a structure lacks inversion symmetry. IIVI compounds are also possible they start to have substantial ionic
character and are called polar semiconductors.
20.5
Semiconductor chemistry
For the group IV elements, the valence shell electronic structure is ns2 np2 , giving 4 electrons
per atom and 8 per primitive cell. We therefore need to fill 4 bands. (Each band holds 2
electrons per primitive cell.) Adopting a tight-binding approach, we can see how these bands
come from the four orbitals of the free atoms: the 3s and three 3p orbitals of Si, and the
4s and three 4p orbitals of Ge. Since we have two electrons per unit cell, our wavefunction
ansatz will consist of Bloch sums of 8 orbitals, giving a total of eight bands. We therefore
need to fill half the bands to accommodate the valence electrons.
In the theory of chemical bonds, the tetrahedral structure is well known. The s and p orbitals
can be combined to form a new basis set, the sp3 hybrids shown in Fig. 20.4, which point in
the direction of the vertices of a tetrahedron. (In the case of the diamond structure, pointing
in (half of) the h111i directions.) The lobes of these orbitals are directional and extend in
the direction of the nearest neighbours.
168
Figure 20.4: sp3 hybridization.
In a tight-binding description, our effective hamiltonian consists of atomic energies and twocentre overlap integrals of the form
Z
tij =
dr i (r)Va (r R)j (r R)
(20.13)
In the case of the tetrahedral diamond structure, the largest overlap integrals by far are
those between pairs of sp3 hybrids in which the lobe of each orbital points directly along
the bond to its neighbour. If we neglect all other terms in the tight-binding model, we
would have a hamiltonian that factors into pairs of noninteracting diatomic molecules. The
band structure would reflect the presence of these 2 2 sub-units in the hamiltonian: the
mixing of degenerate orbitals would give a splitting into bonding and antibonding orbitals.
There would then be four occupied bonding orbitals, split by a hybridization gap from
the four empty antibonding orbitals. However, there would be no dispersion because we
have neglected two things: the energy cost of promoting an s electron into a p state4
and the further hybridization or hopping between non-colinear orbitals. These extra effects
will broaden the bonding and antibonding orbitals into bands in the real material, but the
fundamental origin of the gap is chemical.
20.6. BONDING, NONBONDING AND ANTIBONDING STATES
169
Figure 20.5: Bonding and antibonding orbitals. (From Phillips[20].)
20.6
Bonding, nonbonding and antibonding states
This terminology comes up all the time in discussions of the electronic structure of real
materials, but is never properly explained in physics textbooks. It is therefore worth saying
a few words about it here.
A bonding orbital b (r) consists of a linear combination of two directed orbitals
i (r R) and j (r R0 ) associated with nearest neighbour atoms at sites R and
R0 , combined in phase in such a way that b (r) is large in the bonding region between
atoms.
An antibonding orbital a (r) is similar to a bonding orbital except the phase between
the two hybrid states has been reversed. Therefore a (r) has a node in the bonding
region.
A nonbonding orbital is usually centred on one atom and has little directional character.
Rules for bonding:
The number of independent hybridized orbitals is equal to the number of atomic orbitals.
4
As we will see below, the sp3 hybrids are not quite the right description. The energy of an s-state is
always lower than that of a p state: Ens < Enp . The s electrons penetrate closer to the nucleus than the
p electrons, and therefore feel the attractive core potential more. This energy separation increases as we go
down the periodic table, eventually destabilizing the sp3 hybrids.
170
Figure 20.6: The band structure of silicon. (From Phillips[20].)
In order of increasing energy one has bonding, nonbonding, and antibonding states.
Usually the first two groups are occupied, and the third group is not. The bonding
electrons have the lowest energy because they benefit most from the large attractive
potential produced by the overlap of the Coulomb potentials of the neighbouring atoms.
20.7
Electronic structure
The band structure of silicon is shown in Fig. 20.6. Silicon is an indirect-gap material. The
valence band maximum occurs at the point, k = 0. The conduction band minima lie along
the [100] directions, about 80% of the way to the zone boundary.
Because the properties of semiconductors are determined by relatively small number of electrons and holes, it is usual to focus attention on the levels near the bottom of the conduction
band, which hold electrons, and the levels near the top of the valence band, which will
20.7. ELECTRONIC STRUCTURE
171
Figure 20.7: Constant energy surfaces for the conduction band in a) germanium and b)
silicon. (From M. P. Marder[5].)
contain holes. The energy dispersions are well approximated by quadratic forms
(k) = c +

~2 X
k M1 k
2
electrons
(20.14)
(k) = v

~2 X
k M1 k
2
holes,
(20.15)
where k = (k k0 ) , and k0 is the location in k-space of the conduction band minimum

or valence band maximum. The effective mass tensor is real and symmetric, so it is always
possible to transform to orthogonal coordinates in which it is diagonal.

2
k22
k32
k1
2
+
+
(k) = c + ~
electrons
(20.16)
2m1 2m2 2m3
2

k1
k22
k32
2
+
+
holes
(20.17)
(k) = v ~
2m1 2m2 2m3
The constant energy surfaces are ellipsoidal in shape, with three different effective masses
in general. At the centre of the zone, cubic symmetry maps the different directions into one
another, so the mass tensor is isotropic and the constant energy surfaces spherical. Along
axes of high symmetry, the constant energy surfaces are typically cigar shaped, as shown for
silicon and germanium in Fig. 20.7.
20.7.1
Spinorbit coupling
In heavy atoms there is a strong spinorbit coupling interaction an operator of the form
L S. In free atoms this removes the degeneracy of some states with the same space
172
Figure 20.8: Sketch of the valence bands of diamond and zincblende structures showing the
dispersions with and without the spinorbit interaction. (From Phillips[20].)
wavefunction but opposite electron spin. For example, the 6 atomic p states are split into a
four-fold degenerate P3/2 multiplet and a P1/2 doublet.
When constructing energy bands we usually assume that spin is irrelevant. We just use
a wavefunction in space and for each k assume we can put in two electrons of opposite
spin. However, the spinorbit interaction can resolve this degeneracy. This is particularly
important at points in the Brillouin zone with high symmetry. In the fcc structure, the
point, k = 0, is a point of cubic symmetry. In the tight-binding model our wavefunctions
would consist of linear combinations of p orbitals, giving these bands a six-fold degeneracy
at the point, including spin degeneracy. In the presence of a spinorbit interaction, we
should have started with the four-fold degenerate P3/2 states and the two-fold degenerate
P1/2 states when constructing Bloch sums.
What happens as we move away from k = 0 depends on whether or not our crystal has
a centre of inversion symmetry. It it does, as in silicon and germanium, the spinorbit
interaction will not separate states of opposite spin because, in effect, reversing the spin in a
state k (r) is equivalent to looking at k (r), which has the same energy. The j = 23 band
therefore splits into a band with mj = 32 , and a band with mj = 12 . In a crystal that
lacks inversion symmetry, such as InSb, the bands split again as we move away from k = 0.
20.8
Other semiconductors
The band structures for germanium, another indirect-gap material, and GaAs, a direct-gap
semiconductor are shown in Figs. 20.9 and 20.10.
20.8. OTHER SEMICONDUCTORS
173
Figure 20.9: The band structure of germanium. (From Phillips[20].)
Figure 20.10: The band structure of GaAs. (From Phillips[20].)
174
Lecture 21
Semiconductors
21.1
Homogeneous semiconductors
The technological importance of semiconductors is due to the flexibility of their electrical

properties. For instance, the resistivity can be tuned from 105 .m to 107 .m by making
small changes to the dopant density. (These numbers can be compared to the resistivity
of typical metals, 108 .m and of insulators, where 1020 .m.) The high degree
of tunability is due to the extreme sensitivity of semiconductors to charged defects, and
this initially delayed a proper understanding of semiconductor materials until high-quality,
low-impurity single crystals could be produced. In good quality samples the resistivity is
strongly temperature dependent. This is a unique consequence of the way that charge carriers
in semiconductors are formed by thermally exciting electrons from the valence band into
the conduction band, which leaves behind holes in the valence band.
21.1.1
Carrier density in thermal equilibrium
Calculating the carrier density of a semiconductor in thermal equilibrium requires a straightforward application of Fermi statistics. Let nc be the number of electrons in the conduction
band and pv be the number of holes in the valence band. Although the density of carriers is
very sensitive to the presence of impurities, we start by considering the so-called intrinsic
regime, appropriate to highly pure material. It will turn out that at temperatures not too
far below room temperature, impurities just affect the position of the chemical potential .
Let Dc () be the conduction band density of states and Dv () be the valence band density
of states.
Z
nc (T ) =
d Dc ()f ()
Zc
d Dc ()
c
(21.1)
1

exp ( )/kB T + 1
175
(21.2)
176
LECTURE 21. SEMICONDUCTORS
D( )
acceptor states
donor states
valence band
conduction band
band gap
Figure 21.1: The density of states of a doped semiconductor.

v
Z
pv (T ) =
v
d Dv () [1 f ()]
"
(21.3)
1

=
d Dv () 1
exp ( )/kB T + 1
Z v
1

d Dv ()
=
exp ( )/kB T + 1
#
(21.4)
(21.5)
Impurities affect this picture by introducing defect states in the gap, as shown in Fig. 21.1.
Their presence can be used to tune the position of the chemical potential, which in most
cases still falls within the band gap, allowing us to write:
c kB T
v kB T.
(21.6)
(21.7)
When these assumptions hold, we have a nondegenerate semiconductor. When the assumptions break down, the semiconductor is said to be degenerate, and we need to solve Eqs. 21.2
and 21.5 numerically.
21.1.2
The nondegenerate case
In the nondegnerate case, the Fermi factors in Eqs. 21.2 and 21.5 can be approximated by
classical Boltzmann factors:
1

e()/kB T
(21.8)
exp ( )/kB T + 1
1

e()/kB T .
(21.9)
exp ( )/kB T + 1
We can then write
nc (T ) = Nc (T )e(c )/kB T
pv (T ) = Pv (T )e(v )/kB T ,
(21.10)
(21.11)
21.1. HOMOGENEOUS SEMICONDUCTORS
177
where
Z
Nc (T ) =
Zcv
Pv (T ) =
d Dc ()e(c )/kB T and
(21.12)
d Dv ()e(v )/kB T
(21.13)
are slowly varying functions of T . In the effective mass approximation these can be evaluated
directly. Using
q
3/2
mc,v
Dc,v () = 2| c,v | 3 2 ,
(21.14)
~
where m3c = det(Mc ) and m3v = det(Mv ), we have

3/2
1 2mc kB T
(21.15)
Nc (T ) =
4
~2

3/2
1 2mv kB T
Pv (T ) =
.
(21.16)
4
~2
Although the actual carrier densities are determined by , the product nc pv is independent
of :
nc pv = Nc Pv e(c v )/kB T
= Nc Pv eEg /kB T .
(21.17)
(21.18)
In the language of chemistry, this defines a law of mass action, in which the carriers are
formed by dissociation of electrons and holes. One consequence of Eq. 21.18 is that if we
know the density of one carrier type, we automatically know the other. In addition, as soon
as one carrier type begins to dominate, it will completely overwhelm the other.
21.1.3
The intrinsic case
In the intrinsic case the impurity concentration is neglible. Therefore

nc (T ) = pv (T ) = ni (T ),
(21.19)
where
ni (T ) =
p
Nc Pv eEg /2kB T .
(21.20)
For this to hold, we must have

= i
1
= v + Eg +
2
1
= v + Eg +
2

1
Pv
kB T ln
2
N
c
3
mv
kB T ln
.
4
mc
(21.21)
(21.22)
We can see that as T 0, goes to the middle of the gap. Since ln(mv /mc ) O(1), at
finite temperatures is typically located within several kB T of the middle of the gap, making
the degeneracy condition easy to satisfy.
178
21.1.4
The extrinsic case
In the presence of charged defects,

nc pv n 6= 0.
(21.23)
The law of mass action, Eq. 21.18, still holds, so

nc pv = n2i
= nc (nc n).
(21.24)
(21.25)
Therefore
nc
pv
q
n 1
+
n2 + 4n2i
=
2
2 q
n 1
=
+
n2 + 4n2i
2
2
(21.26)
(21.27)
(21.28)
This can be written in another way:
so that
nc = e(i ) ni
pv = e(i ) ni
(21.29)
(21.30)
n
= 2 sinh ( i ).
ni
(21.31)
When n is large compared to ni , the density of one type of carrier is n, and the density
of the other carrier type is smaller by a factor (ni /n)2 . One type of carrier dominates, and
we have either n-type or p-type material.
21.1.5
Impurities
Two types of impurity are essential to semiconductor electronics:

Donors these are impurities that are easily ionized and supply electrons to the
conduction band. In group IV semiconductors such as silicon and germanium, any
element from group V of the periodic table, such as phosphorous or arsenic, acts as
donor.
Acceptors these are impurities that readily capture an electron, effectively supplying
holes to the valence band. For silicon and germanium, group III elements such as boron
and gallium act as acceptors.
in a crystal, the binding energy of Bloch electrons at impurities is enormously reduced over
the binding energy of electrons in the free atom. This reduction occurs for two reasons:
21.1. HOMOGENEOUS SEMICONDUCTORS
179
The Coulomb attraction is reduced by the static dielectric constant r , which is typically
1020 in a semiconductor. (Large dielectric constants occur as a result of the small
energy gaps.)
An electron moving in a semiconductor medium has semiclassical dynamics, described
by the appropriate effective mass tensor. This is because the impurity level is built out
of Bloch states near the conduction band minimum or valence band maximum. To a
first approximation, m m , where m is an appropriate average of the components
of the effective mass tensor.
For a hydrogen atom in free space, the binding energy is
= me4 /32 2 20 ~2 .
(21.32)
In a crystal, the Bohr radius is increased:

m
A
r0 r a0 100
m
(21.33)
and the binding energy is reduced:

b =
m 1
13.6 eV,
m 2r
(21.34)
lowered by a factor of 1000 or more. The energy of a donor impurity is measured relative to
the energy of the conduction band levels from which it is formed:
d = c b .
(21.35)
A similar argument holds for acceptors, and the binding energies of both types of impurity
are small compared to the energy gap.
21.1.6
Population of impurity levels in thermal equilibrium
To calculate the effect of impurities on the density of carriers, we ignore the interaction of
electrons bound at different impurity sites.1 As discussed in Lecture 2, we usually assume
the each impurity has a single one-electron orbital that can hold electrons of either spin,
but not two electrons, due to their mutual Coulomb repulsion. In this case, the impurity
statistics have a modified FermiDirac form:
nd =
Nd
,
1 + exp (d )
(21.36)
1
2
where Nd is the density of donor atoms. The same is true for acceptors, which have an
average occupation number
Na
na =
,
(21.37)
1
1 + 2 exp ( a )
where Na is the density of acceptor impurities.
1
These interactions can be important at low temperatures where, for example, they can lead to the
impurity levels forming an impurity band through which electrical conduction occurs.
180
21.1.7
Thermal equilibrium carrier density
Consider the electronic configuration at T = 0. If Nd Na , then Na of the donated electrons

drop down into acceptor levels, leaving Nd Na electrons behind in the donor levels.
nc
pv
nd
pa
=
=
=
=
0
0
Nd Na
0
(21.38)
(21.39)
(21.40)
(21.41)
At finite T , the electrons are redistributed among the levels, but the total number remains
the same.
nc + nd pv pa = Nd Na = constant
(21.42)
We can use the expressions for nc , nd , pv and pa to find in terms of Nd and Na . The
general case is complicated, but the following simple case is quite important:
d kB T
a kB T .
(21.43)
(21.44)
In this case, the impurities are fully ionized, and n = nc pv = Nd Na . This approximation
will hold from the predominantly intrinsic regime to well into the extrinsic regime. Using
the expressions we found earlier, we get the following results in the two cases of n-type and
p-type doping.
n-type: Nd > Na
n c Nd Na
n2i
pv
Nd Na
(21.45)
(21.46)
p-type: Na > Nd
n2i
Na Nd
Na Nd
nc
(21.47)
pv
(21.48)
If the temperature is too low, or the impurity concentration too high, inequalities 21.43 and
21.44 fail, and one of the impurity types is no longer completely ionized.
21.1.8
Transport in nondegenerate semiconductors
The velocity distribution for carriers in the conduction or valence band of a semiconductor
is:
)
(
det(M)1/2
X
f (v) = n
exp
v M v .
(21.49)
(2kB T )3/2
2
21.2. INHOMOGENEOUS SEMICONDUCTORS
181
Compare this to the velocity distribution in a classical gas:

f (v) = n
m
2kB T
3/2

exp mv 2 /2kB T .
(21.50)
The two are very similar except that:

in a classical gas the density of molecules n is fixed and independent of temperature;
in a classical gas the effective mass is isotropic.
Other than that, transport in a nondegenerate semiconductor is the same as for a charged
classical gas with several components.
21.2
Inhomogeneous semiconductors
The sensitivity of semiconductor properties to defects permits the electronic structure to be

tuned on a small spatial scale, allowing the fabrication of devices such as quantum wells and,
using interfaces between n-type and p-type material, nonlinear devices such as diodes and
transistors. Here we are usually talking about single crystals in which the dopant densities
are spatially varying.
21.2.1
The p-n junction
We consider an abrupt junction, defined to be narrow compared to the depletion

which the carrier densities are nonuniform.
The doping profile is given by Nd (x) and Na (x). In the model p-n junction we
below, these take a simple form.

Nd , x > 0
Nd (x) =
0, x < 0

0, x > 0
Na (x) =
Na , x < 0
layer, in
consider
(21.51)
(21.52)
We assume we can treat the junction using the semiclassical model, where the effect of an
electric potential is to shift the one-electron levels. This is just what we assumed in the
ThomasFermi theory of screening. Here the approximation is much better justified because
the length scales, typically 100
A to 1000
A, are much larger than atomic dimensions.
In the general the change in e in crossing the junction is Eg but, as we will see below, this
occurs over at least 100 lattice constants. This will satisfy the electric breakdown condition
2
gap (k)
.
(21.53)
eEa
EF
derived in Lecture 17. It is convenient to do the same thing we did for the ThomasFermi
182
d (x)
v (x)
c (x)
a (x)
c
e (x)
d
v
Figure 21.2: Two views of the spatially varying electronic structure in a p-n junction.
theory and define a position-dependent electrochemical potential,

e (x) = + e(x).
(21.54)
Using the results from earlier, the equilibrium carrier densities are

c e (x)
nc (x) = Nc (T ) exp
kB T

e (x) v
pv (x) = Pv (T ) exp
.
kB T
(21.55)
(21.56)
As with the ThomasFermi theory, the potential (x) must be determined self-consistently
by solving Poissons equation, which we will now proceed to do.
When we are a long distance from the junction, uniform extrinsic conditions apply all
impurities are therefore fully ionized. The change in potential on crossing the junction is
e = e () e ().
(21.57)
The two equivalent ways of representing the effect of the potential are shown in Fig. 21.2.
By looking at the position of or e (x) with respect to the band edges, we can see that the
impurities will remain fully ionized at all x.
The spatially varying charge density is given by

(x) = e Nd (x) Na (x) nc (x) + pv (x) .
(21.58)
In this case, the Poisson equation is a nonlinear differential equation that must be solved
21.2. INHOMOGENEOUS SEMICONDUCTORS
Na
183
carrier density
p type
n type
+ + +
nc (x)
+ +
- - - +
+
+
pv (x) - - - - -
+ +
- + + +
depletion layer
dp
Nd
dn
charge density
eNd
dp
-
+ + +
+ +
+ + +
+ +
+ + +
dn
eNa
potential
dp
dn
Figure 21.3: The spatially varying carrier density, charge density and potential in a p-n
junction.
184
numerically. We can find an approximate solution by realizing that except near the edges of
the depletion layer (x = dn and x = dp ) the conduction- and valence-band carrier densities
are negligible compared to Nd and Na . The charge density is therefore

(x) e Nd (x) Na (x) .
(21.59)
in the depletion region and zero elsewhere. This sets the curvature of the potential through
the depletion region:
0
x > dn
2
d
eNd /0 r 0 < x < dn
=
.
(21.60)
2
eNa /0 r dp < x < 0
dx
0
x < dp
This has solution
()
x > dn
2
() (eNd /20 r )(x dn )
0 < x < dn
(x) =
.
2
()
+
(eN
/2

)(x
d
)
d
a
0 r
p
p < x < 0
()
x < dp
(21.61)
A unique solution is obtained by requiring continuity of (x) and 0 (x). This leads to
expressions for dp and dn , giving values in the range 102
A to 104
A for the thickness of the
depletion layer.
21.3
The p-n junction as a rectifier
We now consider the effect of applying an external bias to the p-n junction. Because the
conduction- and valence-band charge density is very low in the depletion layer, the resistance
of the p-n junction is high, and all the voltage drop will occur across the p-n junction. We
define a voltage V so that positive voltage corresponds to a raising of the potential of the
p-type region with respect to the n-type, thereby reducing the total change in potential.
= ()0 V
(21.62)
This will be accompanied by changes in the thickness of the depletion layer, but these have
no important effect on the magnitude of the current that flows. The reason we get diode
action from a p-n junction is that, for each type of carrier, there are two types of current
that flow when the junction is biased, one of which depends nonlinearly on voltage.
The two types of current (for holes) are:
Generation current. A very small density of holes, as the minority carrier, is generated
at the edge of the n-type depletion layer. If these can diffuse into the depletion region,
they are immediately swept over to the p-type region by the strong electric fields in
the depletion layer. This current is Jhgen .
Recombination current. Holes are continuously being formed at the boundary of the
p-type region, but the proportion of these that have enough kinetic energy to surmount

the potential barrier is exponentially small, Jhrec exp e[()0 V ]/kB T .
21.3. THE P-N JUNCTION AS A RECTIFIER
185
V
Figure 21.4: The currentvoltage characteristic of a p-n junction, showing diode action.
At zero bias, the generation and recombination currents must balance, implying
Jhrec = Jhgen eeV /kB T
(21.63)
The net current in the forward direction is

Jh = Jhrec Jhgen = Jhgen eeV /kB T 1 .
(21.64)
A similar contribution, of the same sign, comes from the electrons. The currentvoltage
characteristic of a diode is plotted in Fig. 21.4.
186
Lecture 22
The Boltzmann transport equation
Our aim in this lecture is to develop a framework for calculating the transport of electricity
and heat by Bloch electrons, starting with the main results from the semiclassical theory
of electron dynamics developed in Lectures 16 and 17. As before, we specify the position r
and wavevector k of the Bloch electron simultaneously. This can be done without violating
the uncertainty principle by using wavepackets. That is, our definition of position and
momentum is sufficiently fuzzy that rk > 1. According to the semiclassical equations of
motion, the position and wavevector evolve in time as:
1
r = vn (k) = k n (k)
~

~k = e E(r, t) + vn (k) B(r, t) .
(22.1)
(22.2)
For a system of electrons in a real sample, under the application of external fields, at a
temperature T that in general varies in space and time, and in the presence of static and
dynamic disorder, we have to give up any hope of calculating the states of definite occupation
number. Instead, we describe the electrons in terms of a distribution function f (r, k, t) that
measures the average occupancy of the Bloch state k as a function of space and time. f (r, k, t)
is a function of seven variables, describing the time evolution of electrons in a six-dimensional
phase space. This sounds complicated, but is actually fairly simple if the problem is tackled
systematically. The approach we in this lecture is intended to be somewhat complementary
to that given in Taylor and Heinonen.
22.1
The distribution function
To start with, lets imagine f (r, k, t) in the simplest situation: at zero-temperature, in the
absence of applied fields. Although six dimensions are impossible to visualize, the structure
of f (r, k, t) in the rk phase space is clear enough. f (r, k, t) = 1 within the Fermi sea, and
drops abruptly to zero outside it. In real space f (r, k, t) is constant. The integral
Z
drdk
f (r, k, t) = N
(22.3)
4 3
where N is the number of electrons in the sample.
187
188
LECTURE 22. THE BOLTZMANN TRANSPORT EQUATION
If we now heat the sample uniformly to a temperature T , the effect on f (r, k, t) is to broaden
the sharp step in k-space at the Fermi surface. It is also possible to impose a nonuniform
temperature distribution on the system. The nonuniformity will almost always be in real
space1 and very often be composed of a uniform temperature gradient.
Figure 22.1: Schematic illustration of the time evolution of electron states in the sixdimensional semiclassical phase space. (After Ashcroft and Mermin[4].)
The effect of external fields is to cause electrons to move along well-defined trajectories in
the rk phase space, as sketched in Fig. 22.1. These trajectories obey the Liouville theorem
they sweep out phase space volume at a constant rate. As a result, electrons do not pile
up at particular parts in phase space under the action of the external fields, which would
violate the exclusion principle.
Finally, scattering from impurities, defects, phonons and other excitiations causes electrons
to make random transitions from one point in k-space to another. (The scattering events
are always local in real space.) The scattering probability from state k0 to k is represented
by the function Q(k, k0 ). The net rate of scattering into state k is
X

fk =
fk0 Q(k, k0 )(1 fk ) fk Q(k0 , k)(1 fk0 ) ,
(22.4)
k0
showing how allowance is made for the Pauli exclusion principle. We will not go into any
more detail about the function Q(k, k0 ) much of the complexity of transport theory is
contained within it.
1
It is possible to create a temperature nonuniformity in k-space, by pumping energy into the system at
particular wavevectors. Situations like this are rare, but interesting when they occur. For an example see
N. Gedik et al. [21].
22.2. THE CONTINUITY EQUATION
22.2
189
The continuity equation
Before deriving the Boltzmann transport equation for electrons, it is useful to review how a
conservation law results in a continuity equation. For any conserved quantity, such as fluid
volume or electric charge, the net flux through a surface must be equal to rate at which the
amount of material within the surfaces decreases. Thus conservation of charge, for instance,
results in continuity of electrical current:
Z
Z
dV.
(22.5)
j dA =
t V
S
Using Gauss theorem this can be expressed in differential form as
+ j = 0.
t
(22.6)
The current is related to charge density by

j = u
(22.7)
where u is the velocity. Therefore
22.3
+ (u) = 0
t
(22.8)
+ u + u = 0.
t
(22.9)
The Boltzmann equation
We begin by deriving the equation of continuity of the electron distribution function f (r, k, t)
in the absence of collisions, which is equivalent to the statement that the rate at which the
density of electrons increases in a given volume of phase space is equal to the net rate at
which electrons enter the volume. That is, in the absence of scattering, electrons cannot
spontaneously appear in or disappear from a volume of the phase space. Generalizing the
continuity equation derived above to six dimensions, we have
f
= 0.
+ r (f r ) + k (f k)
t
(22.10)
Carrying out the differentiation gives

f
= v r f k k f f r v + k k .
t
(22.11)
For Bloch electrons, the term in brackets vanishes, which can be shown using Eqs. 1 and 2.
(The net flow into any volume of phase space is equal to the net flow out, by the Liouville
theorem.)
190
Finally, we include a collision term of the form of Eq. 22.4 on the right hand side of the
equation.

1
f
f
= v r f F k f +
,
(22.12)
t
~
t collisions
where F = e(E + v B) is the Lorentz force. This is the Boltzmann transport equation
for electrons in a periodic solid.
If we note that the spatial variation of f is due solely to variation in the temperature, we
can write
f
f
=
T,
(22.13)
r
T
leading, in the steady state (f /T = 0), to

e
f
1
f
= k T
E + v B k f.
t collisions ~
T
~
22.4
(22.14)
The linearized Boltzmann equation
In most cases we are interested in calculating the electrical and thermal currents that flow in
response to small electric fields and temperature gradients. It then suffices to make a series
expansion of f (r, k, t) in powers of the applied fields:
f = f 0 + f 1.
(22.15)
To zeroth order, f = f 0 , the equilibrium FermiDirac distribution. f 1 represents the local

departure from equilibrium. If the applied fields are small, f 1 will be everywhere much smaller
than 1.
The main role of collisions is to return the system to equilibrium, so
0
f
= 0.
(22.16)
t collisions
Also, since f 0 (k) = f 0 (k)
f 0
k .
(22.17)

Putting all this into the Boltzmann equation and keeping only terms linear in the temperature
gradient and electric field we get
1
f
e
f 0
f 0
= vk B k f 1 + vk T
eE
(22.18)
t collisions
~
T

f 0
e
= vk B k f 1 vk ( )T /T + eE
.
(22.19)
~

k f 0 =
This is the linearized Boltzmann equation for f 1 , the departure from equilibrium.
22.5. THE RELAXATION TIME APPROXIMATION
22.5
191
The relaxation time approximation
The main difficulty in solving the linearized Boltzmann equation is in accurately modeling
the collision term. This is discussed in some detail in Taylor and Heinonen. We will instead
focus on a simple but important limit, the relaxation time approximation, in which the
distribution function relaxes to equilibrium with a characteristic relaxation time . In this
case
1
f1
f
= .
(22.20)
t collisions
Although simple, the approximation is quite often valid, especially for impurity scattering.
One simple extension is to let the relaxation time depend on wavevector. In the following,
however, we will assume that is a constant.
Figure 22.2: Solutions of the linearized Boltzmann equation for a free electron metal plotted
for an electrical current (left) and a thermal current (right). Note that the effect of an
electrical current is to displace the Fermi sea, while the electrons are hotter on one side of
the Fermi sea than the other for a thermal current. (After J. R. Waldram[22].)
In the relaxation time approximation, in the absence of magnetic field, the linearized Boltzmann equation is
f 0
f1
= vk ( )T /T + eE
,
(22.21)

with solution
f 0
.
(22.22)
fk1 = vk ( )T /T + eE

192
(f 0 /) peaks sharply near the Fermi level,

f 0

f 0 (1 f 0 )
kB T
( F ) as T 0.
=
(22.23)
(22.24)
so the deviation of the distribution function f from the equilibrium FermiDirac distribution
is localized near the Fermi surface. f 1 is plotted in Fig. 22.2 for situations corresponding
to an electrical current and a thermal current. Note that the main difference is due to the
factor ( ), which makes f 1 antisymmetric about the Fermi level for thermal currents.
This acts to either broaden or sharpen the step in the distribution function at the Fermi
surface. Note that f 1 is always antisymmetric about the origin of k-space and, for a uniform
electrical or thermal current density, is independent of position.
22.6
Transport properties of metals
We can now derive expressions for the transport coefficients of metals. These relate electrical
and thermal currents to electric fields and temperature gradients. The electrical current
density is
1 X
(e)vk fk
(22.25)
j =
V k
1 X
=
(e)vk fk1 ,
(22.26)
V k
because j = 0 in equilibrium.
Similarly, the heat current density can be written
1 X
( )vk fk1 .
j =
V k
(22.27)
(It is necessary to subtract a way a term proportional to the chemical potential, because
that contribution to the energy flux is purely electrical, not thermal.)
We now evaluate these in the relaxation time approximation.
22.6.1
Electrical conductivity
To obtain the electrical conductivity we set the thermal gradient to zero and calculate the
electrical current in the presence of an electric field.
j=
e2 X
f 0
vk (vk E)
V k

(22.28)
e2 X
f 0
v k vk
.
V k

(22.29)
j = E, so
=
22.7. THE WIEDEMANNFRANZ LAW
193
In the simple case of metal with a spherical Fermi surface, the conductivity is a diagonal
tensor and
1
Tr()
(22.30)
xx =
3
e2 X
f 0
=
(22.31)
|vk |2
3V k

e2 vF2 X
(k F ) as T 0
(22.32)
3V
k
=
2e2 F
D(F ),
3mV
(22.33)
where D(F ) is the density of states at the Fermi level. We previously showed that
D(F ) =
3N
,
2F
(22.34)
so
N e2
ne2
=
,
mV
m
where n = N/V is the density of electrons.
xx =
22.6.2
(22.35)
Thermal conductivity
The heat current density is

j =
X
f 0
vk (vk T )( )2
.
VT k

(22.36)
The thermal conductivity is defined

j = T.
(22.37)
The ()2 (f 0 /) term has a double peaked structure about F . However, the summation
is straightforward to evaluate by converting it to an integral and using the Sommerfeld
expansion that we saw in Lecture 3. The result is
=
2 nkB2
T
3 m
(22.38)
for the isotropic metal.
22.7
The WiedemannFranz law
For isotropic scattering (either by impurities or phonons) the ratio of the electrical and
thermal conductivities takes on a universal value, independent of the band structure of the
metal. The Lorenz ratio is
2 kB2
=
.
(22.39)
T
3e2
194
The electrical and thermal conductivities and Lorenz ratio of copper are plotted in Fig. 22.3.
The Lorentz ratio becomes small at intermediate temperatures because there small-angle
scattering by phonons dominates.
Figure 22.3: Electrical and thermal conductivities and Lorenz ratio /T for copper, measured by Berman and MacDonald[23].
Lecture 23
Time-dependent perturbation theory
References: The introduction to time-dependent perturbation theory is based on the excellent treatment
given by Shankar[6].
23.1
Time-dependent perturbation theory
In the time independent case, solving the Schrodinger equation
|i = H0 |i
(23.1)
t
reduces to solving the eigenvalue problem of H0 to find the stationary states. We assume we
can do this, and label the eigenstates and eigenenergies of the time-independent hamiltonian
by |ni and En .
We now introduce a time-dependent potential U (t) to the hamiltonian as a perturbation.
i~
H0 H(t) = H0 + U (t).
(23.2)
As with all perturbative methods, we require the perturbation U (t) to be small, but delay
our definition of small until later.
In what follows we will only be interested in first order perturbation theory.
The states |ni form a complete set, so the wavefunction at time t can be expanded in terms
of them.
X
|(t)i =
cn (t)|ni
(23.3)
n
The process of calculating the cn (t) given cn (0) is equivalent to finding |(t)i given |(0)i.
cn (t) changes with time due to the action of both the time-independent hamiltonian H0 and
the time-dependent perturbation U (t). Had U (t) been absent, we would have
cn (t) = cn (0)eiEn t/~ .
(23.4)
Lets take this into account explicitly by carrying out a slightly different expansion.
X
|(t)i =
dn (t)eiEn t/~ |ni
(23.5)
n
195
196
LECTURE 23. TIME-DEPENDENT PERTURBATION THEORY
Now, if dn changes with time it is due solely to the action of U (t).

The next step is to operate on both sides of Eq. 23.5 with i~ /t H0 U (t) . Because
|(t)i is an eigenstate of H(t), we then have
0 =
X
i~dn (t) + En dn (t) En dn (t) U (t)dn (t) eiEn t/~ |ni
(23.6)
i~dn (t) U (t)dn (t) eiEn t/~ |ni.
(23.7)
X
n
We now project out one term from the last equation by multiplying by hf| exp(iEf t/~), which
gives
X
i~df (t) =
hf|U (t)|nieifn t dn (t),
(23.8)
n
where ~fn = Ef En .
We imagine the system starts at time t = 0 in one of its eigenstates, which we call the initial
state and label it |ii. Therefore
dn (t = 0) = ni .
(23.9)
We want to know how the system evolves at later times under the action of the timedependent perturbation. That is, we want to know df (t).
To zeroth order we ignore the perturbation and find that df = 0, dn (t) = ni .
To first order in the perturbation, we use the zeroth-order dn , resulting in the equation
i
df = hf|U (t)|iieifi t .
~
(23.10)
This can be integrated to obtain the solution

i
df (t) = fi
~
hf|U (t0 )|iieifi t dt0 .
(23.11)
The first order calculation will be reliable if |df (t)| 1 for all f 6= i.
Substituting back into the original expansion we obtain
|(t)i = N
df (t)eiEf t/~ |fi
(23.12)
Z

i t
0
ifi t0 0
= N
fi
hf|U (t )|iie
dt eiEf t/~ |fi
~
f
Z

i X t
0
iEi t/~
hf|U (t0 )|iieifi t dt0 eiEf t/~ |fi.
= e
|ii
~ f6=i
X
(23.13)
(23.14)
In the last line, the normalization factor N has been taken into account, to first order, by
excluding |ii from the sum over final states |fi.
23.2. SUDDEN PERTURBATIONS
23.2
197
Sudden perturbations
In many cases our perturbation amounts to a sudden change in potential at time t = 0. We

can solve this by integrating the Schrodinger equation between t = /2 and t = /2.
|( 2 )i |( 2 )i = |after i |before i
Z
2
i
=
H(t)|(t))idt.
~
(23.15)
(23.16)
If H(t) is finite, then there is no change in |(t)i in the limit 0.

|after i = |before i
(23.17)
However, the wavefunction is no longer an eigenstate of the hamiltonian, as the hamiltonian

itself has changed. Sudden perturbations are very important in the theory of angle-resolved
photoemission spectroscopy, which we will discuss in Lecture 27.
23.3
Adiabatic perturbations
The adiabatic theorem states that if the rate of change of the hamiltonian H(t) is slow
enough, the system, starting at t = 0 in an eigenstate |n(0)i of H(0), will end up in the
corresponding eigenstate |n( )i of H( ) at a later time .
This result is true to all orders in perturbation theory, but places stringent requirements
on how slowly the perturbation must be switched on. The condition is that T , where
T = ~/Emin and Emin is the minimum energy separation between the initial state and all
other eigenstates. For any system that is near degenerate, the required rate is very slow. For
degenerate systems , and it becomes impossible to make an adiabatic perturbation.
This result is very important in Landaus Fermi liquid theory, where it allows a connection
to be made between the excited states of an interacting electron system and those of a model
noninteracting system.
23.4
Periodic perturbations
Let the time dependent potential have the form

U (t) = U0 eit ,
(23.18)
where has a small imaginary part that causes the perturbation to be switched on slowly
from some time in the distance past:
+ i.
(23.19)
Also, lets define the frequencies n = En /~.

198
Then, substituting into Eq. 23.14, our main perturbation theory result, we obtain
Z

i X t
0
0
ii t
hf|U0 |iieit ei(f i )t dt0 eif t |fi.
|(t)i = e
|ii
~ f6=i
The integral over t0 can be evaluated:

Z t
0
ei(f i i)t dt0 =
i
ei(f i i)t .
i f + + i
(23.20)
(23.21)
The expression for the wavefunction is then

|(t)i = eii t |ii +
1X
hf|U0 |ii
ei(i ++i)t |fi.
~ f6=i i f + + i
(23.22)
The adjoint equation, which we will need later, is

h(t)| = eii t hi| +
1X
hi|U0 |fi
ei(i +i)t hf|.
~ f6=i i f + i
(23.23)
If the perturbation is U (t) = U0 exp(it), then we require to have a small negative imaginary part. The corresponding expression for the wavefunction is
|(t)i = eii t |ii +
1X
hf|U0 |ii
ei(i +i)t |fi.
~ f6=i i f + i
(23.24)
This last point is important. Any linearly polarized field applied to the system can be
decomposed into equal amplitudes of left- and right-circularly polarized radiation, so the
perturbation must consist of negative and positive frequencies.
23.5
Fermis golden rule
As well as following the time evolution of the wavefunction, we can also calculate the transition rate between the initial state |ii and a particular final state |fi under the influence of a
periodic perturbation U (t) = U0 eit . Lets assume we start in state |ii at time t = T /2 and
integrate Eq. 23.10 until a later time t = T /2. We wish to calculate the average transition
rate in the limit T . Then
Z
i T /2
0
hf|U0 |iiei(fi )t dt0
(23.25)
df (t) = lim
T
~ T /2
2i
=
hf|U0 |ii(fi ).
(23.26)
~
The transition probability is
Pif = |df |2
4 2
=
|hf|U0 |ii|2 (fi )(fi ).
~2
(23.27)
(23.28)
23.6. THE KUBO FORMULA
199
The double delta function requires special care:

1
(fi )(fi ) = lim (fi )
T
2
T /2
ei(fi )t dt.
(23.29)
T /2
Set = fi in the integral:

T
.
T 2
(fi )(fi ) = (fi ) lim
(23.30)
The average transition rate is

Pif
T
2
|hf|U0 |ii|2 (Ef Ei ~).
=
~
Rif =
(23.31)
(23.32)
This is Fermis golden rule. The delta function explicitly enforces conservation of energy. In
the context of solid state physics, we are usually trying to calculate the net transition rate
out of a particular Bloch state. We then integrate over all final states of the same energy and
obtain the result that the transition rate or scattering rate is proportional to the density
of final states.
23.6
The Kubo formula
We now use time dependent perturbation theory to calculate the electrical conductivity. The
electromagnetic field is introduced through the vector potential A.
A
t
if E = E0 eit + complex conjugate
E0 it
A =
e
+ complex conjugate
i
E =
(23.33)
(23.34)
(23.35)
How does the vector potential couple to the electron? In the presence of a field the canonical
momentum is p = mv eA, which implies that kinematic momentum is mv = p + eA.
That is, the kinematic momentum acquires a kick from the field when the field is switched
on. It is the kinematic momentum that goes into the Schrodinger equation, so p is replaced
by p + eA.

p2
(p + eA)2
p2
e
=
+
A p + p A + ...
(23.36)
2m
2m
2m 2m
If we specialize to the transverse gauge A = 0, we can show that p A = A p, and
therefore
(p + eA)2
p2
e
+ A p.
(23.37)
2m
2m m
To linear order, the perturbation to the hamiltonian is
U (t) =
e
e
E0 p eit
E0 p ei t .
mi
mi
(23.38)
200
We can now use the first order perturbation theory results to calculate the current.
e
h(t)|mv|(t)i
m
e
= h(t)|p + eA|(t)i,
m
hJi = V j =
(23.39)
(23.40)
where V is the volume of the sample.

The current carried by the perturbed state, evaluated to first order in E0 , is
e
e2 E0 it e2 E0 i t
hi|p|ii hi|
e
e |ii
(23.41)
m
im
im

ei t
e2 X
eit
(23.42)
hi|p|fihf|E
p|ii
0
i~m2 f6=i
(i f + + i) (i f + i)

e2 X
eit
ei t
hi|E0 p|fihf|p|ii
(23.43)
.
i~m2 f6=i
(i f i) (i f + i)
J =
We assume that the current in the ground state, J0 = me hi|p|ii, vanishes.

The electrical conductivity () is the coefficient of exp(it) that relates j to the applied
electric field and can be isolated from this expression.
j (t) = j eit + complex conjugate
X
=
E0, eit + complex conjugate
(23.44)
(23.45)
We assume that the initial state is occupied with probability fi , and sum over all initial
states to get the Kubo formula for the conductivity:
"
#
X 1 hi|p |fihf|p |ii
hi|p |fihf|p |ii
e2 X
fi +
+
=
. (23.46)
imV i
~m i f + + i i f i
f6=i
If all the n are real (the imaginary part of n represents the lifetime of the state |ni) then
we can exchange f and i in the final term.
"
#
X fi ff hi|p |fihf|p |ii
e2 X
.
(23.47)
=
fi +
imV i
~m i f + + i
f6=i
Absorption of energy is given by the real part of the conductivity, which we can obtain using
the identity

1
1
lim
=P
i(x),
(23.48)
0 x + i
x
where P denotes the principle part of the integral.
Re[ ] =
e2 X
(fi ff )hi|p |fihf|p |ii(~f ~i ~).
m2 V i,f
(23.49)
23.6. THE KUBO FORMULA
201
For small values of (and with a finite lifetime for the excited states) this reduces to the
Boltzmann result for a single band. For high frequencies, where the semiclassical approach
fails due to interband transitions, we get transitions between levels whenever the resonance
condition f i = is satisfied.
Eq. 23.49 also applies if the system is prepared out of equilibrium, as in a laser.
202
Lecture 24
Density response of the electron gas
In Lecture 8 we used the ThomasFermi theory of screening to calculate the response of
the electron gas to an external potential. The nature of the approximation meant that the
theory would only be accurate for long wavelength, low frequency perturbations. However,
we went ahead anyway and used the theory to calculate how the potential of a point charge
is screened. We will now develop a more accurate method for calculating the response of the
electron gas to time-dependent potentials of arbitrary wavelength.
We define the density response function (q, ) by
(q, ) = (q, )V (q, ),
(24.1)
where (q, ) is the charge density induced by the total potential V (q, ).
We will carry out the calculation for a noninteracting, free Fermi gas. The calculation will
remain valid for Fermi liquids, which we will meet in Lecture 28.
24.1
Time and space dependent perturbations
We again use time dependent perturbation theory to calculate solutions of the Schrodinger
equation in the presence of a time and space dependent potential U (r, t).
i~

(r, t)
= H0 + U (r, t) (r, t)
t
(24.2)
As before, we assume that we can solve H0 , which has eigenfunctions n (r) and eigenvalues
n . (We will soon specialize to the case of free-electron plane waves.) We look for a general
solution of the form
X
(r, t) =
an (t)ein t/~ n (r)
(24.3)
n
to first order in the perturbation. Using the result from the previous lecture,
i
am (t) = m,n
~
hm|U (r, t0 )|nieimn t dt0 .
203
(24.4)
204
LECTURE 24. DENSITY RESPONSE OF THE ELECTRON GAS
To calculate the effect of fields that vary in time and space, we apply a perturbation of the
form
U (r, t) = U0 eiqr ei(+i)t ,
(24.5)
where the infinitesimal causes the perturbation to be switched on slowly from some time
in the distant past. In all our calculations we will set to zero in the final result.
As basis states for our problem we choose the eigenstates of the time-independent part of
the hamiltonian, which in this case will be the free-electron plane waves
1
|ki = eikr .
V
(24.6)
To begin with, we assume our initial state at time t = is a particular plane wave state
|ki and calculate the wavefunction |(r, t)i at a later time t. We will eventually extend this
to a sum over all occupied initial states.
X
|(r, t)i =
ak0 (t)eik0 t/~ |k0 i,
(24.7)
k0
where
i
ak0 (t) = k0 ,k
~
hk0 |U (r, t)|kiei(k0 k )t /~ dt0 .
(24.8)
The matrix element between plane wave states can be evaluated:

Z
0
0
i(+i)t 1
hk |U (r, t)|ki = U0 e
eik r eiqr eikr dr
V
i(+i)t
= U0 e
k0 ,k+q .
(24.9)
(24.10)
Therefore, the amplitude to be in state |k0 i at a later time t is

i
ak0 (t) = k0 ,k U0 k0 ,k+q
~
= k0 ,k + U0 k0 ,k+q
ei(k0 k ~(+i))t /~ dt0
(24.11)
i(k+q k ~)t/~
k+q k ~( + i)
(24.12)
On inserting this into the wavefunction ansatz we obtain

U0
eit eik t/~
k+q k ~( + i)
= a(t)|ki + b(t)|k + qi.
|k (r, t)i = |kieik t/~ + |k + qi
(24.13)
(24.14)
This is a simple and physically appealing result. A time dependent perturbation of wavevector q couples the state |ki to state |k + qi. The transition between states is not sudden
when the perturbation is applied the initial state starts to evolve into a quantum superposition of |ki and |k + qi. (Remember, as we saw in the last lecture, the states are normalized
to first order in the perturbation.)
24.2. DENSITY RESPONSE
24.2
205
Density response
We are now in a position to calculate the density response of the electron gas. We need to
take all the k-states that were initially occupied (these will be occupied with probability nk ,
where nk is the FermiDirac function at temperature T ) and use Eq. 24.13 to follow their
time evolution under the action of the applied field. We then evaluate the density at the
later time. The change in the density is
Xn
1o
,
(24.15)
(r, t) =
|k (r, t)|2
V
k
where the sum is over initially occupied k-states. Working to first order, we have
o
1n
|a(t)|2 eikr eikr +a(t) b(t)eikr ei(k+q)r +b(t) a(t)ei(k+q)r eikr +... (24.16)
|k (r, t)|2 =
V
The first term on the right hand side is the unperturbed density. The phase factor exp(ik t/~)
is common to a(t) and b(t) and makes no contribution, so
(r, t) =
o
U0 X n
eiqr eit
+ complex conjugate .
V k k+q k ~( + i)
(24.17)
In an actual experiment, the potentials we apply are real functions of space and time, so we
add to the potential its complex conjugate
U (r, t) = U0 eiqr ei(i)t
(24.18)
This is equivalent to q q and + i + i, which gives

o
eiqr eit
U0 X n
+ complex conjugate .
(r, t) =
V k kq k + ~( i)
(24.19)
We collect everything together and include a factor of 2 for spin.

tot = 2 (r, t) + (r, t)
(24.20)

n
2U0 X iqr it
1
1
=
e e
+
(24.21)
V k
k+q k ~( + i) kq k + ~( + i)
o

1
1
iqr it
+ e
e
+
.
(24.22)
k+q k ~( i) kq k + ~( i)
Implicit in this expression is that the sum is over occupied initial states. We now include
the occupation numbers nk explicitly, and carry out the sum over all k-states.

2U0 X n iqr it
nk
nk
tot
=
e e
+
(24.23)
V k
k+q k ~( + i) kq k + ~( + i)
o

nk
nk
iqr it
+ e
e
+
.
(24.24)
k+q k ~( i) kq k + ~( i)
206
Because we are now summing over all k-states, we are free to redefine the summation index
k. We let k k + q in the right hand fractions.

nk
nk+q
2U0 X n iqr it
tot
e e
+
(24.25)
=
V k
k+q k ~( + i) k k+q + ~( + i)

o
nk
nk+q
iqr it
+ e
e
+
(24.26)
k+q k ~( i) k k+q + ~( i)

nk nk+q
2U0 X
iqr it
e e
+ complex conjugate
(24.27)
=
V k
k+q k ~( + i)
We define the density response function (q, ) to be the coefficient of U0 exp(iq r it).
2 X
nk nk+q
(q, ) =
(24.28)
V k k+q k ~( + i)
24.3
Energy loss
Using the identity

1
lim
=P
0 x + i

1
i(x)
x
(24.29)
we obtain the imaginary part of (q, ).

2 X

Im (q, ) =
nk nk+q (k+q k ~).
V k
(24.30)
We will now show that this is associated with energy loss.

We use Fermis golden rule
2
|hf|U0 |ii|2 (Ef Ei ~)
~
to calculate the power absorption. In our case the perturbing potential is
Rif =
(24.31)
U (r, t) = U0 eiqr eit + U0 eiqr eit .
(24.32)
The relevant matrix elements are

hk0 |eiqr |ki = k0 ,kq .
(24.33)
The transition rate from state |ki to |k0 i is

o
2 2 n
U0 k0 ,k+q (k0 k ~) + k0 ,kq (k0 k + ~) .
Wkk0 =
~
The total transition rate out of state k is
X
Wk =
Wkk0
(24.34)
(24.35)
k0
o
2 2 n
U0 (k+q k ~) + (kq k + ~) .
~
(24.36)
24.4. SCREENING AND THE DIELECTRIC FUNCTION
207
In each transition the system absorbs or emits a quantum of energy ~. The mean energy
absorbed per unit time by the state |ki is
Qk =
o
2 2 n
U0 ~ (k+q k ~) (kq k + ~) .
~
(24.37)
Note the difference in sign for emission and absorption. If we now sum this over all occupied
states, we have the total rate of energy absorption P for a perturbation of wavevector q and
frequency . Normalizing to unit volume, we have
P
V
o
2 X n
=
nk (k+q k ~) (kq k + ~)
V k

2 X
= 2U02
nk nk+q (k+q k ~)
V k

= 2U02 Im (q, ) ,
2U02
(24.38)
(24.39)
(24.40)
confirming that energy loss is proportional to the imaginary part of the density response
function.
24.4
Screening and the dielectric function
We now have a much more accurate model of the density response of the electron gas than
the ThomasFermi theory we used in Lecture 8. Lets use it to examine the issue of screening
again.
A q and dependent external potential V ext (q, ) will induce a density response that partially screens the applied (external) potential, to give a screened potential V scr (q, ).
V scr (q, ) = V ext (q, ) (q, )V coul (q).
where
V
coul
e2
(q) =
0 q 2
(24.41)
(24.42)
is the spatial Fourier transform of the Coulomb potential.

From the calculation above
(q, ) = (q, )V scr (q, ).
(24.43)
Therefore
V scr (q, ) = V ext (q, ) (q, )V coul (q)V scr (q, ) (24.44)

V scr (q, ) 1 + (q, )V coul (q) = V ext (q, )
(24.45)
(q, ) = (q, )V scr (q, )
(q, )V ext (q, )
=
1 + (q, )V coul (q)
(24.46)
(24.47)
208
Another way to write this is in terms of the dielectric function:

1
V scr (q, )
ext
V (q, )
r (q, )
=
(24.48)
1
1 + V coul (q)(q, )
(24.49)
This defines the dielectric function in the random phase approximation.

RPA
(q, ) = 1 +
r
2e2 1 X
nk nk+q
.
2
0 q V k k+q k ~( + i)
(24.50)
This is the dynamical generalization of ThomasFermi theory.
24.5
Properties of the RPA dielectric function
In the static limit 0

RPA
(q, 0) = 1 +
r
2
qTF
F (q/2kF ),
q2
(24.51)
where F (x) 1 as x 0.
F (x) is plotted for 1, 2 and 3 dimensions in Fig. 24.1. At q = 2kF , 0 is singular in 1D,
and has discontinuous derivatives in 2D and 3D. The singular response leads to the Peierls
distortion, which we will discuss in the next lecture. In higher dimensions the singular
derivative means that (q, ) oscillates in real space as a function of distance. Near a
defect in a metal of charge Q, the induced charge density has the following form
ind (r)
Q
cos(2kF r),
r3
(24.52)
which is plotted in Fig. 24.2. These variations of the charge density are called Friedel oscillations and can nowadays been seen directly in scanning tunneling microscopy experiments.
Similar oscillations occur in the spin density response when a local exchange potential (in
other words a spin-dependent potential) is applied. This is usually due to the presence of a
local magnetic moment, such as those found in transition-metal and rare earth ions.
The spin-density oscillations mediate the magnetic interaction between neighbouring ions.
The details of this were worked out by Ruderman, Kittel, Kasuya and Yoshida, so the effect
is called the RKKY interaction. The very interesting thing is that the sign of the magnetic
interaction oscillates between ferromagnetic and antiferromagnetic as a function of distance.
In modern magnetic multilayer devices such as those use in hard-disk media, accurate control
of layer thicknesses is used to tune the sign and strength of the magnetic interaction between
neighbouring ferromagnetic layers.
24.5. PROPERTIES OF THE RPA DIELECTRIC FUNCTION
209
Figure 24.1: Static susceptibility (q, 0) in one, two and three dimensions. (From
Kagoshima et al.[24])
Figure 24.2: The charge density induced by a point-like potential, showing Freidel oscillations. (From Kagoshima et al.[24])
210
Lecture 25
Electrons in one dimension
A characteristic property of electronic systems in one dimension is their instability to perturbations of wavevector 2kF . The static density response function (q, = 0) diverges at
q = 2kF , leading to an instability towards a collective state of the electrons called a charge
density wave. This instability opens an energy gap at the Fermi level and leads to a metal
insulator transition called the Peierls transition. This is not just exotic physics confined to
a small class of materials. In real 3D systems, such as chromium, part of the Fermi surface
behaves as though it were one dimensional, due to a process called nesting.
25.1
One dimensional conductors
In Lecture 24 we derived the density response function

nk nk+q
2 X
.
(q, ) =
V k k+q k ~( + i)
(25.1)
We now want to evaluate this for a one dimensional metal in the static limit, at zero temperature.
The energy dispersion for free electrons, = ~2 k 2 /2m, is plotted in Fig. 25.1. At zero
temperature, states with k in the range kF < k < kF are occupied. Other states are empty.
(q, = 0) has contributions when nk = 1, nk+q = 0 and when nk = 0, nk+q = 1. The
calculation is straightforward. We convert the sum to an integral, and the bounds on the
integral are set by the requirement that only one of |ki or |k + qi be occupied.
Z kF

Z kF
dk
dk
2 L
(25.2)
(q, = 0) =
L 2 kF q k+q k
kF q k+q k
Z kF

Z kF
1 m
dk
dk
=
(25.3)
~2 q kF q k + q/2
kF q k + q/2

q + 2kF
m

=
2 ln
(25.4)
~2 q
q 2kF
This result is plotted in Fig. 24.1, showing the strong divergence at q = 2kF in one dimension.
211
212
LECTURE 25. ELECTRONS IN ONE DIMENSION
Figure 25.1: The energy dispersion for free electrons in one dimension. (From Kagoshima et
al.[24])
In higher dimensions, the divergence is replaced by a discontinuous derivative, leading to

Friedel oscillations but no instability.
25.2
The Peierls instability
We now switch to a lattice system in one dimension. The band structure and crystal structure
are shown in Figs. 25.2a and 25.2b. The energy bands are free-electron like apart from energy
gaps at the Bragg planes. We consider a one-dimensional conductor, with the first Brillouin
zone partially filled.
25.2.1
Static lattice distortions
Consider a static lattice distortion of wavenumber Q,

u(x) = uQ cos(Qx),
(25.5)
where u(x) measures the displacement from equilibrium of each atom in the lattice. An
example is sketched in Fig. 25.2d. This distortion produces a potential V that acts on the
electronic system,
V (x) VQ cos(Qx) = guQ cos(Qx),
(25.6)
where g is a coupling constant that measures the strength of the electronlattice interaction.
25.2. THE PEIERLS INSTABILITY
213
The electron system responds to the external potential by forming a charge density wave
Q = VQ (q).
(25.7)
This must reduce the energy of the electron system, or it would not occur. The periodic
lattice distortion increases the energy it costs an elastic energy
U = 12 cLu2Q ,
(25.8)
where c is the elastic stiffness. If the decrease in the electronic energy is greater than the
increase in elastic energy, a spontaneous lattice distortion of wavevector Q will form and
be frozen into the system. In one dimensional metals this phenomenon readily occurs for
Q = 2kF .
25.2.2
The energy balance
A potential of wavevector Q opens a band gap at k = Q/2, as shown in Fig. 25.2c. The
magnitude of the gap is Eg = 2|VQ | = 2g|uQ |. The bands in the vicinity of k = Q/2 bend
apart to form the gap, and the perturbed energy dispersons are
q
0
0
(0k 0k+Q )2 + 4|VQ |2
k + k+Q
k =
.
(25.9)
2
2
The change in electron energy is
K = 2

k n(k ) 2
0k n(0k ).
(25.10)
If VQ EF then
K = 2|VQ |2
X nk nk+Q
k
(25.11)
k+Q k
= L|VQ | (Q, 0).
(25.12)
The total change in energy is

K + U = |VQ |2 L(Q, 0) + 21 cLu2Q

c
K + U
2
= |VQ | (Q, 0) 2 .
L
2g
(25.13)
(25.14)
At zero temperature, (Q, 0) diverges at Q = 2kF , while the elastic stiffness remains finite.
The system will therefore always be unstable to a charge density wave of wavevector 2kF .
The peak in (Q, 0) weakens as temperature increases and the Fermi-functions in the density
response function broaden. As a result, there is an upper bound on the temperature at which
the Peierls instability can occur.
Because the energy gap is opened right at k = kF , we end up with an energy band that is
completely filled, corresponding to an insulating state. The Peierls instability is an example
of a metalinsulator transition.
214
Figure 25.2: (a) Electron dispersion for a 1D lattice. (b) The crystal structure of such a
lattice it is a chain of atoms or other structural units. (c) and (d) Dimerization leads to
a doubling of the unit cell size and opens up energy gaps at new Bragg planes following a
Peierls transition. (From Kagoshima et al.[24])
25.3. KOHN ANOMALIES
215
(a)
(b)
Figure 25.3: (a) Softening of the phonon frequency as the Peierls transistion is approached.
(b) In one dimension, the phonon at Q = 2kF is pulled down to zero frequency at the
Peierls transition. In two and three dimensions the effect is present but much weaker. (From
25.3
Kohn anomalies
The onset of the Peierls transition changes the restoring force of the mechanical oscillation
of the ions. The phonon frequencies at wavevector Q = 2kF start to decrease or soften
well above the Peierls transition temperature, giving an early sign of what is about to occur.
The phonon frequency goes to zero right at the Peierls transition, at which point the phonon
quite literally freezes into the system as a static lattice distortion. This is illustrated in
Fig. 25.3. The depression of phonon frequency at Q = 2kF is called the Kohn anomaly. The
effect is much weaker in two and three dimensions.
216
Figure 25.4: (a) The Fermi surface in 1D is a set of two isolated points. (b) We can
imagine extending these points in perpendicular directions to get a Fermi surface. (c) Most
Fermi surfaces in two and three dimensions do not show nesting. (d) Nesting occurs when
a substantial fraction of the Fermi surface is spanned by one wavevector. Equivalently, a
large section of the Fermi surface is mapped onto itself by translation in k-space. (From
25.4. NESTING OF THE FERMI SURFACE
25.4
217
Nesting of the Fermi surface
Can the Peierls instability occur in two or three dimensional metals? The instability arises
from the singular nature of (q, ), which for a free electron Fermi surface is much weaker
in two and three dimensions. It turns out that some higher-dimensional Fermi surfaces have
strong one-dimensional character and retain some of the singular nature of (q, ). For this
to occur, large sections of the Fermi surface must be spanned by the same wavevector, Q0 .
Fig. 25.4(d) shows an example: translating the Fermi surface by wavevector Q0 maps a large
section of the Fermi surface on to itself. The density response will be very strong near Q0 ,
with (Q0 , 0) showing a divergence. This is called nesting.
Nesting is perfect in one dimension, where the Fermi surface consists of two isolated points.
Nesting in higher dimensions leads to spin and charge density wave instabilities, but does
not give rise to a metalinsulator transition, because nesting only opens a gap along the
parts of the Fermi surface spanned by the nesting vector. In this case it is common to refer
to parts of the Fermi surface being consumed by the spin or charge density wave instability.
Metallic antiferromagnetism in chromium is an example of a spin density wave instability.
25.5
Spincharge separation
A remarkable phenomenon occurs in interacting electron systems in one dimension. This is

spincharge separation, in which the electron quasiparticles are spinons and holons, particles
that respectively carry the electrons spin and charge, separately. This electron fractionalization really does occur in one dimension, and has been confirmed experimentally.
What is special about 1D? In one dimension all excitations of wavevector q have the same
energy q = vF q. This is not the case in two or three dimensions.
The Hamiltonian for a general interacting electron system in 1D is
=
H
k ck, ck, +
k,
1 XXX
v(q)ckq, ck0 +q,0 ck0 ,0 ck, .
2L k,k0 q ,0
(25.15)
As we saw, in Lecture
P 8, the interaction term can be rewritten in terms of the density
operators q = k ck, ck+q, :
V
X1
V (q)q, q, .
L
q,
(25.16)
This shows that the eigenmodes of interaction are density waves. The peculiar thing about
1D is that the eigenmodes of kinetic energy are also density waves.
25.6
The LuttingerTomonaga model
The LuttingerTomonaga model begins by replacing the quadratic energy spectrum by a

linearized spectrum that extends to infinite negative energies. We will focus on the positive
218
k side of the spectrum. These electrons are called right movers. We assume here that
they do not couple to the left movers, but that is not a necessary condition for spincharge
separation to occur.
The commutation relations for bosons are:

(25.17)
bq0 , bq = q,q0

bq0 , bq = 0
(25.18)

(25.19)
bq0 , bq = 0.
The anticommutation relations for fermions are:

cq0 , cq = q,q0

cq0 , cq = 0

cq0 , cq = 0.
(25.20)
(25.21)
(25.22)
Using these, it is straightforward to show that the commutator of two density operators is

X

q0 , q =
cp+q+q0 cp cp+q cpq0 .
(25.23)
p
This must be evaluated separately for two cases:

q 6= q 0
Let p0 = p + q 0 , then
X
X
q0 , q =
cp0 +q cp0 q0
cp+q cpq0 .
p0
(25.24)
For the linearized spectrum the sums run from to +. p0 is just a dummy index,
so the two sums are the same and cancel.

q0 , q = 0, q 6= q 0 .
(25.25)
q = q 0
X

q , q = q , q =
cp cp cp+q cp+q
(25.26)
n
p n
p+q
(25.27)
= number of states in interval q

Lq
=
2
(25.28)
(25.29)
In this last step we have used the fact that the energy dispersion continues to :
it has only one Fermi point, and the difference in occupation number is due to states
around that point.
25.6. THE LUTTINGERTOMONAGA MODEL
219

Lq
q0 , q = q,q0 ,
2
which means our boson operators are
r
2
bq =
q
Lq
r
2
bq =
q .
Lq
(25.30)
(25.31)
(25.32)
(25.33)
The eigenstates of kinetic energy in one dimension are density waves. The linearized kinetic
energy spectrum is
X
H0 =
~vF kck ck .
(25.34)
k
We can use an equation of motion approach to rewrite this in terms of density operators. It
is straightforward to show that

H0 , q = ~vF qq ,
(25.35)
which implies that

H0 , bq = ~vF qbq .
(25.36)
Therefore
H0 =
~vF q bq bq .
(25.37)
The interaction term is already diagonal in the density operators:

1X
V (q)q q
HI =
L q
1X
Lq
=
V (q) bq bq
L q
2
1 X
V (q)q bq bq .
=
2 q
At this point we reintroduce spin,
X
1 X
V (q, )q bq, bq, .
H=
~vF q bq, bq, +
2
q,
q,
and split the interaction into spin-symmetric and spin-antisymmetric parts:

spin symmetric :
S(q) q q + q q

spin antisymmetric :
A(q) q q q q
(25.38)
(25.39)
(25.40)
(25.41)
(25.42)
(25.43)
Then the hamiltonian is

X

1 X
1 X
H=
~vF q bq, bq, +
S(q)q bq bq + bq bq +
A(q)q bq bq bq bq .
2 q
2 q
q,
(25.44)
220
The hamiltonian can be diagonalized by a bosonic Bogoliubov transformation.
H=
X
q
q = bq + bq
charge density operator
(25.45)
q = bq bq
spin density operator
(25.46)
S(q) A(q)
~vF +
+
2
2

q
q q
S(q) A(q)
+ ~vF +
2
2

q
q q

(25.47)
The velocities of the charge and spin density excitations are

1
q S(q) + A(q)
2~ q

1
= vF +
q S(q) A(q) .
2~ q
v = vF +
(25.48)
(25.49)
The separation of spin and charge is complete the original electrons are replaced by
bosonic quasiparticles that carry the spin and charge separately. That this occurs is firmly
established, both theoretically and experimentally, for one-dimensional electron systems. An
open question is whether it occurs in two dimensions and, if so, whether it is responsible for
the very unusual physical properties of the cuprate superconductors.
Lecture 26
Collective modes and response
functions
26.1
Response functions
Very generally, we define a linear response function as a susceptibility (r, t; r0 , t0 ) that

relates a response u (r, t) at point r and time t to a disturbance due to an external field
F (r0 , t0 ) at point r0 and time t0 .
Z Z
u (r, t) = dr0 dt0 (r, t; r0 , t0 )F (r0 , t0 )
(26.1)
If the system is translationally invariant (we are usually concerned with wavelengths much
greater than the interatomic spacing) then is a function of the relative distance r r0 . If
the system is already in equilibrium then is a function of t t0 .
Z Z
u (r, t) = dr0 dt0 (r r0 , t t0 )F (r0 , t0 ).
(26.2)
This is a convolution integral and the usual theorems to do with convolutions apply. In
particular, the convolution becomes a simple product in Fourier space.
u (q, ) = (q, )F (q, )
(26.3)
While the susceptibility is clearly useful for describing the response of a system to a general
stimulus, what is less obvious is that it contains information about the collective modes of
the system.
26.2
Collective modes
There is fundamental relationship between response functions and collective modes. If a

response function (q, ) is divergent at certain wavevectors q and frequencies 0 (q), then
applying a driving force at the correct and q produces an infinite response. Equivalently,
221
222
LECTURE 26. COLLECTIVE MODES AND RESPONSE FUNCTIONS
an infinitesimal driving force at the same frequencies and wavevectors will produce a finite
response. The frequencies 0 (q) describe modes of free oscillation of the system, which we
call collective modes.
In many senses, the collective modes of a system are particles that are just as real as the
atoms and nuclei which the solid was built from in the first place. This is in spite of the fact
that the collective modes only exist inside the solid. The spectrum of collective excitations
often represents the most we can know about many systems, and so a system for which we
can accurately predict the observed spectrum of collective modes is a system we can regard
as understood. This is one of the reasons that low temperature physics has played such a
central role in the development of solid state physics weakly excited collective modes are
usually much simpler to understand.
Collective modes are directly related to the pole structure of the response function (q, ).
Poles close to the real frequency axis correspond to sharp resonances, while a continuum of
excitations gives broad features in the spectrum. (A continuum of poles can be represented
by a branch cut.)
Examples of collective modes in solids include
phonons (elastic waves)
plasmons (charge fluctuations with longitudinal polarization)
exitons (bound electronhole pairs)
magnons (spin density waves)
spinons and holons (fractionalized electrons)
Landau quasiparticles (electron-like quasiparticles)
Laughlin quasiparticles (charge e/3 carriers in the fractional quantum Hall effect)
Bogoliubov quasiparticles (linear combinations of particles and holes that are the fundamental excitations of a superconductor)
26.3
Inelastic scattering
Collective modes may be directly visible in an inelastic scattering experiment. The idea is
to send in a beam of radiation or particles of momentum q and frequency , and measure
the frequency and momentum of the scattered particles or radiation. The energy absorption
is proportional to Im{(q, )}. Experiments of this sort include:
Raman and Brillouin scattering (inelastic scattering of visible light)
Inelastic x-ray scattering
Angle resolved photoemission (the ejection of electrons from solids using UV light)
26.4. CAUSALITY
80
CHAPTER 4. COLLECTIVE PHENOMENA
223
Figure 4.2: Generic description of an inelastic scattering experiment
Figure 26.1: Inelastic scattering probes excite collective excitations of the solid.
both in frequency and energy. By comparing the incident and outgoing
energy and momenta, one can then deduce the spectrum of excitations. If
excitations(inelastic
are underdamped
(polesofclose
to the neutron
real frequency
axis) then
Neutronthe
scattering
scattering
thermal
beams)
the features will appear as sharp resonances; continuum excitations will lead
to broad features. Very generally , the probability of making an excitation
momentum qspectroscopy
and energy is(inelastic
proportional
to
Electronof energy-loss
scattering
of an incident electron beam)
=(q, )
(4.33)
In all cases a direct measure of the spectrum of excitations is obtained by comparing the
of course multiplied by matrix elements and selection rules appropriate for
incident and outgoing
energy and
momenta.
4
26.4
the probe at hand.

The collective modes are just waves propagating through the solid; in
the examples above they are waves of atomic vibration (phonons), of longitudinal polarisation (plasmons),or of transverse electric field (light). Later
on we shall see other examples, e.g. spin waves.
Causality
Causality
andsystems
Kramers-Kr
nigcausal.
relations
The response4.1.6
functions
of physical
must obe
Causality requires that
The response functions we are using must be causal or retarded, so that
there is no possibility of(t
a response
t0 ) =before
0 if thet force
< t0 . is applied, i.e. a causal
response function must satisfy
(26.4)
(t
) = 0response
if t0 > t function
.
(4.34)concentrate on
(We neglect the position dependence
oft0the
for now and
the time dependence.) That is, the state of the system cannot depend on things that have
The principle of causality imposes conditions on the behaviour of () in
not yet happened.
This sounds obvious and simple, but it has important consequences and
Fourier space (we shall drop the momentum or space coordinate for the
is extremely useful
for ()
experimentalists,
allowing
themof to
infer
about
the system that
function
in
the things
upper half
plane,
moment):
must be an analytic
are not easily or4 We
directly
accessible
by
experiment.
shall use the symbols = (Imaginary part), < (Real part) and (Principal value).
To see the utility of the causal nature of response functions, we need to turn to the complex
frequency plane. (t t0 ) is the inverse Fourier transform of (), and for it to be zero
for t < t0 , () must be analytic in the upper half plane. This analyticity in turn enforces
strict relationships, called KramersKronig relations, between the real and imaginary parts
of (), which we respectively label 0 () and 00 (). (i.e. () = 0 () + i00 ().)
We will derive the KramersKronig relations in two ways. First, using complex function theory, and second, using a physical argument for the specific case of the electrical conductivity.
224
We start by defining the Fourier-transform pair:

Z
(t)eit dt
() =
Z
1
(t) =
()eit d.
2
(26.5)
(26.6)
>
Figure 26.2: Contours for evaluating the Fourier transform.

We can obtain (t) by evaluating the inverse Fourier transform as a contour integral, using
one of two contours depending on whether t > 0 or t < 0: if t < 0 we close the contour in the
upper half plane; and if t > 0 in the lower half plane. Provided |()| falls off faster than
1/, the closing contour at infinity doesnt contribute to the integral. Using the calculus of
residues
Z
1
()eit d
(26.7)
(t) =
2
I
1
=
()eit d
(26.8)
2
X
= 2i
residues.
(26.9)
By causality (t) = 0 for t < 0 so there can be no poles in the upper half plane. Therefore
() is analytic for Im{} > 0. In order to show that this places strict constraints on the
real and imaginary parts of (), we need a way of relating 0 () and 00 (). We do this
using Cauchys theorem, another result from the calculus of residues.
I
d 0 ( 0 )
() ( + i) =
,
(26.10)
2i 0 i
where, because () is analytic in the upper half plane, the contour enclosing the pole at
+ i can be deformed to run along the entire length of the real axis.
26.5. OPTICAL CONDUCTIVITY
225
'=+i
'=+i
Figure 26.3: Contours used for evaluating the Cauchy integral.
Setting to zero,
d 0 ( 0 )
2i 0
Z
I
d 0 ( 0 )
1
d 0 ( 0 )
= P
+
2i 0 2
2i 0
Z
d 0 ( 0 )
= P
+ 12 ().
0
2i
() =
(26.11)
(26.12)
(26.13)
Here P denotes the principle-part integral (i.e. the integral along the real axis, taking symmetric limits when approaching any poles on the axis.) Therefore
Z
d 0 ( 0 )
() = P
.
(26.14)
0
i
We can now use this to relate 0 () to 00 () and vice versa.
Z
d 0 00 ( 0 )
0
() = P
0

Z
d 0 0 ( 0 )
00 () = P
0

(26.15)
(26.16)
(26.17)
These are the KramersKronig relations for causal response functions. We usually write
KramersKronig relations in terms of positive frequency, but this requires us to know the
symmetry of 0 () and 00 () under the tranformation , which is different for the
various response functions. We will now look at how this applies in the specific case of the
electrical conductivity.
26.5
Optical conductivity
The electrical conductivity or optical conductivity relates the current to the electric field
at earlier times.
Z
J(t) =
(t t0 )E(t0 )dt0
(26.18)
226
By causality (t t0 ) ( ) = 0 for < 0. We can therefore multiply ( ) by ( ), the

unit step function, without changing anything.
( ) = ( )( )
(26.19)
The convolution theorem states that the Fourier transform of a product is the convolution
of the Fourier transforms, so
Z
d 0
( 0 )( 0 )
() =
,
(26.20)
2
where () is the transform of the step function:

Z
eitt dt.
() =
(26.21)
Here is an infinitesimal that makes the integral converge. For 6= 0,

h
() = lim
i
1
eitt
i
0
(26.22)
i
.
(26.23)
For = 0, we can use the definition of the Dirac delta function,

Z
1
() =
eit dt.
2
(26.24)
This can all be brought together as

i
() = () + P
,
(26.25)
Both () and P() are well defined only within an integral.

Using this result
Z
d 0
() =
( 0 )( 0 )
2

0
Z
i
d
0
0
=
( ) ( ) + P
0
Z
0
d
i
= 12 () + P
( 0 )
.
0
2
This implies that
Z
() = P
d 0 ( 0 )
,
i 0
(26.27)
(26.28)
(26.29)
the same result we obtained using Cauchys theorem.

(26.26)
26.6. OSCILLATOR STRENGTH SUM RULE
227
Let () = 1 () + i2 (), where 1 and 2 are real. Then the KramersKronig relations
for the optical conductivity are
Z
2 ( 0 ) 0
1
P
d ,
(26.30)
1 () =
0

Z
1 ( 0 ) 0
1
d .
(26.31)
2 () = P
0

One consequence of this is that, for a superconductor, which has an infinite dc conductivity
1 () = C(),
(26.32)
there must be a corresponding term in the imaginary part of the conductivity,

2 () =
C1
,
(26.33)
which is purely inductive and correponds to the kinetic energy of the superelectrons.
We have already seen, in the context of the periodic potential, that the Fourier transform of
a real function, in this case ( ), has the property
() = ().
(26.34)
() = 1 () + i2 () = 1 () i2 ().
(26.35)
1 () = 1 (),
2 () = 2 ().
(26.36)
(26.37)
Therefore
This implies that
We can therefore write the KramersKronig relations as integrals over positive frequencies.
Z 0
2 ( 0 ) 0
2
1 () =
P
d
(26.38)
02 2
0
Z
2
1 ( 0 )
2 () = P
d 0
(26.39)
02 2
26.6
Oscillator strength sum rule
If we evaluate the electrical conductivity in the relaxation time approximation, we find that
() =
ne2
1
,
m 1 i
(26.40)
where is the relaxation time of the system. We now imagine hitting the system with
an impulse of electric field, so that the time over which the field is applied is so short the
system cannot relax to equilibrium. This is equivalent to going to very high frequencies
228
in the conductivity. The details of the relaxation processes are then unimportant and the
following discussion is completely general.1 In the high frequency limit,
ine2
()
m
ne2
2 () =
m
ne2
.
lim 2 () =
(26.41)
(26.42)
(26.43)
We now bring in the second KramersKronig relation, and find that

Z
2 2
1 ( 0 )
lim 2 () = lim
P
d 0
2 02
0
Z
2
=
P
1 ( 0 )d 0
0
ne2
.
=
m
(26.44)
(26.45)
(26.46)
This is usually written in the form

Z
P
0
1 ( 0 )d 0 =
ne2
,
2 m
(26.47)
where it is called the oscillator-strength sum rule or f-sum rule. Oscillator strength refers to
the frequency integral of the conductivity. What the rule says is that as the temperature of a
system is changed, or as the effective interaction strength is tuned, the oscillator strength can
be redistributed in frequency subject to the constraint that its frequency integral be fixed.
As an example, consider a superconductor. As it is cooled through the superconducting
transition temperature, the onset of superconductivity suppresses all electronic transitions
below an energy 2. This opens a gap in the optical conductivity, up to a frequency ~ = 2.
Any conductivity spectral weight that was in this frequency range above the transition
temperature must now condense into a zero-frequency delta function, and becomes associated
with the reactive response of the superfluid.
Not only are scattering processes unimportant but, if the applied impulse is short enough, so are the
interactions of the electrons with the nuclei and the other electrons. For the purposes of the sum rule
argument, the electron density is the total electron density, and the mass the bare electron mass. In practice
there is a hierarchy of time and frequency scales, corresponding to interaction effects at low energies, band
formation, and atomic energies, and a corresponding hierarchy of effective masses.
Lecture 27
The electron spectral function
27.1
The Schr
odinger representation
The most familiar representation of quantum mechanics is the Schrodinger representation.

In it, the wavefunction |S (t)i evolves in time according to the Schrodinger equation
i~
|S (t)i
= H|S (t)i.
t
(27.1)
This has a formal solution

|(t)i = eiH(tt0 )/~ |(t0 )i.
(27.2)
S . Measurements of
Physical observables are represented by time-independent operators O
the observable involve calculation of matrix elements and expectation values.
S i = hS |O
S |S i
hO
(27.3)
In many body systems it is more convenient to factor the time dependence out of the wavefunctions.
27.2
The Heisenberg representation
In the Heisenberg representation, the state vectors |H i are time independent. All the time
H (t).
dependence goes into the operators O
We can go between Schrodinger and Heisenberg representations by a unitary transformation:
|H i = eiH(tt0 )/~ |S (t)i = |S (t0 )i
S eiH(tt0 )/~ .
H (t) = eiH(tt0 )/~ O
O
(27.4)
(27.5)
This transformation leaves all matrix elements (and all physical observables) unchanged.
The hamiltonian is also unchanged by the transformation, because it commutes with itself
in the exponential factors.
229
230
LECTURE 27. THE ELECTRON SPECTRAL FUNCTION
The time dependence of the operators (instead of the state functions) is computed using the
following equation of motion:
i~
H (t)
O
HH H O
H = [O
H , H].
=O
t
(27.6)
This is called the Heisenberg equation of motion.
27.3
Particles and quasiparticles
We usually think of electrons as fundamental particles. But this no longer makes sense in
a solid, because an individual electron cannot be separated from the rest of the interacting
electron liquid. The best we can do is think of experiments we might perform to study the
electron-like excitations. One of the most direct experiments is to insert an electron into
a state |pi at time t = 0, and remove an electron from a state |p0 i at a later time t. The
probability of propagating from one state to the other is related to the expectation value
G(p0 , t; p, 0) = ihG |T [cp0 (t)cp (0)]|G i.
(27.7)
Here G is the ground state wavefunction of the many-body system, and T is the timeordering operator. That is,
T [c(t)c (t0 )] = c(t)c (t0 ), t > t0
= c (t0 )c(t), t0 > t.
(27.8)
(27.9)
This orders the operators according to which one is earlier and is necessary because we
want to calculate a causal response function. G(p0 , t; p, 0) is called the Greens function or
propagator.
These operators are in the Heisenberg representation, so
c(t) = eiHt/~ ceiHt/~ ,
(27.10)
where c(t = 0) c.
We will now look at some examples.
27.4
A single free particle
A single free particle has the hamiltonian

H0 =
p cp cp .
(27.11)
27.4. A SINGLE FREE PARTICLE
231
The Heisenberg equation of motion is

i~
cp (t)
= [cp (t), H]
t
= eiHt/~ p [cp , cp cp ]eiHt/~
(27.12)
(27.13)
= eiHt/~ p (cp cp cp cp cp cp )eiHt/~
(27.14)
= eiHt/~ p (1 cp cp )cp eiHt/~

= p cp (t).
(27.15)
(27.16)
This has solution

cp (t) = cp eip t/~ .
(27.17)
cp (t)
= p cp (t),
t
(27.18)
cp (t) = cp eip t/~ .
(27.19)
Similarly
i~
and
We can now evaluate the free particle propagator or Greens function, by taking the expectation value in the vacuum state.
G0 (p0 , t; p, 0) = ih0|T [cp0 (t)cp (0)|0i
(27.20)
For t > 0
G0 (p0 , t; p, 0) = ieip t/~ h0|cp0 (0)cp (0)|0i
(27.21)
= ieip t/~ h0|(1 cp cp |0ip0 p
(27.22)
= ieip t/~ p0 p .
(27.23)
For t < 0, G0 = 0. (cp0 acts directly on the vacuum.) The time-ordering operator enforces
causality. Momentum is also conserved.
(In a solid, G(p, t < 0) represents the propagation of holes. In a solid the vaccum is a filled
Fermi sea, and acting on it with an annhilation operator just creates a hole.)
We are often interested in the Fourier transform of G, which gives us its energy dependence.
Z
G(p, t)eit dt
G(p, ) =
(27.24)
1
G(p, t) =
2
G(p, )eit d
(27.25)
232
For a free particle

Z
G0 (p, t)eit dt
G0 (p, ) =
(27.26)
ei(p /~+i)t dt
0
h
i
1
ei(p /~+i)t
=
p /~ + i
0
1
.
=
p /~ + i
= i
(27.27)
(27.28)
(27.29)
Here is a positive infinitesimal convergence factor. In a solid we have the possibility of

propagating holes and would in that case use a negative infinitesimal = 0 .
Using the identity

1
1
lim+
=P
i(x)
(27.30)
0 x + i
x
we can write the free-particle Greens function as

1
i( p /~).
G0 (p, ) = P
p /~
27.5
(27.31)
The spectral function
The spectral function A(p, ) is defined to be the imaginary part of the Greens function.
1
A(p, ) = Im{G(p, )}
(27.32)
A(p, ) = ( p /~).
(27.33)
For noninteracting particles

The spectral function has a straightforward interpretation it is the probability of finding
a quasiparticle excitation of momentum p with energy ~. For noninteracting particles, we
only find excitations at the band energy p , hence the delta function. This is illustrated in
Fig. 27.1.
The Greens function as we have defined it above is a causal response function. As a result,
its imaginary part the spectral function contains all the information of the full Greens
function. This is made explicit using the Lehmann representation:
Z
A(p, 0 )
G(p, ) =
d 0 .
(27.34)
0 + i
The causal Greens function is also known as the retarded Greens function, because it describes how a particle propagates to a distant point at a later time. In a solid, the Greens
function for holes is an advanced Greens function.
27.6. INTERACTING SYSTEMS
233
Figure 27.1: The spectral function of a noninteracting electron system. (From Damascelli,
Hussain and Shen[25].)
27.6
Interacting systems
The Greens function for an interacting system must be different from a noninteracting
Greens function. But if the interactions are weak, as they are in many real systems, the
Greens function should not be too different from a free particle propagator. We can guess
what the answer would look like a single state interacting with a continuum of levels will
decay in time. In the Schrodinger representation we would expect our wavefunction to look
like
S (t) eip t/~p t ,
(27.35)
where is the (momentum-dependent) decay rate. If p /~ the quasiparticle will still
be well defined. We would then expect for the Greens function
G(p, t) = iZp eip t/~ ep t (t),
(27.36)
where (t) is the unit step function and the amplitude Zp is the so-called quasiparticle
renormalization factor. Zp 1. In frequency space this is
Zp
.
p /~ + ip
(27.37)
1
Zp p
.
( p /~)2 + 2p
(27.38)
G(p, ) =
The corresponding spectral function is
A(p, ) =
This is a Lorentzian with total weight
Z
A(p, )d = Zp .
(27.39)
234
It can be shown rigorously that

Z
A(p, )d = 1.
(27.40)
That is, the probability of finding the excitation of momentum p at some energy is 1, even
in the presence of interactions. The effect of interactions is to move some of the spectral
weight from the quasiparticle peak to a broad, incoherent part of the Greens function.
Figure 27.2: The spectral function for an interacting electron system. (From Damascelli,
Hussain and Shen[25].)
In general, the exact Greens function for the interacting system can be written
G(p, ) =
1
.
p /~ (p, )
(27.41)
(p, ) is called the self energy. Its real part, 0 (p, ), shifts the excitation energies and
describes the effect of interactions on the velocity of the quasiparticle. Its imaginary part,
00 (p, ), is related to damping. The Greens function can also be written
G(p, ) =
1
+ Gincoh (p, ),
p /~ + ip
(27.42)
where p is the renormalized quasiparticle energy dispersion (frequency independent) and

Gincoh (p, ) is the incoherent part of the Greens function, which usually contributes a broad
background to the spectral function that continues up to high energies. The spectral function
for an interacting system is plotted in Fig. 27.2.
27.7. ANGLE RESOLVED PHOTOEMISSION SPECTROSCOPY
27.7
235
Angle resolved photoemission spectroscopy
The most direct way to measure the electron spectral function is by angle resolved photoemission spectroscopy, or ARPES. Photons are incident on a single crystal sample, and cause
transitions from low-energy occupied states to empty, plane-wave-like states well above the
vacuum energy. The excited photoelectron leaves the sample and is collected in a detector
that measures both the energy and momentum of the photoelectron. The photons typically
have ultraviolet wavelengths, with energies of about 20 eV, and carry very little momentum
compared to electrons. The transitions are therefore vertical (i.e. do not appreciably change
the momentum of the electron) so the component of the momentum of the photo-emitted
electron parallel to the sample surface is the same as the parallel component of the momentum
of the low-energy initial state. The perpendicular component of the momentum is not
conserved, because the presence of the sample surface breaks translational symmetry. The
process is sketched in Fig. 27.3 and the geometry is shown in Fig. 27.4.
Figure 27.3: The energetics of photoemission. (From Damascelli, Hussain and Shen[25].)
236
Figure 27.4: The experimental geometry for angle-resolved photoemission. (From Damascelli, Hussain and Shen[25].)
In angle resolved photoemission, an analyzer measures the kinetic energy

of the emitted
electrons, Ekin . This also sets the magnitude of the momentum |p| = 2mEkin . The components of the momentum perpendicular and parallel to the surface are determined by the
polar angle and azimuthal angle .
p
= cos
|p|
px
= sin cos
|p|
py
= sin sin
|p|
(27.43)
(27.44)
(27.45)
The energy of the electron before being photoexcited can be calculated by energy conservation. This quantity is also called the binding energy EB , measured down in energy from
the chemical potential .
EB = .
(27.46)
This is obtained from the kinetic energy of the emitted electron:
Ekin = h |EB |,
(27.47)
where is the work function of the surface.

A typical experimental set up is shown in Fig. 27.5. Because only parallel components of
the momentum are conserved, ARPES works best on materials with two-dimensional or
one-dimensional electronic structure. As an example, the ARPES-measured Fermi surface
of Sr2 RuO4 is shown in Fig. 27.6.
27.7. ANGLE RESOLVED PHOTOEMISSION SPECTROSCOPY
237
Figure 27.5: The experimental configuration of a synchrotron-based photoemission experiment. (From Damascelli, Hussain and Shen[25].)
238
Figure 27.6: ARPES spectra for Sr2 RuO4 , with the ARPES-derived Fermi surface and a
theoretical Fermi surface. (From Damascelli et al. [26].)
Lecture 28
Landaus Fermi Liquid theory
Fermi liquid theory was originally developed by Lev Landau to describe the physics of 3 He.
It has been useful far beyond its initial application, being generally applicable to degenerate
interacting Fermi systems as diverse as neutron stars and atomic nuclei. In addition, it has
become the Standard Model of the metallic state of solids. Indeed, in analogy to particle
physics, much current research is devoted to looking for physics beyond this standard model.
Landaus Fermi liquid theory explains why a system of strongly interacting particles can
behave to a very high degree like a set of independent particles, and provides a way of
incorporating the effects of interactions in a phenomenological way. The basic idea is to
focus on the excitations of the interacting system without worrying about the precise form
of the ground state. The elementary excitations act like particles, and are therefore called
quasiparticles. The energies of the quasiparticles are nearly additive.1 Complicated states,
such as conventional superconducting states, can be formed by adding together many quasiparticles. The quasiparticles interact with each other, but far less strongly than the original
particles of the theory from which they are constructed.
28.1
The noninteracting Fermi gas
In the limit that T 0, the FermiDirac distribution becomes a step function, and the
electron system is said to be fully degenerate. In this regime, the number of excited states
available to the system is greatly reduced, with striking consequences for the physical properties of the system: the specific heat becomes proportional to T , instead of T -independent; and
the spin susceptibility becomes temperature independent instead of varying with a Curie-like
1/T power law.
In a real fermion system, particle interactions and the exclusion principle are both important,
leading to the study of degenerate Fermi liquids. Sometimes the properties of the interacting
system are drastically modified by interactions, such as in superconductors and Mott insulators. In many cases, however, the interacting liquid retains many properties of the gas. It
is then called a normal Fermi liquid.
1
Remember, our definition of a noninteracting system is one in which the total energy can be found by
adding up the single-particle energies.
239
240
LECTURE 28. LANDAUS FERMI LIQUID THEORY
n0
1
pF
Figure 28.1: The ground state distribution function.
Consider a system of N noninteracting free fermions, each of mass m, enclosed in a volume V .

Eigenstates are antisymmetrized combinations of N different single particle states, with each
particle represented by is momentum p and spin = 12 and corresponding wavefunction
1
p (r) = eipr/~ .
V
(28.1)
The eigenstates of the system can be characterized by the distribution function np :

np = 1 if |p, i is occupied,
= 0 otherwise.
(28.2)
(28.3)
The eigenenergies are

p =
p2
,
2m
(28.4)
and the total energy is additive:

E=
X
p,
np
p2
.
2m
(28.5)
The states are filled according to the exclusion principle, up to the Fermi momentum
1
pF = ~(3 2 N/V ) 3 .
(28.6)
The Fermi surface is a sphere of radius pF .

Now add a single particle. In the ground state of the N + 1 particle system, the additional
particle occupies a state on the Fermi surface, and adds an energy equal to the chemical
potential . The change in ground state energy is
= E0 (N + 1) E0 (N ) =
E0
p2
= F.
N
2m
(28.7)
28.2. EXCITED STATES
28.2
241
Excited states
Excited states are specified with respect to the ground state. A given excited state is obtained
by exciting a certain number of particles across the Fermi surface. This creates an equal
number of particles outside the Fermi surface and holes inside the Fermi surface. Particles
and holes are therefore the elementary excitations of the system, as illustrated in Fig. 28.2.
The amount of excitation is characterized by the departure of the distribution function from
Figure 28.2: Particle and hole excitations near the Fermi surface. (From Schofield[1].)
its ground-state value. (We will ignore spin for now.)
np = np n0p .
(28.8)
If we have a particle excitation of momentum p0 > pF ,

np = pp0 .
(28.9)
A hole excitation with p0 < pF corresponds to

np = pp0 .
(28.10)
For a noninteracting system

E E0 =
X p2
np .
2m
p
(28.11)
At low temperature, np is O(1) only in the immediate vicinity of the Fermi surface.
In an isolated system, the total number of particles is conserved, which requires that the
number of excited particles equals the number of excited holes. This restriction can be
inconvenient, so we switch to the grand canonical ensemble. The free energy is
F = E N

X p2
F F0 =
np .
2m
p
(28.12)
(28.13)
242
The free energy associated with particles is p2 /2m . Inside the Fermi surface, np < 0, so
the free energy for holes is p2 /2m. The free energy for elementary excitations if therefore
2

p

.
(28.14)
2m

The excitation energy is always positive, ensuring the stability of the ground state.
28.2.1
Heat capacity
We calculated the heat capacity of a noninteracting Fermi gas in Lecture 3 using the Sommerfeld expansion. The result was
cV =
2 2
k T D(F ),
3 B
(28.15)
where D(F ) is the density of states at the Fermi level.
28.2.2
Pauli spin susceptibility
We now calculate the Pauli spin suscepstibility, ignoring orbital effects. In that case, the
application of a magnetic field leads to Zeeman splitting of the energy levels. The field will
raise the energy of the up-spin electrons by an amount
= gB B
B B.
(28.16)
(28.17)
The down-spin electrons are lowered in energy by

= B B.
(28.18)
The two spin sub-bands will come into equilibrium with equal chemical potentials, as shown
in Fig. 28.3. The number of up spins is
N =
N
12 B BD(F )V.
2
(28.19)
N
+ 12 B BD(F )V.
2
(28.20)
Similarly, the number of down spins is

N =
The spin polarization is N N = B BV D(F ) and the net magnetization M = B (N N ).

The magnetization per unit volume is m = M/V . The susceptibility is
dm
dm
0
dH
dB
= 0 2B D(F ).
(28.21)
(28.22)
The Pauli spin susceptibility is temperature independent, because the number of excitations
( T ) goes oppositely to the Curie susceptibility ( 1/T ).
28.3. LANDAU QUASIPARTICLES
243
}2BB
}2BB
D()
D()
D()
Figure 28.3: Partial spin polarization of a Fermi gas by the application of a magnetic field.
28.3
Landau quasiparticles
Landau considered a fictitious model in which the interactions between particles could be
switched on and off at will. He then imagined starting in the distant past with a noninteracting system and slowly switching the inter-particle interactions on. According to the
adiabatic principle of quantum mechanics (see Lecture 23), if the interaction is switched
on slowly enough a system starting in an eigenstate of the noninteracting system will remain in the corresponding eigenstate of the interacting system at a later time t. That is,
the particles of the noninteracting system will smoothly become the quasiparticles of the
interacting system, with a rigorous one-to-one correspondence. We can imagine carrying
out a procedure in which we map out the spectrum of the excited quasiparticle states by
starting off in an excited state of the noninteracting system and following its development
as we switch on interactions.2 This exposes the chief limitation of Fermi liquid theory in
2
There is no guarantee that this will generate all eigenstates and, in particular, the ground state. We will
assume, however, that is does, thereby restricting ourselves to normal Fermi liquids.
244
order for the adiabatic theorem to apply, the time taken to switch on the interactions must
be large compared to ~/, where is the minimum spacing between the energy levels of
the system. If a degeneracy occurs while we are switching on the interaction it will become
impossible to proceed any further. We will then have found an instability of the Fermi liquid.
In addition, in order to map out the excitation spectrum of the Fermi liquid, we will need
to be able to switch the interaction on in a time that is short compared to the decay time
of the excited state, 1/(). A calculation of the decay rate shows that there should exist a
range of energies for which this is possible.
Figure 28.4: Illustration of the adiabatic principle using an example from single particle
quantum mechanics. A harmonic potential is gradually added to the square-well potential, smoothing perturbing the eigenstates and energies. The states of the perturbed and
unperturbed systems exist in one-to-one correspondence. (From Schofield[1].)
28.4
Quasiparticle decay rate
Imagine a single particle of momentum |p1 | > pF above a filled Fermi sea. It interacts with
a particle of momentum |p2 | < pF within the Fermi sea. As a result, the particles scatter
and two particles appear above the Fermi sea, with momenta p3 and p4 = p1 + p2 p3 .
|p3 |, |p4 | > pF . Another way of looking at the same process is to say the particle with
momentum p1 has decayed into two particles, of momenta p3 and p4 respectively, and a
hole with momentum p2 .
The total probability of this process is given by Fermis golden rule and is proportional to
Z
(1 + 2 3 4 )dp2 dp3 ,
(28.23)
28.4. QUASIPARTICLE DECAY RATE
245
p3
p1
p2
p4
Figure 28.5: Kinematics places tight constraints on the decay of quasiparticles near the Fermi
surface.
subject to the constraint that |p2 | < pF , |p3 | > pF and |p4 | = |p1 + p2 p3 | > pF . For
|p1 | pF pF ,
2pF |p1 | < |p2 | < pF
pF < |p3 | < |p1 | + |p2 | pF
(28.24)
(28.25)
The angle between p1 and p2 is arbitrary. The angle between p3 and p1 + p2 is fixed by
energy conservation. This leaves integrals over the magnitudes of p2 and p3 . The decay rate
is then proportional to
Z
pF
p1 +p2 pF
dp2
2pF p1
dp3 =
pF
1
(p1 pF )2
2
(1 F )2 .
(28.26)
(28.27)
As the particle gets closer and closer to the Fermi surface, it becomes increasingly difficult
to satisfy the kinematic constraints and find final states for it to recoil into after scattering.
At finite temperature, T plays the role of energy, setting the characteristic spread of the
thermal distribution about the Fermi surface. The Fermi liquid decay rate is then
1
= a(1 F )2 + b(kB T )2 ,
(28.28)
where a and b are constants. The larger of temperature or energy dominates. For states
near the Fermi surface, becomes arbitrarily long, and we can apply the adiabatic principle.
The kinematic constraints on the decay rate lead to a characteristic form for the electrical
resistivity
1
(T ) T 2 .
(28.29)
This is often taken as an identifying signature of Fermi liquid behaviour.

246
28.5
Landaus Fermi liquid theory
The total energy of the system is a functional of the departure from the ground state distribution.
X
E[np ] = E0 +
p np + O(n)2
(28.30)
p
The functional derivative E/(np ) is the quasiparticle excitation energy qp

p . The quasiparticle velocity is defined in terms of this energy:
vp = p qp
p .
(28.31)
We can also define an effective mass m through

pF
vF = .
(28.32)
m
Mass renormalization is not the only difference between the an electron gas and a Fermi
liquid!
28.5.1
Interactions between quasiparticles
For the calculation of most physical properties it is necessary to extend the expansion of
the energy to second order in the distribution function. We will now include spin explicitly
again.
X
1 X
f (p, ; p0 , 0 )np, np0 ,0 + O(n)3
(28.33)
0p np, +
E E0 =
2V
0
0
p,
p,;p ,
Here 0p = vF (p pF ). The quasiparticle energies are again given by the functional derivative
1 X
E
=
v
(p
p
)
+
qp
=
f (p, ; p0 , 0 )np0 ,0 .
(28.34)
F
F
p
(np, )
V p0 ,0
The energy of an individual quasiparticle excitation now depends on the occupation of other
quasiparticle states! This is a new feature of the Fermi liquid theory and represents interaction between the quasiparticles. All details of the interactions (which are weak) are
contained in the Landau f -function f (p, ; p0 , 0 ).
At low temperatures, where the Landau Fermi liquid theory holds, np, is O(1) only in the
immediate vicinity of the Fermi surface. It is therefore only necessary to define f on the Fermi
surface. (That is, the interaction function f (p, ; p0 , 0 ) wont depend on the magnitude of
the momenta, only on the angles). For the problem Landau first considered, that of 3 He,
the system is spherically symmetric. This rotational invariance means that the interaction
energy only depends on the angle between p and p0 . In addition, it must be symmetric under
interchange of p and p0 , so it can be expanded as a function of cos = p p0 /p2F . The usual
method is to use a set of orthogonal polynomials called the Legendre polynomials P` (cos ).
P0 (cos ) = 1
P1 (cos ) = cos
P2 (cos ) = 12 (3 cos2 1) etc.
(28.35)
(28.36)
(28.37)
28.6. EXPERIMENTAL CONSEQUENCES OF FERMI LIQUID THEORY
247
The most important spin-dependent part of the interaction is the exchange interaction, which
is invariant under a global spin rotation and therefore only depends on the relative angle of
the spins 0 . In the Russian literature the f function is written in a compact way as
f (p, ; p0 , 0 ) pp0 + 0 pp0 .
(28.38)
Another way to do the same thing is to break the interaction up into spin-symmetric and
spin-antisymmetric parts. This is more transparent but less compact. The up-spin and
down-spin quasiparticle energies are then

o
1 Xn S
qp
A
f P` (cos ) np0 + np0 + f` P` (cos ) np0 np0
(28.39)
p = vF (p pF ) +
V p0 ,` `
qp
p
o

1 Xn S
A
0
0
0
0
= vF (p pF ) +
f P` (cos ) np + np f` P` (cos ) np np , (28.40)
V p0 ,` `
where S and A stand for spin-symmetric and spin-antisymmetric parts of the interaction
respectively.
28.6
Experimental consequences of Fermi liquid theory
Different experimental probes polarize the Fermi surface in different ways, and therefore
couple to different angular harmonics of the Landau f function. Examples include:
Heat capacity
By changing the temperature we broaden the FermiDirac distribution as shown in
Fig. 28.6(a). We dont couple to any angular harmonics, because the broadening leads
to a change in the distribution function that averages to zero about the Fermi energy.
The heat capacity is therefore unrenormalized by Fermi liquid interactions.
Compressibility
In a compressibility experiment we shrink or expand the Fermi distribution symmetrically in k-space, as shown in Fig. 28.6(b). The change in pF is uniform around the
Fermi surface and is achieved by changing the density of the particles. A compressive polarization couples to the spin-symmetric, ` = 0 (monopolar) component of the
interaction. The speed of sound will be renormalized by the f0S Landau parameter.
Susceptibility
In an applied magnetic field the density of spin-up particles decreases with a corresponding increase in the density of spin-down particles. The distribution functions change as in Fig. 28.6(c). Like a hydrostatic compression, this is an ` = 0
(monopolar) polarization of the distribution function, but in this case the change is
spin-antisymmetric. A magnetic polarization therefore couples to the f0A Landau parameter.
Charge currents. A charge current displaces the Fermi surface in k-space, as shown
in Fig. 28.6(d). This is a spin-symmetric, dipolar perturbation that couples to the f1S
Landau parameter.
248
(a)
(b)
(c)
(d)
Figure 28.6: Different polarizations of the distribution function: (a) heating the distribution;
(b) compression; (c) spin polarization; and (d) a charge current.
28.6.1
Heat capacity
Because heating the Fermi liquid doesnt couple to any angular harmonic, the heat capacity
does not depend on the Landau interaction parameters and retains the free electron form
cV =
2 2
k T D(F ).
3 B
(28.41)
However, the Fermi velocity is renormalized in a Fermi liquid, which affects the density of
states D(F ).
m kF
D(F ) = 2 2 ,
(28.42)
~
so
m kF 2
cV =
k T
(28.43)
3~2 B
for the interacting Fermi liquid. Measurements of heat capacity therefore have the ability
to directly probe the effective mass enhancement, without additional affects from Landau
parameters.
28.6.2
Spin susceptibility
A magnetic field B spin polarizes the quasiparticles, as we saw above for the noninteracting
system. However, the energetics are changed by the presence of the Landau parameters. A
spin polarization will couple to the spin-antisymmetric, monopolar parameter f0A . In the
presence of a magnetic field, the change in energy of the up-spin electrons will be
E = B B +
1 X S
f (np + np ) + f0A (np np )
V p 0
(28.44)
The magnetization is given by

M = B
(np np )
(28.45)
28.6. EXPERIMENTAL CONSEQUENCES OF FERMI LIQUID THEORY

and there is an overall constraint of fixed particle number
X
(np + np ) = 0.
249
(28.46)
We can therefore write the energy shift as

E = B B
M f0A
.
B V
(28.47)
This lets us determine the degree of spin polarization.

N
12 ED(F )V
2
N
=
+ 12 ED(F )V
2
N =
(28.48)
(28.49)
The net magnetization is then

M = B (N N )

M f0A
= B D(F )V B B
B V
2
= B D(F )V B M D(F )f0A
2B D(F )V B
=
1 + D(F )f0A
2B D(F )V B
=
,
1 + F0A
(28.50)
(28.51)
(28.52)
(28.53)
(28.54)
where F0A is a dimensionless Landau parameter, obtained by scaling the interaction parameters by the density of states.
The susceptibility is
0 dM
V dB
0 2B D(F )
=
.
1 + F0A
(28.55)
(28.56)
This is modified from the free electron result by D(F ) m and by the presence of F0A .
This is not as innocuous a change as for the heat capacity when F0A = 1 there is a
transition to a ferromagnetic state. This is called the Stoner instability.
250
Lecture 29
Superconductivity I
phenomenology
References: the two books giving the best introduction to superconductivity are those by Tinkham[27] and
Waldram[28]. Taylor and Heinonen[7] give good, succinct explanations of some of the key phenomena.
29.1
Superconductivity
We finish this lecture course with a short survey of superconductivity, a subject that has
been at the forefront of experimental and theoretical physics research for almost one hundred years. With no disrespect for theory intended, superconductivity is an example of a
phenomenon that could only have been discovered by experiment. The physical effects associated with superconductivity are so diverse and fantastic that had they been predicted
ahead of time the theory would not have been believed. As it was, it took almost 50 years
and a complete quantum theory of solids before a satisfactory explanation of superconductivity was obtained. Every detail of the resulting BardeenCooperSchrieffer (BCS) theory
has since been confirmed experimentally. The microscopic theory in turn led to many new
discoveries and applications, most notable among them the Josephson effect. Superconductivity continues to be a vibrant field with whole new classes of superconductors discovered
every decade or so. The most famous of these discoveries was high temperature superconductivity in copper oxide or cuprate materials, in 1986. Over 20 years later, this remains
one of the most important unsolved problems in correlated electron physics. Other classes
of superconductors include organic superconductors and the so-called heavy fermion superconductors, in which the electron quasiparticles have effective masses approaching that of a
proton or a neutron.
29.2
Perfect conductivity
Shortly after liquefying helium in Leiden, Kammerlingh Onnes started studying the electrical
resistivity of various metals in the zero-temperature limit, with a view to testing how far the
251
252
LECTURE 29. SUPERCONDUCTIVITY I PHENOMENOLOGY
Figure 29.1: The superconducting transition of mercury[29].
electrical resistivity could be reduced. He began with mercury, which could easily be purified
by distillation. What he discovered was nothing short of amazing at a temperature of
4.2 K, the electrical resistance of mercury dropped abruptly to zero. Other common metals,
such as lead and tin, showed a similar transition. The phenomenon was named superconductivity. Increasingly sophisticated measurements to quantify the electrical resistance have all
obtained the same result that the resistance is zero to within experimental error. These
experiments take the form of a persistent current flowing in a loop and use sensitive magnetometers to detect small changes in the magnetic field produced by the loop. Theoretical
estimates have shown that such a configuration, if kept cooled below the superconducting
transition temperature, should be stable for longer than the age of the universe.
29.3
The MeissnerOchsenfeld effect
The next experimental signature to be discovered was perfect diamagnetism, observed in

1933 by Meissner and Ochsenfeld. In a perfect conductor, we expect Lenz law to apply
perfectly. That is, any attempt to change the magnetic flux linking the perfect conductor
would be met with a self-generated flux, induced by the Faraday electric fields, that perfectly
cancels the change. (In a perfect conductor, even in the presence of a large, time-varying
current, the electric field is everywhere zero. Therefore
Z
I
d
d
B dA = .
(29.1)
E d` = 0 =
dt
dt
Magnetic flux is therefore trapped in place.)
29.4. THE LONDON THEORY
253
Figure 29.2: The MeissnerOchsenfeld effect.
Meissner and Ochsenfeld discovered that not only is a magnetic field prevented from entering
a superconductor, as would be expected from the perfect conductivity, but when a pure
specimen is cooled in the presence of a small field, the field is expelled as the sample cools
through Tc . This phenomenon cannot be explained by perfect conductivity, and gives a
far more important clue as to the nature of superconductivity than the lack of electrical
resistance, because it indicates that the onset of superconductivity is a transition to a new
thermodynamic ground state. Zero resistance, on the other hand, could be explained by a
sudden switching off of scattering processes in the conductor.
29.4
The London theory
The first successful theory of superconductivity was the phenomenological model put forward
by Fritz and Heinz London in 1935. The Londons proposed the existence of a superfluid
wavefunction (r) that extended coherently throughout the superconductor. We now know
that superconductors are described in microscopic detail by the BardeenCooperSchrieffer
(BCS) pairing theory, which we will look at in the next lecture. The London model survives if
we identify the superfluid wavefunction with the centre-of-mass motion of the Cooper pairs.
In that case, a wavefunction (r) of the form exp(is r) corresponds to a state in which
every Cooper pair has the same centre-of-mass momentum ~s and pair velocity ~s/2me . We
will carry on using this pairing language while discussing the London theory, although it
should be remembered that the Londons had no inkling that their theory actually referred
to electron pairs.
The London wavefunction is usually normalized to the effective density of Cooper pairs ns .
(r) =
ns ei(r)
(29.2)
254
The supercurrent density is js = 2ens vs = 2e vs or, more generally,

ie~
,
js =
2me
(29.3)
which is the usual quantum mechanical form for a current density.

We will now show how the London theory leads to perfect conductivity and the expulsion of
magnetic flux. In the presence of a magnetic field, the quantum-mechanical current operator
takes the gauge invariant form
2e2
ie~

A,
(29.4)
2me
me
where A is the vector potential. If we write as ns ei(r) , then this becomes

~
+ A ,
(29.5)
js =
2e
where is the London paramater = me /2ns e2 . ~ is the local canonical pair momentum.
The rate of change of the wavefunction gives the local pair energy 2. That is
js =
i(r)
ns e
= 2 ns ei(r)
t
~
= 2.
t
Taking the time derivative of Eq. 29.5 leads to the first London equation:
i~
(js )
A
=
+
t
t
e
= Eeff ,
(29.6)
(29.7)
(29.8)
(29.9)
where Eeff is the effective electric field. This is an acceleration equation for the superelectrons,
representing dissipationless motion.
Taking the curl of Eq. 29.5 gives
(js ) = B,
(29.10)
since the gradient of a scalar is always irrotational. Writing Amp`eres law as B = 0 js ,
we have
B = 0 j s
0
= B.
Using B = ( B) 2 B and B = 0, we have

2 B =
(29.11)
(29.12)
B
,
2L
(29.13)
p
p
where L = /0 = me /20 ns e2 is the London penetration depth. This is a screening
equation for the magnetic field whose solutions decay exponentially into the superconductor
with depth z as exp(z/L ). L is typically of the order of 107 m in superconductors so,
for all intents and purposes, the expulsion of magnetic flux from a macroscopic sample is
perfect.
29.5. FLUX TRAPPING AND QUANTIZATION
29.5
255
Flux trapping and quantization
It is very common for a superonducting sample to have a geometry that is not simply connected. (A simply connected geometry is one in which any contour within the superconductor
can be continuously deformed into any other contour, without any part of the contour leaving
the sample.) The simplest such case is a ring of superconductor. According to the London
theory, the phase of the superfluid wavefunction is related to the supercurrent density
=

2e
A + js .
~
(29.14)
The superfluid wavefunction must be single valued, so the change in around the loop must
be an integer multiple of 2.
I
I
2e
d` =
(A + js ) d` = n2.
(29.15)
~
The line integral of the vector potential is the magnetic flux linking the ring:
I
Z
A d` = B dA =
so
(29.16)
I
h
me
vs d` = n .
(29.17)
+ js d` =
e
2e
If we take the integral over a contour deep inside the superconductor where js and vs vanish,
then the flux through the loop is quantized in units of the flux quantum 0 = h/2e. The pair
nature of the superfluid wavefunction shows up directly in the value of the flux quantum. The
argument for the quantization of flux breaks down when the thickness of the superconducting
ring is small compared to the penetration depth. However, the fluxoid,
I
me
vs d` = n0 ,
(29.18)
e
I
remains quantized.
29.6
The Josephson effect
We are accustomed to the idea of quantum mechanical tunneling where, for example, an
electron can quantum mechanically hop through a thin insulating barrier separating two
conducting electrodes. The amplitude for this process is small, and decreases exponentially
with the barrier thickness. Early on, electron tunneling became a very important experimental probe of superconductivity because it permitted a direct measure of the energy-dependent
density of states. In these experiments it was single electrons that were transferred across
the tunneling barrier. Following the development of the BCS theory it became clear that
superconductivity is associated with electron pairs, but no one gave much serious consideration to the possibility that these may tunnel through an insulating barrier, because it was
256
thought that such a process, involving two electrons, would be second order in the tunneling
amplitude and therefore be immeasurably small. This is not the case. While a graduate
student at Cambridge, Brian Josephson carried out a difficult calculation that showed that
pair tunneling was a coherent process, and as such had an amplitude comparable to single
electron tunneling. After establishing that a measurable supercurrent could tunnel through
an insulating barrier, Josephson explored the experimental consequences of such a device,
and discovered several remarkable phenomena that now go by the name of the Josephson
effects[30]. For this work, described in a short paper in 1962, he won the Nobel prize.
Figure 29.3: Geometry of a superconducting ring containing a Josephson junction. (From

Taylor and Heinonen[7].)
Consider a superconducting ring that contains a thin, insulating tunneling barrier, like the
one shown in Fig. 29.3. This small slit now allows us to move magnetic flux in and out
of the ring without having to warm it through Tc , but is small enough that is contains no
appreciable flux itself. Given Josephsons result that a supercurrent can still circulate in the
ring, we expect the fluxoid equation, Eq. 29.18, to remain valid.
I
me
vs d` = n0 ,
(29.19)
e
We are assuming that our ring has cylindrical symmetry, which allows us to carry out the
line integral of the velocity. We do so and find that

e
vs =
n0 .
(29.20)
2Rme
This is the speed of a Cooper pair that moves on a circle of radius R enclosing a flux .
The Cooper pairs can only move with certain quantized speeds, corresponding to different
integers n. We will usually be concerned with the lowest speed. The pair kinetic energy is
1
2me vs2
2

2
e2
= 2 2
n0 .
4 R me
(29.21)
29.6. THE JOSEPHSON EFFECT
257
This energyflux relation is plotted in Fig. 29.4. As a magnetic flux is applied to the ring,
the kinetic energy increases quadratically. The energy relation has a different branch for
each n, and when the flux linking the ring is equal to a half odd integer, the kinetic energy
becomes degenerate with the energy of a different branch. The Cooper pairs will generally
stay in the lowest kinetic energy state so, when the degeneracy point is crossed, a phase slip
of 2 occurs in the phase difference across the junction and the system jumps to the next
energy branch. The ground-state energy is therefore periodic in the applied magnetic flux.
Figure 29.4: The multiple quadratic branches of the Cooper pair kinetic energy as a function
of the applied magnetic flux, in units of a flux quantum. (From Taylor and Heinonen[7].)
The total energy tot is a sum of similar contributions from all the Cooper pairs. The total
current flowing in the ring is proportional to dtot /d. It has the sawtooth form shown in
Fig. 29.5. If the flux is maintained at a value different from n0 , a current flows through
the junction and a difference in the phase of the superfluid wavefunction across the junction
forms. Because the flux through the loop is held constant, there is no electromotive force
around the ring and the current flows at zero voltage it is therefore a supercurrent. This
is the dc-Josephson effect.
Figure 29.5: The supercurrent that flows in the ground state of a superconducting ring is a
periodic function of the applied flux. (From Taylor and Heinonen[7].)
If we now apply a flux that increases linearly in time there will be an electromotive force
V = d/dt. The current through the junction will then alternate in sign with frequency
=
2eV
.
~
(29.22)
This is the ac Josephson effect. The standard volt is now defined in terms of it.
258
The beauty of the Josephson effect is that it leads to experimentally observable effects that
depend on the phase of the superfluid wavefunction. This is a quantity that is not normally
experimentally accessible. The effect has been put to great use in building superconducting
interferometers that are exquisitely sensitive to magnetic flux. These go by the name of
SQUIDs (Superconducting QUantum Interference Devices) and can detect magnetic flux
(and any
other physical quantity
that can be converted to a flux) with a sensitivity of about
106 0 / Hz (about 1021 Wb/ Hz).
Lecture 30
Superconductivity II pairing
theory
30.1
The Cooper problem
The ground state of the electron gas is a filled Fermi sea. The Fermi surface of a real solid
may have a complicated shape, and the Fermi sea may only show a sharp surface when
viewed in the Landau quasiparticle basis, but a metallic state can none the less be identified
with the presence of a special surface in momentum space that holds weakly interacting,
electron-like states.
In 1957 Cooper made a breakthrough, and showed that in the presence of an attractive
interaction, no matter how weak, the Fermi sea is unstable to the formation of a two-electron
bound state that has since been named the Cooper pair[31]. Although Coopers calculation
stops well short of explaining superconductivity, it provided the necessary toehold to begin
development of the final theory, by demonstrating the existence of a state with lower energy
than the filled Fermi sea.
Coopers calculation focuses on the two electrons of the pair, with coordinates r1 and r2 .
The other electrons are inert and simply serve to block occupation of k-states inside the
Fermi surface by the exclusion principle. The calculation further specializes to the case of
pair states with zero centre-of-mass momentum,
(r1 , r2 ) = (r1 r2 ).
(30.1)
A general state of this form can be expanded in plane waves:

X
(r1 r2 ) =
gk eik(r1 r2 ) .
(30.2)
gk is the amplitude to find one electron in the plane wave state |ki and the other in state
| ki. Pauli exclusion requires that gk = 0 for |k| < kF .
The two-particle Schrodinger equation is

~2 kF2
~2
2
2
+ 2 (r1 , r2 ) + V (r1 , r2 ) = E + 2
(r1 , r2 ),
(30.3)
2m 1
2m
259
260
LECTURE 30. SUPERCONDUCTIVITY II PAIRING THEORY
where E is the energy of the pair measured with respect to 2EF . Inserting the plane wave
expansion of the wavefunction, Eq. 30.2, we can recast the Schrodinger equation as an
algebraic equation in k-space.
X
~2 2
k gk +
gk0 Vkk0 = (E + 2EF )gk ,
2
2m
k0
where the matrix elements of the interaction between states |ki and |k0 i are
Z
1
0
Vkk0 = 3 V (r)ei(kk )r dr.
L
(30.4)
(30.5)
We are looking for bound state solutions (E < 0), when Vkk0 is attractive. We postpone
for now any discussion of why an attractive interaction between electrons might exist, and
just examine what its consequences would be if it did. Cooper used the simplest possible
approximation he assumed the matrix element was attractive (negative) if both states |ki
and |k0 i were within an energy cut-off ~D of the Fermi surface. Later on we will see that
D is a characteristic frequency of the phonons.
~2 k 2
~2 k 02
V
,
<
E
+
~
and
< EF + ~D
F
D
L3
2m
2m
= 0 otherwise.
Vkk0 =
On rearranging Eq. 30.4, we have

~2 k 2
V X
+ E + 2EF gk = 3
gk0 ,
2
2m
L k0
(30.6)
(30.7)
(30.8)
where the sum over k0 is for EF < ~2 k 02 /2m < EF + ~D . Lets now measure excitation
energy from the Fermi energy, by defining
k =
~2 k 2
EF .
2m
Then
(E 2k )gk =
(30.9)
V X
gk0 ,
L3 k0 >k
(30.10)
and
gk =
X
V
1
gk0 .
L3 2k E k0 >k
(30.11)
We can deal with the sum over k by summing both sides over k,
X
k>kF
gk =
X
V X
1
gk0 ,
L3 k>k 2k E k0 >k
F
(30.12)
and canceling the sums:

1=
V X
1
.
3
L k>k 2k E
(30.13)
30.2. THE ORIGIN OF THE ATTRACTIVE INTERACTION
261
The sum now only depends on k through the energy k , so we can rewrite it as an integral,
by introducing the density of states D() in the usual way.
Z ~D
D()d
(30.14)
1 = V
2 E
0
Z ~D
1
1
d
D(0)
(30.15)
V
2
E/2
0

E 2~D
1

=
D(0) ln
(30.16)

2
E
In the weak coupling limit, D(0)V 1, then E ~D , and the solution becomes

2
.
(30.17)
E 2~D exp
D(0)V
Although exponentially small, there is a bound state solution (E < 0) for arbitrarily weak
attractive interactions. The importance of Coopers result, derived for a single pair of electrons, was to show that the Fermi surface was unstable to the formation of Cooper pairs. It
was realized straight away that pair formation would continue until a new equilibrium was
reached, but further work was required before this could be described mathematically.
30.2
The origin of the attractive interaction
We spent some time at the beginning of the course calculating the interaction between
electrons in solids. The dominant force between two electrons is the repulsive Coulomb
interaction
e2
1
.
(30.18)
V (r1 , r2 ) =
40 |r1 r2 |
This has matrix element
V (q) =
e2
.
0 q 2
(30.19)
We also saw that in the presence of a medium the matrix element becomes screened by the
dielectric function r (q, ):
V (q) V (q, ) =
e2
.
r (q, )0 q 2
(30.20)
Without going into the details, a polarizable lattice has long wavelength resonances at the
frequencies of the optical phonons. This leads to a dielectric function of the form
r (q, ) = elec +
p2
,
2 2
(30.21)
p
where p = ne2 /m0 is the unbound plasma frequency of the ions and is the frequency
of the optical phonon.
262

Veff(q,)
Figure 30.1: Veff (q, ) = VCoulomb (q) + Vphonon (q, ) is repulsive at low energy transfer but
becomes attractive over a range of energies below the phonon frequency.
Figure 30.2: Polarization of the lattice by electron 1 leads to dynamical overscreening, and
a net attractive interaction with electron 2.
The effective electronelectron interaction is plotted as a function of frequency in the longwavelength limit in Fig. 30.1. It is repulsive at low frequencies but becomes attractive for a
range of energies below the phonon frequency.
The phonon mediated interaction between electrons is effective because the time scales for
electrons and phonons are so different. An electron propagating through the solid polarizes
the lattice around it. The electron moves on a time scale of the order of ~/EF . The lattice
relaxes much more slowly, on a time scale 1/, leading to a residual polarization that
survives long after the original electron has left. A second electron moving through the
lattice sees this as an excess of positive charge and is attracted to it. This process, known
as dynamical overscreening, is illustrated in Fig. 30.2.
30.3. BARDEENCOOPERSCHRIEFFER THEORY
30.3
263
BardeenCooperSchrieffer theory
In the presence of an attractive interaction, Cooper showed that the Fermi sea was unstable
to the formation of zero centre-of-mass-momentum Cooper pairs. The pairs are formed from
electrons above the Fermi sea, so the electrons in a Cooper pair have a kinetic energy that
is greater than the Fermi energy. It is this that sets a limit on the Cooper-pairing process
pairing will proceed until the kinetic energy cost of forming another pair outweighs the
potential energy gain from the attractive interaction, which is only available between kstates with opposite wavevector. The problem of describing the system when there is more
than one Cooper pair present is a difficult one, and it was the great insight of Schrieffer, a
graduate student at the time, to guess a very good approximate form for the many-body
wavefunction.
This time using second quantization, we can write a state |N i with N/2 Cooper pairs, using
a form similar to the single pair wavefunction:
|N i =
g(k1 , ..., kN/2 )ck1 ck1 ...ckN/2 ckN/2 |0 i,
(30.22)
where |0 i is the vacuum state. g(k1 , ..., kN/2 ) is the weighting coefficient of each term in
the expansion. We have specialized to the case where the centre-of-mass momentum is zero,
although we would relax this constraint if we wanted to represent the flow of a supercurrent.
This wavefunction is horribly complicated. The sum is over all choices of N/2 wavevectors
from M possible wavevectors, where M is of the order of the number of electrons in the
system. There are
M!
20
1010
(30.23)
(M N2 )!( N2 )!
different terms and as many g(k1 , ..., kN/2 ) to determine. Part of the complication stems
from the fact that we constrained the number of pairs to a fixed value. This is not only
mathematically inconvenient we would also find it impossible to describe the Josephson
effect with such a wavefunction.
Bardeen, Cooper and Schrieffer (BCS) found a much simpler wavefunction that captured the
essential physics[32]. They used a mean-field approach that depended solely on the average
occupancy of the pair states, which, however, works very well in the limit of large N . The
BCS ground state is
Y

|BCSi =
uk + vk ck ck |0 i,
(30.24)
k
subject to the constraint that |uk |2 + |vk |2 = 1. (That is, any particular pair of electrons is
either occupied or unoccupied.) The number of pairs in the BCS ground state is not fixed
if we multiply out the product we will find terms with different numbers of pairs but the
distribution of terms is sharply peaked around the average number of pairs. By relaxing the
number constraint we can also work with a wavefunction with a well-defined phase, which
is essential to the physics of the Josephson effect. The BCS state is a wavefunction of spinsinglet pairs. Triplet states are also possible but were considered later, in the context of
superfluid 3 He.
264
BCS also made the simplification of using a reduced Hamiltonian

X
X
H=
k n
k +
Vk` ck ck c` c` .
k
(30.25)
k`
The interaction term in the BCS Hamiltonian includes only terms that scatter one electron
pair (`, `) into another (k, k). This is a gross simplification of the actual electronelectron
interaction but captures the essential physics of the phonon-mediated pairing interaction.
BCS employed a variational method to optimize the choice of uk and vk : they used a Lagrange
multiplier (the chemical potential ) to fix the average particle number and minimized the
in the BCS ground state by adjusting uk and vk . We will use
expectation value of H N
an algebraically simpler method and solve the problem by canonical transformation.
30.4
The Bogoliubov transformation
The Bogoliubov method works by diagonalizing a mean-field approximation to the Hamiltonian and in the process finds the operators that generate the excited states of the system.
It is therefore better than the BCS method at dealing with excitations, which are necessary
in order to understand experiments such as spectroscopies, tunneling and thermodynamics.
The BCS wavefunction |BCSi is a phase-coherent superposition of pairs, without fixed pair
number. Operators such as ck ck can therefore have nonzero expectation value. Let
bk = hBCS|ck ck |BCSi.
(30.26)
This would average to zero in a normal metal. We can write

ck ck = bk + ck ck bk ,
(30.27)
where the term in brackets is a small fluctuation term, and use this to rewrite the BCS
hamiltonian in the following approximate form:

X
X
H=
k n
k +
Vk` ck ck b` + bk c` c` bk b` ,
(30.28)
k
k`
where k = k . This mean-field approximation effectively turns the quartic interaction

term into a quadratic term, making the hamiltonian bilinear. It can therefore be diagonalized
by a canonical transformation. To see this, let
X
k =
Vk` b`
(30.29)
`
Vk` hc` c` i.
(30.30)
The hamiltonian can then be rewritten

X
X
H=
k n
k
k ck ck + k ck ck k bk .
k
(30.31)
30.4. THE BOGOLIUBOV TRANSFORMATION
265
Bogoliubov and Valatin independently showed that this could be diagonalized by the transformation
ck = uk k0 + vk k1
ck
vk k0
(30.32)
.
uk k1
(30.33)
k0 participates in destroying an electron |k i and creating an electron | k i. In both

cases the momentum is reduced by k and Sz is reduced by ~/2. k0 on the other hand
increases momentum by k and Sz by ~/2.
The procedure is to substitute the new operators into the hamiltonian. The constraint on
uk and vk (|uk |2 + |vk |2 = 1) makes this a canonical transformation the canonical commutation relations of the electron operators are preserved. This means that the Bogoliubov
quasiparticles are fermions.
1
1
2
2
k
uk
0.8
0.8
Fermi function at Tc
(a)
-6
-4
-2
0.6
0.6
0.4
0.4
0.2
0.2
(b)
-4
-2
vk2 at T = 0
Figure 30.3: (a) Coefficients of the variational wavefunction, u2k and vk2 . (b) vk2 at T = 0 and
the Fermi function at Tc .
The condition that the hamiltonian be diagonal places additional constraints on uk and vk :

1
k
2
2
|vk | = 1 |uk | =
1
,
(30.34)
2
Ek
where
Ek =
k2 + |k |2 .
(30.35)
uk and vk are plotted in Fig. 30.3. The occupation of pair states at T = 0 is not very
different from the FermiDirac function at T = Tc .
The hamiltonian, in diagonal form, is
X
H = const +
Ek k0
k0 + k1
k1 .
(30.36)
k
The k are the elementary excitations, with energy Ek . k is the minimum excitation energy,
and is referred to as the energy gap. The energy gap is best seen in the density of states
which can be calculated as follows. The states of the superconducting phase and the normal
phase must exist in one to one correspondence. Therefore
Ds (E)dE = Dn ()d.
(30.37)
266
The density of states in the normal state is constant, Dn () = D(0), so

D(E) = D(0)
E
d
=
.
2
dE
E 2
(30.38)
The energy gap shows up in many experiments, giving an activated temperature dependence
to thermodynamic properties, and a gap in the optical conductivity and tunneling density
of states.
4
= (2 + 2)1/2
3
||
-4
-2
Figure 30.4: Excitation energies of the normal and superconducting states.
Ds()/D(0)
4
-2
-1
Figure 30.5: The density of states Ds (E) of a BCS superconductor. There is gap 2 wide
that appears in tunneling measurements and the optical conductivity.
Lecture 31
Superconductivity III exotic
pairing
31.1
Conventional superconductors
BCS theory has been fantastically successful at describing the physical properties of the
vast number of materials that were known to superconduct at the time of its inception.
Most of these are elemental superconductors, but the theory, in a form modified to allow for
strong spatial variations of the pairing field, also describes the alloy superconductors that
became technologically important with the advent of high field superconducting magnets.
The success of the BCS theory is owed to two things: the inspired guess, by Schrieffer,
of a good approximate form for the mean-field, ground-state wavefunction; and the clean
separation of phonon and electronic energy scales (the Debye energy ~D and the Fermi
energy F , respectively) that allows for a perturbative treatment of the phonon-mediated
interaction.
This phonon mechanism lies at the heart of the pairing theory of conventional superconductors. It leads to an attractive interaction that is approximately isotropic in k-space, and
opens a correspondingly isotropic energy gap on the Fermi surface.1
31.2
Pairing glue
While important and ubiquitous, phonons are not the only bosonic mode that emerges when
atoms are combined to form an electronic solid. It is therefore interesting to ask if other
excitations can play the role of pairing glue, giving rise to exotic types of superconductivity.
Some of the collective modes one might consider include:
1
Even in the elemental superconductors, strong coupling effects and crystalline anisotropy lead to some
variation of the energy gap magnitude over the Fermi surface. The energy gap in tin, for instance, has
one of the stronger variations of all classic elemental superconductors, with a modulation in magnitude of
about 30%. Transition metal superconductors, such iridium, which have multiple Fermi surface sheets for
the partially filled s and d bands, also show strong variation in || from sheet to sheet.
267
which occurs when electrons at low temper- forces created by phonons could be elegantly favour p- or d-wave p
ature pair up and flow without resistance. incorporated into BCS theory using a set of because magnetic flu
Now, on page 340 of this issue, Sato et al.1 equations that now bear his name. It turns metals with strongly
p- or d-wave pairs for
of
phonons
between
reveal a magnetic
origin for
glue out that the exchangeIII
268
LECTURE
31.theSUPERCONDUCTIVITY
EXOTIC
PAIRING
lowering the mutual r
electrons by keeping t
the unconventional su
a
tron scattering exper
Phonon wave
large fluctuations in
s-wave
temperatures, which c
pairs
pairing, and several ot
vide good evidence for
d-wave electron pairs i
But despite strong
Electron
dence for magnetica
Electron
conductivity, definiti
fluctuations are the glu
ing has been hard to c
because magnetic fluc
difficult to characteriz
b
also because, unlike ph
tuations interact with e
Magnetic
d-wave
exciton wave
theoretical description
pairs
ated pairing a far more
Sato et al.1 provid
Figure 1 Two ways to make a metallic superconductor. a, In conventional superconductivity the glue
Figure 31.1:
In conventional superconductors the exchange of phonons binds electrons this
intomagnetic glue. Th
fermion superconduc
responsible for binding electrons into superconducting pairs is derived from the exchange of quanta
s-wave Cooper
pairs. Magnetic excitations provide a possible route to exotic pairing states,
because the conduc
of lattice vibrations phonons, shown here as a wave passing through the lattice atoms that
1
with antiferromagnetic
spin waves
to d-wave
Cooper
pairs.
(After Coleman[33].)
acquire very large ef
bind electrons into s-wave
pairs. b, giving
Sato et al.rise
provide
new evidence
that, in
the unconventional
hundreds of times th
superconductor UPd2Al3, the glue responsible for the electron pairing derives from the exchange of
UPd2Al3 is one of a han
magnetic quanta magnetic excitons that bind the electrons into d-wave pairs (blue arrows
superconductors in w
indicate direction of spin).
ferromagnetic spin waves. In a metal, direct exchange causes the spin of an electron to
2001 Macmillan Magazines Ltd
320
NATURE | VOL 410 | 15 MA
locally
polarize the electron gas surrounding it. In a ferromagnet this effect is strong
and leads to a state with a uniform, ordered magnetic moment a spontaneous
breaking of time reversal symmetry. The Goldstone boson2 of such a broken symmetry
is a ferromagnetic magnon that takes the form of a wavelike variation in the direction
of the magnetization. The lowest energy spin waves in this case are located near
q = 0, like phonons, but disperse quadratically in wavevector, due to the softness of
the exchange coupling, 0 , which goes like the cosine of the angle between the
spins. In a nascent ferromagnet (e.g. near a ferromagnetic quantum critical point)
there is no spontaneous magnetic order, but the exchange coupling of the electron
spin to the surrounding electron fluid is still strong. If this induced polarization decays
slowly, it can mediate an interaction with a second electron. In this case the interaction
favours parallel alignment of the electron spins, leading to spin-triplet pairing. Overall
fermionic antisymmetry then requires the orbital wavefunction to have odd angular
momentum. This type of pairing is important in superfluid 3 He.
antiferromagnetic spin waves. An antiferromagnet consists of an alternating ordering
Goldstones theorem states that whenever a continuous symmetry is broken, a new massless scalar
particle appears in the spectrum of excitations. Liquids break Galilean symmetry, and the Goldstone mode
is a longitudinal acoustic phonon, dispersing like = cq for small q, with vanishingly small energy as
q 0. Solids also break Galilean symmetry, but the presence of a lattice introduces shear stiffness and
gives separate transverse and longitudinal phonons as the Goldstone bosons. Magnets break spin-rotation
symmetry, leading to the emergence of magnons as the new, low energy bosonic mode.
31.3. ANDERSONS THEOREM
269
of magnetic moments, with the spatial modulation occurring at some wavevector Q.

The antiferromagnetic interaction favours antiparallel alignment of spins, binding the
electrons of the Cooper pair into a spin singlet, as in conventional superconductors.
Overall fermion antisymmetry then requires a spatially even wavefunction, leading to
pairing in a even angular momentum channel. However, the antiferromagnetic interaction is strongly anisotropic in k-space, with the static spin susceptibility (analogous to
the 0 limit of the electron density response function (q, )) strongly peaked near
q = Q. Moreover, the interaction is fundamentally repulsive, but we will see below
how this can be turned to the superconductors benefit by pairing in higher angular
momentum channels.
other excitations. Excitations such as electric quadrupolar fluctuations of orbital order
and unscreened currentcurrent fluctuations have been proposed as very exotic pairing
mechanisms.
31.3
Andersons theorem
In the presence of disorder, Bloch waves of well-defined momentum cease to be good eigenstates. We can think of disorder as giving a finite range to the wavefunction, imposing an
exponential envelope with a characteristic decay length equal to the mean free path `. Using
uncertainty arguments, we see that this imparts a finite spread in wavevector, k = 1/`, to
the electron state in k-space. The stronger the disorder, the more the electron state spreads
out around the Fermi surface.
Surprisingly, this smearing has little effect on conventional superconductivity. Substitutional
impurity studies show that after an initial decline in Tc , addition of further impurities gives
no further suppression of transition temperature. In fact, superconductivity is known to
occur in materials such amorphous MoGe, in which the atoms themselves have glass-like,
not crystalline, arrangements.
The explanation of how this can occur was given by P. W. Anderson in 1959[34]. In one
of his many strokes of genius, he realized that the (k , k ) pairing of BCS theory was
just a special case of a more general pairing of time-reversed states. In the absence of
perturbations from magnetic fields and magnetic impurities, the hamiltonian of a solid has
time reversal symmetry, irrespective of the amount of disorder. That is, for every eigenstate
n (r), the conjugate wavefunction n (r) will also be an eigenstate, and will have the same
energy. The time reversed states will have opposite spin, and are the states that combine to
form Cooper pairs in the presence of strong disorder. These states are inherently smearedout in k-space. For conventional materials this is not harmful to the superconductivity: the
phonon-mediated interaction is quite isotropic, and the effect of disorder is simply to average
the superconducting energy gap over the Fermi surface. However, as we will see below,
unconventional superconductors form Cooper pairs in finite angular momentum channels.
These states have the property that the energy gap changes sign over the Fermi surface.
Andersons results still apply, but the smearing of the energy gap rapidly causes it to average
to zero, destroying the superconductivity. This makes unconventional superconductivity
exceedingly delicate, and helps explain why it took so long to be observed.
270
LECTURE 31. SUPERCONDUCTIVITY III EXOTIC PAIRING
Figure 31.2: The dopingtemperature phase diagram of the cuprate superconductors. (After
Bonn[35].)
31.4
Unconventional pairing in specific materials
Rather than survey the full range of possible exotic superconducting states, which is vast
and has been thoroughly explored by theorists, we will look at a number of specific examples
of materials that exhibit unconventional superconductivity. Our definition of unconventional
superconductivity will be taken to mean pairing states that break symmetries in addition
to the broken gauge symmetry found in all superconductors. We will begin with the high
temperature superconductors, not because their transition temperatures are highest, but
because their form of unconventionality, the d-wave pairing state, is simplest to understand
and lays the groundwork for similar pairing states in the heavy fermion materials. We will
then look at heavy fermion superconductivity, which is remarkable because it occurs in the
vicinity of magnetic quantum critical points.
31.4.1
Cuprate superconductivity
Discovered in 1986, the cuprate superconductors hold the record for highest Tc , with superconductivity observed under pressure at temperatures up to 160 K. Many aspects of the
cuprates, particularly their strange normal-state properties, remain poorly understood. We
will focus here on the superconductivity. The details of the mechanism are still a matter of
great contention and debate, but what is clear is that superconductivity emerges from the
physics of strong Coulomb repulsion.
primarily in La(2x)SrxCuO4, found that

between stripes is a/2x (where a is the
broadened versions of the antiferromagCu-Cu separation). This distance gives the
netic Bragg peaks persist in samples with
charge periodicity; the antiphase property
the highest Tcs (6 9). Further, the spin
means that the spin period is twice this
31.4. UNCONVENTIONAL
IN SPECIFIC
correlations were found toPAIRING
be incommensuvalue, or MATERIALS
a/x. This spin periodicity causes
Fig.
2. Schematic phase
271
perature superconductors
indicates the region in w
mensurate antiferromagn
A
B
shown by the red arrows
shaded blue area indicate
superconducting long-ran
carrier concentration at
3+
La
ducting transition tempe
ary of blue region) is max
defined as optimal doping
Cu2+
and higher carrier conce
to as underdoped and ov
O2In the regime between t
tiferromagnetic phase an
phase, a different, more
order occurs; this is discu
c
text, and is shown here
This order is observed t
b
conductivity in some m
a
the two phases exist in sp
of a sample or coexist in
not fully clear. The shade
Fig. 1. (A) Crystal structure of La2CuO4, the parent compound of the La(2x)SrxCuO4 family of
Figure 31.3:
The superconducting
of subunit
layers isofthe
CuO
The copper
itatively defined crossove
high-temperature
superconductors.cuprates
The crucialconsist
structural
Cu-O
2 planes.
2 plane, which
which materials, althoug
in the a-b
direction;
parts of three
CuOantiferromagnetically[36].
2 planes are shown. Electronic couplings in the
spins of extends
the undoped
parent
compound
order
cally in the normal phas
interplane (c) direction are very weak. In the La2CuO4 family of materials, doping is achieved by
iors discussed in more de
substituting Sr ions for some of the La ions indicated, or by adding interstitial oxygen. In other
figure shows the phasefamilies of high-Tc materials (e.g., YBa2Cu3O6x) the crystal structure and mechanism of doping are
hole doping. A few elec
slightly different, but all materials share the feature of CuO2 planes weakly coupled in the
have been made; becaus
transverse direction. (B) Schematic of CuO2 plane, the crucial structural subunit for high-Tc
The cuprates
are layered
consisting
stacks ofof spins
CuOin2 the
planes,
as shown intion
Fig-difficulties, their pr
superconductivity.
Red materials,
arrows indicate
a possible of
alignment
antiferromagnetic
determined
than those
of La2CuOdiffer
.
Speckled
shading
indicates
oxygen
p
orbitals;
coupling
through
these
ure 31.3.ground
Thestate
materials
in
the
number
of
planes
per
unit
cell,
and
in
the
types
of
4
materials.)
orbitals leads to superexchange in the insulator and carrier motion in the doped, metallic state.
cations found between the planes. However, the CuO2 plane is common to all high Tc superconductors, and there is ample evidence to suggest that it is the seat of superconductivity.
www.sciencemag.org SCIENCE VOL 288 21 APRIL 2000
As a result, most attempts to understand the superconductivity start with an isolated CuO2
layer.
The parent compounds of the cuprate superconductors are Mott insulators, which order
antiferromagnetically below TN 300 K. This physics is driven by strong Coulomb repulsion.
As we saw in Lecture 20, Coulomb repulsion leads to the splitting of the conduction band
into two Hubbard bands. At half filling, which applies to the cuprate parent material, the
lower Hubbard band is filled and the upper Hubbard band is empty, creating an insulator.
An antiferromagnetic interaction between the localized electrons on neighbouring sites arises
from superexchange.3 The spin arrangement in the antiferromagnetic state is shown in
Figure 31.3. This can be thought of as a spin density wave with Fourier components Q =
(/a, /a).
As mobile holes (or electrons) are doped in the cuprate parent compound, the antiferromagnetic state weakens and disappears, and is replaced by superconductivity. Signatures
of the antiferromagnetic order persist to superconducting dopings, showing up as strong
peaks in the spin response function near Q = (/a, /a). Some theories use these spin
fluctuations as the glue that binds charge carriers into high Tc Cooper pairs.
To see how this works, we look again at BCS theory, generalized to allow for the possibility
that the energy gap k be a strongly varying function of k. In the last lecture we studied
3
Superexchange is due to the small energy lowering that occurs as a fluctuation in second order perturbation theory, if the localized electron can tunnel to a neighbouring site and back again. This is only allowed
by the Pauli exclusion principle if the electron on the neighbouring site has antiparallel spin.
272
Figure 31.4: Magnetic excitations at wavevectors Q = (/a, /a) couple parts of the
Fermi surface having different sign of the energy gap. This turns a repulsive interaction into
a means of binding finite angular momentum Cooper pairs.
the Bogoliubov approach, in which an average pair field

bk = hBCS|ck ck |BCSi
(31.1)
was introduced in order to recast the hamiltonian as a mean field theory. bk is intimately
connected to the opening of the energy gap. The BCS gap parameter
X
Vk` b`
(31.2)
k =
`
expresses the effect of the pairing fields at wavevectors `, acting through the matrix elements
Vk` , on the magnitude of the energy gap k . This process must be treated self consistently,
leading to the BCS gap equation
k =
X `
Vk` .
2E
`
`
(31.3)
p
Note the overall minus sign. The excitation energy E` = `2 + 2` is inherently positive. For
an attractive interaction (Vk` < 0) the gap equation yields an isotropic solution. Repulsive
interactions at first sight appear to give k = 0, but this is only the case if the interactions are
uniformly repulsive. If the Vk` are sufficiently anisotropic, the gap equation allows solutions
in higher angular momentum channels.
To picture how this applies in the case of the cuprates, we imagine that Vk` is positive
(repulsive) and sharply peaked at momentum transfers q = k ` equal to the dominant
Fourier components of the antiferromagnetic state, Q = (/a, /a). We see in Figure 31.4
REVIEW ARTICLE
31.4. UNCONVENTIONAL PAIRING IN SPECIFIC MATERIALS
273
1/2 (m2)
superuid density,
of superuid 4 He. M
but a tensor quanti
determines a superc
8.0
in the phase of the s
As the temperature
excitations deplete
to zero when the no
N(E )
state would possess
Fermi surface expec
and there would th
4.0
possible down to ze
varying linearly wit
dependence of 1/l2
earlier measuremen
conrmed when it
o
impurities on the C
E
low-temperature po
0
the eld to produce
0
20
40
60
80
nd the d-wave sup
Temperature (K)
given us a delicate p
dicult materials p
Figure 31.5: The point nodes in a d-wave superconductor give rise to a linear energy depenintrinsic behaviour
3 Measurement
of the superuid
density derived
from be
microwave
measurements.
Thetemperature
dence ofFigure
the density
of quasiparticle
states.
This can
probed
through the
development of ma
Londonofpenetration
depth candensity
be measured
depth that microwave elds
dependence
the superfluid
1/2by
(Tdetermining
). (Afterthe
Bonn[35].)
with high crystallin
penetrate into the surface of a superconductor. The inverse square of this length scale is a measure
the level that has be
of superuid density, or phase stiffness, which sets a superconductors resistance to variation in the
semiconductor dev
phase of the superconducting wavefunction. The linear behaviour at low temperatures is a
exceptional in trans
consequence of the linear density of states N on energy E (inset) of a d x2 y2 superconductor with a
Further identi
cylindrical Fermi surface. The energy gap of this state has a maximum 0 for momenta in the
techniques far beyo
direction
of the CuOconnect
bonds, butparts
nodesof
in the
give(/a,
rise to the
that these
wavevectors
thediagonal
Fermidirections
surface that
near
0) linear
and density
(0, /a).One
By of these is angl
of
states
at
low
energy.
choosing an energy gap that changes sign along the zone diagonals, we can obtain a finite
spectroscopy (ARP
solution to the gap equation. Such a state is called a dx2 y2 state, and one of its defining
eect to map the en
characteristics is the presence of cone-shaped excitation-energy surfaces that vanish at pointstates near the Ferm
like nodes on the diagonals. Thesecandidates:
energy surfaces
are
similar
to
those
in
graphene,
and
have
a
particularly
suited t
the organic superconductors,
materials, and had
characteristic linear energy dependence
of the density
of states (see
Figure
very different
heavy-fermion
superconductors
and
most 31.5)
recently
1990s that was close
from the gapped density of statesstrontium
of a conventional
superconductor.
Thethat
nodal
quasiparticle
ruthenate.
The primary issue
makes
superconducting en
excitations dominate the low temperature
thermodynamic
response,
are seen clearly
this quest dicult
is sample quality.
Theand
s-wave,
The extraordinary d
spin-singlet
superconductors
in a veryconductivity.
special
in experiments such as penetration
depth, heat
capacity andarethermal
Other
fuelled
state of matter,
protected
from the
experiments, using clever arrangements
of Josephson
junctions,
areinuence
sensitiveofto the phase
of by the prize
37
unconventional
ene
defects
Andersons
. They
possess
an the zone
the Cooper pair wavefunction, and
have by
shown
that it theorem
really does
change
sign along
quest that led to an
energy gap in their excitation spectrum that is little
diagonals.
than an order
by non-magnetic
impurities
because it means formore
As a final point, we can think ofaected
the d-wave
state as providing
an alternative
the
decade. The materi
breaksofnoCoulomb
symmetries
of the materials
crystal
charge carriers to minimize the effects
repulsion.
By forming
a Cooper pair with
Bi2 Sr2 CaCu2 O8+ , w
structure. Non-s-wave superconductors break
finite angular momentum, the carriers set up a centrifugal barrier, preventing them from
between two weakly
additional symmetries, possess energy gaps that
simultaneously being at the same place.
layers, providing an
change sign on reection or rotation, and also
with no surface stat
possess nodes on the Fermi surface. When the sign of
gap mapped out by
the superconducting wavefunction
can change
(Fig. 4) was indeed
through a scattering event, impurities become highly
function, which AR
disruptive, masking many of the low-temperature
direction, rotated 4
properties, or even killing superconductivity entirely.
274
Figure 31.6: In CePd2 Si2 , superconductivity appears in a narrow range of pressure when
antiferromagnetism is suppressed[37].
31.4.2
Heavy fermion superconductivity
Heavy fermion metallic states emerge in materials with partially filled f orbitals. These are
typically intermetallic componds containing cerium or uranium, although a number of other
materials, based on atoms such as praseodymium and ytterbium, are now known. At high
temperatures the f electrons act as localized magnetic moments, which can be inferred from
the spin susceptibility (T ) 1/T and from the strong, Kondo-like magnetic scattering in
the electrical resistivity. At low temperatures the f electrons hybridize with the surrounding
conduction electrons to form a coherent but narrow band of heavy Landau quasiparticles. It
is the narrowness of these bands, with correspondingly large densities of states, that leads
to the term heavy fermion.
Heavy fermion compounds are interesting enough on their own, without the appearance
of superconductivity. (The Kondo-lattice problem, for instance, remains a major, open
theoretical topic.) However, many of these materials are also superconducting, and the
superconductivity appears in an unusual way, often tied to a magnetic quantum critical
point. In the heavy fermion compounds, the narrow-band, nearly localized f electrons make
the balance between kinetic and potential energies very delicate. In many of the compounds,
under ambient conditions, this balance tips in favour of potential energy, resulting in the
formation of magnetic states at low temperatures. The balance can be tipped back in favour
of kinetic energy by the application of pressure. This increases the density, reducing the
spacing between atoms and increasing orbital overlap. The tendency to form a magnetic state
31.4. UNCONVENTIONAL PAIRING IN SPECIFIC MATERIALS
275
is reduced, driving the ordering temperature smoothly to zero, as shown in Figure 31.6. This
is called a quantum phase transition, because we have made a new ground state energetically
favourable by tuning a parameter in the hamiltonian. Temperature and entropy are not
important here the quantum phase transition occurs at T = 0.
Near the quantum critical point, even in the absence of magnetism, the electronic medium is
readily polarized magnetically. Magnetic fluctuations are strong their excitation energy
is very small. This then provides a new mechanism for mediating superconducting pairing.
Each heavy quasiparticle is surrounded by an electronic fluid that acts as a spin liquid. The
spin of the quasiparticle couples to the fluid and polarizes it magnetically. The response
of the fluid is strongest at particular wavevectors near q = 0 for a nearly ferromagnetic
metal, and at finite Q for an incipient antiferromagnet. The quasiparticle then propagates
off, but the polarization it induces is left behind and diffuses away slowly. A second heavy
quasiparticle can then pass through the polarized spin liquid and experience an attraction.
Superconductivity has now been observed in heavy fermion compounds at both antiferromagnetic and ferromagnetic quantum critical points. In the antiferromagnetic case, the pairing
symmetry is thought to be d-wave, as in the cuprates. The ferromagnetic case is particularly
exotic: pairing must be occurring in a spin triplet state, and it is not immediately clear how
the superconductivity coexists spatially with the ferromagnetism.
276
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Lett. 84, 2662 (2000).
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uck, R. Ph.D. thesis, Technische Hochschule, Stuttgart (1965).
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Solid State Theory

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Introduction to Solid State Physics

Introduction to Solid State Physics

2 Thermodynamics and statistical mechanics

3 Thermal properties of the Fermi gas

4 Review of single-particle quantum mechanics

5 Many-particle quantum systems

Introduction to Solid State Physics

Representation of operators in second quantization . . . . . . . . . .

6 Applications of second quantization

8 Screening and the random phase approximation

11 The nearly free electron model and tight binding

9 Scattering and periodic structures

nearly free electron model

Introduction to Solid State Physics

12 The tight-binding approximation

15 Density functional theory

dynamics of Bloch electrons I

17 The dynamics of Bloch electrons II

19 Electronic structure of selected metals

Introduction to Solid State Physics

Boltzmann transport equation

23 Time-dependent perturbation theory

24 Density response of the electron gas

25 Electrons in one dimension

26 Collective modes and response functions

electron spectral function

28 Landaus Fermi Liquid theory

31 Superconductivity III exotic pairing

Introduction to Solid State Physics

Introduction to Solid State Physics

Allowed momentum states in two dimensions . . . . . . . . . . . . . . . . . .

Gibbs energy surface . . . . . . . . . . . . . . . . . . . . . .

Density of states of the electron gas . . . . . . . . . . . . . . . . . . . . . . .

Energy eigenstates of the harmonic oscillator. . . . . . . . . . . . . . . . . .

Tight binding on a square lattice . . . . . . . . . . . . . . . . . . . . . . . .

HartreeFock self consistency loop . . . . . . . . . . . . . . . . . . . . . . . .

The response of the electron gas to an external charge. . . . . . . . . . . . .

10.1 Bragg scattering. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Degenerate energy bands . . . . . . . . . . . . .

Introduction to Solid State Physics

12.1 s-like band in a FCC crystal . . . . . . . . . . . . . . . . . . . . . . . . . . .

Bragg planes and reciprocal lattice vectors . . . . . . . . . . .

14.1 Pseudopotentials and pseudowavefunctions . . . . . . . . . . . . . . . . . . . 107

Cyclotron orbits in a magnetic field . . . . . . . .

Quantum states in a strong magnetic field .

Bragg planes and Brillouin zones in two dimensions . . . .

Introduction to Solid State Physics

19.6 Free-electron Fermi surfaces for HCP structure . . . .

The density of states of a doped semiconductor. . . . . . . . . . . . . . . .

20.1 Density of states in a Mott insulator . . . . . . . . . . .

22.1 Evolution of electron states in the semiclassical phase space . . . . . . . . . . 188

Free electrons in one dimension . . . . .

Introduction to Solid State Physics

Electron spectral function of a noninteracting system . .

The ground state distribution function. . . . . . . . . . . . . . . . . . . . . .

The superconducting transition of mercury . . . . . .

Effective interaction in an elastic solid . . . . . . . . . . . . . . .

Magnetic fluctuations as a pairing glue . . . . . . .

Introduction to Solid State Physics

Introduction to Solid State Physics

Introduction to Solid State Physics

The free Fermi gas

Sommerfeld free electrons

1.2. SOMMERFELD FREE ELECTRONS

Tri e(i )ni

Since k 2 , we have (taking the logarithmic derivative)

Rearranging for D(), we get

where H() vanishes as and is polynomial in as +.

d = K() {f () f (+)} = K() =

D()d + ( F )D(F ) + (kB T )2 D0 (F ),

For electrons in 3 D, D() 1/2 , so that

D()d + ( F )F D(F ) + (kB T )2 [F D0 (F ) + D(F )]