Thermodynamics of Crystalline States (2nd Edition) Fujimoto
Thermodynamics of Crystalline States
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Thermodynamics of Crystalline States (2nd Edition) Fujimoto
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Thermodynamics of Crystalline States (2nd Edition) Fujimoto
Minoru Fujimoto
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Thermodynamics
of Crystalline States
Second Edition
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Thermodynamics of Crystalline States (2nd Edition) Fujimoto
Minoru Fujimoto
Department of Physics
University of Guelph
Guelph, ON NIG 2W1
Canada
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ISBN 978-1-4614-5084-9 ISBN 978-1-4614-5085-6 (eBook)
DOI 10.1007/978-1-4614-5085-6
Springer New York Heidelberg Dordrecht London
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Thermodynamics of Crystalline States (2nd Edition) Fujimoto
Preface
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Originated from steam engines, in thermodynamics the energy exchange is
formulated traditionally for homogeneous states of materials. Applying to
condensed matters however, laws of thermodynamics have to be used with respect
to the structural detail. Following Kirkwood’s Chemical Thermodynamics, this
book is written for lattice dynamics in crystalline states under the laws of thermo-
dynamics. It is noted that lattice symmetry remains implicit in thermodynamic
functions of crystalline states, if assumed as homogeneous. In contrast, deformed
crystals with disrupted symmetry are not stable and inhomogeneous, exhibiting
mesoscopic properties, for which the lattice dynamics should be redefined under
thermodynamic principles. I have selected the topics of structural changes, mag-
netic crystals, and superconducting transitions in this book to discuss these basic
thermodynamic processes in crystalline states.
Born and Huang have laid ground for thermodynamics of crystalline states in
their book Dynamical Theory of Crystal Lattices. However, they considered that
order–disorder phenomena was independent from the lattice dynamics, and so
excluded it from their book. On the other hand, today new evidence indicates that
the problem should be treated otherwise; in fact, the lattice plays a vital role in
ordering processes. Accordingly, I was motivated to write about the physics of
crystal lattice in the light of Born-Huang’s principles, which constitutes my primary
objective in this book.
In modern experiments, mesoscopic objects in crystals can be investigated
within the timescale of observation, yielding results that appear somewhat unusual,
if compared with macroscopic experiments. It is important that thermodynamic
relations in mesoscopic states should be described with respect to the timescale of
observation. Also significant is that mesoscopic quantities in crystals are driven by
internal interactions in nonlinear character. I have therefore discussed thermody-
namic quantities with regard to the timescale of observation, including elementary
accounts of nonlinear physics to deal with long-range correlations. For the conve-
nience of readers who are not particularly familiar with nonlinear dynamics,
Appendix is attached for some useful formula of elliptic functions.
v
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vi Preface
Thermodynamics of Crystalline States (2nd Edition) Fujimoto
I have rewritten this second edition for advanced students in physics and
material science, assuming basic knowledge of traditional thermodynamics
and quantum theories. This book is designed for serving as a useful textbook for
classroom and seminar discussions. I hope that it will stimulate advanced studies of
condensed matter.
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I should mention with my sincere appreciation that I have benefited for my
writing from numerous discussions with and comments from my colleagues
and students. Finally, I thank my wife Haruko for her continuous support and
encouragements.
Mississauga, Ontario Minoru Fujimoto
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Thermodynamics of Crystalline States (2nd Edition) Fujimoto
Contents
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1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 Crystalline Phases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.2 Structural Changes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.3 New Concepts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.3.1 Modulated Phases and Renormalized Coordinates . . . . 7
1.3.2 Thermodynamic Changes and Nonlinear Dynamics . . . 8
1.3.3 Fields within Thermodynamic Boundaries . . . . . . . . . . 8
1.3.4 Adiabatic Potentials . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.4 Sampling Modulated States . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Exercise 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
2 Phonons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.1 Normal Modes in a Simple Crystal . . . . . . . . . . . . . . . . . . . . . 11
2.2 Quantized Normal Modes . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.3 Phonon Field and Momentum . . . . . . . . . . . . . . . . . . . . . . . . . 16
2.4 Thermal Equilibrium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
2.5 Specific Heat of a Monatomic Crystal . . . . . . . . . . . . . . . . . . . 20
2.6 Approximate Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.6.1 Einstein’s Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.6.2 Debye’s Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.7 Phonon Statistics Part 1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2.8 Compressibility of a Crystal . . . . . . . . . . . . . . . . . . . . . . . . . . 28
Exercise 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
3 Order Variables and the Adiabatic Potential . . . . . . . . . . . . . . . . 33
3.1 A One-dimensional Ionic Chain . . . . . . . . . . . . . . . . . . . . . . . 33
3.2 Displacive Variables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
3.3 Born-Oppenheimer’s Approximation . . . . . . . . . . . . . . . . . . . 39
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viii Contents
Thermodynamics of Crystalline States (2nd Edition) Fujimoto
3.4
Equilibrium Crystals and the Bloch Theorem . . . . . . . . . . . . . 45
3.4.1 Reciprocal Lattice and Renormalized Coordinates . . . . 45
3.4.2 The Bloch Theorem . . . . . . . . . . . . . . . . . . . . . . . . . . 47
3.4.3 Lattice Symmetry and the Brillouin Zone . . . . . . . . . . . 49
3.5 Phonon Scatterings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
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3.5.1 Phonon Scatterings in Crystals . . . . . . . . . . . . . . . . . . 51
3.5.2 The Born-Huang Relaxation and Soft Modes . . . . . . . . 52
Exercise 3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
4 Mean-Field Theories of Binary Ordering . . . . . . . . . . . . . . . . . . . 55
4.1 Probabilities in Binary Alloys . . . . . . . . . . . . . . . . . . . . . . . . . 55
4.2 The Bragg-Williams Theory . . . . . . . . . . . . . . . . . . . . . . . . . . 57
4.3 Becker’s Interpretation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
4.4 Ferromagnetic Order . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
4.5 Ferromagnetic Transition in Applied Magnetic Field . . . . . . . . 64
Exercise 4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
5 Pseudospin Clusters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67
5.1 Pseudospins for Binary Displacements . . . . . . . . . . . . . . . . . . 67
5.2 A Tunneling Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
5.3 Pseudospin Correlations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
5.4 Pseudospin Clusters in Crystals . . . . . . . . . . . . . . . . . . . . . . . 73
5.4.1 Classical Pseudospins in Crystals . . . . . . . . . . . . . . . . . 73
5.4.2 Clusters of Pseudospins . . . . . . . . . . . . . . . . . . . . . . . . 74
5.5 Examples of Pseudospin Clusters . . . . . . . . . . . . . . . . . . . . . . 78
5.5.1 Cubic to Tetragonal Transition in SrTiO3 . . . . . . . . . . . 78
5.5.2 Monoclinic Crystals of Tris-Sarcosine Calcium
Chloride (TSCC) . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
Exercise 5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
6 Critical Fluctuations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
6.1 The Landau Theory of Binary Transitions . . . . . . . . . . . . . . . . 83
6.2 Internal Pinning of Adiabatic Fluctuations . . . . . . . . . . . . . . . 87
6.3 Critical Anomalies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
6.4 Observing Anomalies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
6.5 Extrinsic Pinning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
6.5.1 Pinning by Point Defects . . . . . . . . . . . . . . . . . . . . . . . 93
6.5.2 Pinning by an Electric Field . . . . . . . . . . . . . . . . . . . . 93
6.5.3 Surface Pinning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
Exercise 6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
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Thermodynamics of Crystalline States (2nd Edition) Fujimoto
7
Pseudospin Correlations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
7.1 Propagation of a Collective Pseudospin Mode . . . . . . . . . . . . . 97
7.2 Transverse Components and the Cnoidal Potential . . . . . . . . . 101
7.3 The Lifshitz Condition for Incommensurability . . . . . . . . . . . . 103
7.4 Pseudopotentials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
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Exercise 7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
8 Soliton Theory of Long-Range Order . . . . . . . . . . . . . . . . . . . . . 111
8.1 A Longitudinal Dispersive Mode of Collective Pseudospins . . . 111
8.2 The Korteweg–deVries Equation . . . . . . . . . . . . . . . . . . . . . . 115
8.3 Solutions of the Korteweg–deVries Equation . . . . . . . . . . . . . 117
8.4 Cnoidal Theorem and the Eckart Potential . . . . . . . . . . . . . . . 120
8.5 Condensate Pinning by the Eckart Potentials . . . . . . . . . . . . . . 122
8.6 Born–Huang’s Transitions . . . . . . . . . . . . . . . . . . . . . . . . . . . 126
8.7 Topological Mapping of Mesoscopic Fields . . . . . . . . . . . . . . 129
Exercise 8 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 132
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
9 Soft Modes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
9.1 The Lyddane–Sachs–Teller Relation . . . . . . . . . . . . . . . . . . . . 137
9.2 Soft Lattice Modes of Condensates . . . . . . . . . . . . . . . . . . . . . 141
9.2.1 The Lattice Response to Collective Pseudospins . . . . . . 141
9.2.2 Temperature Dependence of Soft-Mode
Frequencies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
9.2.3 Cochran’s Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148
9.3 Symmetry Change at Tc . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
Exercise 9 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
10 Experimental Studies on Critical Fluctuations . . . . . . . . . . . . . . . 155
10.1 Diffuse X-Ray Diffraction . . . . . . . . . . . . . . . . . . . . . . . . . . 155
10.2 Neutron Inelastic Scatterings . . . . . . . . . . . . . . . . . . . . . . . . 160
10.3 Light Scattering Experiments . . . . . . . . . . . . . . . . . . . . . . . . 164
10.3.1 Brillouin Scatterings . . . . . . . . . . . . . . . . . . . . . . . . 165
10.3.2 Raman Scatterings . . . . . . . . . . . . . . . . . . . . . . . . . 169
10.4 Magnetic Resonance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
10.4.1 Principles of Nuclear Magnetic Resonance
and Relaxation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
10.4.2 Paramagnetic Resonance of Impurity Probes . . . . . . 175
10.4.3 The Spin Hamiltonian . . . . . . . . . . . . . . . . . . . . . . . 176
10.4.4 Hyperfine Interactions . . . . . . . . . . . . . . . . . . . . . . . 180
10.5 Magnetic Resonance in Modulated Crystals . . . . . . . . . . . . . 180
10.6 Examples of Transition Anomalies . . . . . . . . . . . . . . . . . . . . 183
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
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Thermodynamics of Crystalline States (2nd Edition) Fujimoto
11
Magnetic Crystals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
11.1 Microscopic Magnetic Moments in Crystals . . . . . . . . . . . . . 189
11.2 Paramagnetism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
11.3 Spin–Spin Correlations . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
11.4 Spin Clusters and Magnetic Symmetry . . . . . . . . . . . . . . . . . 198
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11.5 Magnetic Weiss Field . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
11.6 Spin Waves . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
11.7 Magnetic Anisotropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
11.8 Antiferromagnetic and Ferrimagnetic States . . . . . . . . . . . . . 208
11.9 Fluctuations in Ferromagnetic and Antiferromagnetic
States . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
11.9.1 Ferromagnetic Resonance . . . . . . . . . . . . . . . . . . . . 211
11.9.2 Antiferromagnetic Resonance . . . . . . . . . . . . . . . . . 212
Exercise 11 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214
12 Phonon and Electron Statistics in Metals . . . . . . . . . . . . . . . . . . . 215
12.1 Phonon Statistics Part 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . 215
12.2 Conduction Electrons in Metals . . . . . . . . . . . . . . . . . . . . . . 218
12.2.1 The Pauli Principle . . . . . . . . . . . . . . . . . . . . . . . . . 218
12.2.2 The Coulomb Interaction . . . . . . . . . . . . . . . . . . . . . 220
12.2.3 The Bloch Theorem in Equilibrium Crystals . . . . . . . 221
12.3 Many-Electron Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222
12.4 Fermi–Dirac Statistics for Conduction Electrons . . . . . . . . . . 226
Exercise 12 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
13 Superconducting Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
13.1 Superconducting States . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
13.1.1 Near-Zero Electrical Resistance . . . . . . . . . . . . . . . . 229
13.1.2 The Meissner Effect . . . . . . . . . . . . . . . . . . . . . . . . 231
13.1.3 Thermodynamic Equilibrium Between Normal
and Superconducting Phases . . . . . . . . . . . . . . . . . . 233
13.2 Long-Range Order in Superconducting States . . . . . . . . . . . . 235
13.3 Electromagnetic Properties of Superconductors . . . . . . . . . . . 237
13.4 The Ginzburg–Landau Equation and the
Coherence Length . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
Exercise 13 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 248
14 Theories of Superconducting Transitions . . . . . . . . . . . . . . . . . . . 249
14.1 The Fröhlich’s Condensate . . . . . . . . . . . . . . . . . . . . . . . . . . 249
14.2 The Cooper Pair . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
14.3 Critical Anomalies and the Superconducting Ground State . . . 255
14.3.1 Critical Anomalies and a Gap in a
Superconducting Energy Spectrum . . . . . . . . . . . . . . 255
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