1 The Basic Approach

1．Quantum Mechanics

A．Waves and Observables

B．Atomic States

2．Tight-Binding Theory and the Simplest Molecule

A．Molecular Orbitals

B．Extended Hückel Theory

C．Electronic Structure of Li2

D．The Total Energy

3．The Simplest Many-Atom System,a Metal

A．Energy Bands

B．Matching to Free-Electron Bands

C．Cohesion

4．Hybrid States and Semiconductors

A．Needed Parameters

B．The Nitrogen Molecule

C．sp-Hybrids

D．Semiconductors

E．Overall Organization of Solid-State Systems

5．Ionic Insulators

A．Independent Ions

B．Couplings and Perturbation Theory

6．Simple Metals and Pseudopotentials

A．Empty-Core Pseudopotentials

B．Effective Interaction Between Ions

C．Partly-Filled Bands

7．Transition-Metal and f-Shell Systems

A．Coupling of d-States

B．The Coulomb Ud

C．The Energy Bands and the Friedel Model

D．Correlated States in f-Shell Metals

E．Transition-Metal and f-Shell-Metal Compounds

8．Surfaces and Other Bonding Types

A．Surface Energies

B．Other Systems

2 Bonding in Tetrahedral Semiconductors

1．The Crystal Structure and Notation

2．Hybrids and Their Coupling

A．sp3-Hybrids

B．The Covalent Energy,V2

C．The Polar Energy,V3

D．The Metallic Energy,V1

E．The Overlap Repulsion.,V0(d)

F．Total Energies and Coulomb Effects

3．The Cohesive Energy

A．The Bond Orbital Approximation and Matrices

B．Metallization

C．Homopolar Systems

D．Polar Systems

E．Coulomb Corrections

4．The Dependence of Energy upon Volume

A．Trends in Bond Lengths

B．The Radial Force Constant

C．The Grüneisen Constant

5．Structural Stability and Moments

A．The Second Moment

B．The Dependence Upon Structure

C．The Fourth Moment

D．Structural Stability

E．Angular Rigidity

3 Elastic Properties of Semiconductors

1．Elastic Constants and Bulk Modulus

2．Shear Constants

A．Twist Distortion

B．Graphitic Distortion and Internal Displacements

C．Interatomic Metallization and Effects of Polarity

3．Vibrational Frequencies

A．Acoustic Modes

B．Optical Modes

C．Effects of Polarity

4．Interatomic-Interaction Models

A．Traditional Models

B．The Angular Force Puzzle

C．A Solution for Carbyne

D．Application to Tetrahedral Semiconductors

4 The Dielectric Properties of Semiconductors

1．Bond Dipoles and Effective Charges

2．Electronic Susceptibilities

A．The Linear Response

B．The Effect of Metallization

C．Higher-Order Susceptibilities

D．Magnetic Susceptibility

3．Internal Displacement Properties

A．The Transverse Charge

B．Optical Mode Splitting

C．The Static Dielectric Constant

D．The Piezoelectric Effect

E．Elastooptic Effect

F．Electrooptic Effect

G．Dielectric Response in the Infrared

5 Semiconductor Energy Bands

1．Wavenumbers and Brillouin Zones.

2．Bonding and Antibonding Bands

A．Bands from the coupling V1

B．Bands for polar crystals

C．The effects of V1x

3．Full Tight-Binding Bands

A．sp3-bands

B．A Peripheral s＊-State

C．Fitting the Free-Electron Bands

D．Obtaining Universal Parameters

E．Application to Polar Systems

F．The Band States

G．Spin-Oribit Coupling

4．More Accurate Bands

5．Corrections to the Bands

A．Coulomb Enhancement of the Gaps

B．Polarons

C．Wannier Functions

6 Electronic Properties

1．The Valence-Band Maximum.

2．Optical Absorption

A．Vertical Transitions

B．The Optical Matrix Elements

C．The Absorption Threshold

D．Indirect Gaps

E．The Optical Absorption Peaks

3．Effective Masses

A．Conduction-Band Mass at г

B．Light-Hole Mass

C．Heavy-Hole Mass

D．Masses for Indirect Minima

4．Dynamics of Band States

A．The Dynamical Equations

B．Limitations of the Theory

C．The Dynamics of Holes

5．The Form of the Hole Bands

A．Heavy- and Light-Hole Bands

B．Negative Gaps

C．Spin-Orbit-Split Bands

D．Density of States

6．The Optical Absorption Rate

A．The Matrix elements

B．The Rate

7 Effects of Lattice Distortions

1．Deformation Potentials for Dilatations

A．Nonorthogonality and Electrostatic Contributions

B．Predicted Deformation Potentials

C．Experimental Values

2．Band Shifts Due to Shear Distortions

A．The Effects of Nonorthogonality

B．Indirect Gap Conduction Bands

C．Valence Bands

D．Shifts of the Spin-Orbit Split Bands

3．The Electron-Phonon Interaction

A．Interactions for Simple Systems

B．Acoustic Modes and Conduction Electrons

C．Electrostatic Contributions in Polar Crystals

D．Interaction with Optical Modes

E．Holes and Local Lattice Rotations

F．Acoustic Modes and Holes

a．Light Holes and Longitudinal Modes

b．Light Holes and Shear Modes

c．Heavy Holes and Light-Heavy Matrix Elements

G．Electrostatic Potentials and Screening

H．Electron Scattering by Acoustic Modes

8 Impurities and Defects

1．Semiconductor Alloys

A．Enthalpies of Solution

B．Lattice Distortions

C．Doping and Energies of Substitution

D．Alloy Energy Bands and Scattering

2．Impurity States

3．Vacancies and Interstitials

A．The Ideal Vacancy

B．Jahn-Teller Distortion

C．The Tetrahedral and Shared-Site Interstitials

D．The Role in Diffusion

9 Bonding In Ionic Crystals

1．The Independent-Ion Model

A．Coulomb Effects and Closed-Shell Ions

B．Crystal Structures and Electrostatic Energy

C．The Band Gap

D．The Cohesive Energy

E．The Born Electrostatic Model

F．Coulomb Enhancements of the Gap.

2．Coupled Ions

A．Covalent Corrections to the Energy

B．The Energy Bands

C．Special Points

D．Volume-Dependent Properties in Second Order

10 Elastic Properties of Ionic Crystals

1．The Overlap Repulsion

A．Based upon Local-Density Theory

B．Fitting the Power-Law Form

C．Second-Neighbor Repulsions

2．Resonant Bonds

3．Volume-Dependent Properties

A．Equilibrium Spacing

B．Cohesive Energy

C．Bulk Modulus

D．Grüneisen Constant

4．Elastic Constants

A．The Shear Constant,(c11-c12)/2

B．The Shear Constant,c44,and the Chemical Grip

C．Vibrational Frequencies

5．Coulomb Contributions

A．Volume-Dependent Properties

B．Elastic Constants

11 Dielectric Properties of Ionic Solids

1．The Optical Dielectric Susceptibility

A．The Alkali Halides

B．Noble-Metal Halides

C．Divalent Compounds

D．Ten-Electron Compounds

E．The Implication of the Errors

F．Local-Field Effects

G．Application to Other Ionic Solids

2．Effective Ionic Charges

A．The Static Effective Charge

B．The Transverse Charge

C．The Static Dielectric Constant

12 Covalent Insulators,SiO2

1．The Structure and Bonding Unit

2．The Parameters

3．Cohesive Energy

A．Metallization

B．Inter-atomic Metallization

4．Radial Force Constant

5．The Angle at Oxygen

6．Elasticity and the Bonding Unit

7．The Vibrational Frequencies

8．The Refractive Index

9．Effective Transverse Charge

10．Energy Bands

11．Summary of the SiO2 Study

12．Other Covalent Insulators

A．GeO2

B．Oxyanions,Sulfates,etc.

C．Thallium Arsenic Selenide

D．Other Mixed Covalent-Ionic Solids

E．A Complex Semiconductor,SiP2

13 Simple Metals,Electronic Structure

1．Crystal Structures

2．Free-Electron States

3．Tight-Binding Theory

A．Cohesive Energy

B．The Bulk Modulus

4．Pseudopotentials

A．Empty-Core Pseudopotentials

B．Madelung and Total Free-Electron Energy

C．Equilibrium Spacing and Bulk Modulus

D．Higher-Order Terms

5．Structure Factors and Form Factors

6．Screening of Pseudopotentials

A．Fermi-Thomas Theory

B．Screened Form Factors

C．The Real-Space Pseudopotential,w(r)

D．More Accurate Screening

7．Diffraction and Fermi Surfaces

A．Motion in a Uniform Magnetic Field

B．Construction of Fermi Surfaces

C．Fermi-Surface Distortions

D．Magnetic Breakdown

8．Scattering by Defects

9．Electron-Phonon Interaction

A．The Structure Factor

B．Electron Scattering

14 Simpla Metals,Bonding Properties

1．The Band-Structure Energy

A．Vibrational Frequencies and the Kohn Effect

B．Other Properties

2．Interatomic Interactions

A．The Effective Interaction

B．The Total Energy

C．Volume Dependence of the Total Energy

3．Properties from Interatomic Interactions

A．The Bulk Modulus

B．Deviations from the Cauchy Relations

C．Poisson's Ratio

D．The Grüneisen Constant

4．Calculation of Vibration Spectra

5．Liquid Metals.

A．Liquid Structure Factors

B．Resistivity

6．Pseudopotentials and Covalent Bonding

A．Coupling Through the[100]2π/a States

B．Polar Systems

7．Alloys

A．Heats of Solution

a．Homovalent solutions.

b．Heterovalent solutions.

B．Alloy Formation Energies

15 Transition Metals

1．Transition-Metal Pseudopotentials

A．Pseudopotentials and OPW's

B．Atomic d-States

C．Hybridization with d-States

D．Contribution to the Pseudopotential

2．Coupling Between d-States

A．The dd-Coupling

B．The Slater-Koster Tables

C．Energy Bands

D．Fermi Surfaces and Density of States

3．The Atomic Sphere Approximation

A．The Atomic Surface Method

B．Values for rd

C．Further Approximations

4．The Friedel Model

A．Band Width from the Second Moment

B．Coulomb Shifts and Values for εd

C．Hybridization Already Included

D．The Total Energy

E．The Cohesive Energy

F．Volume-Dependent Properties

G．Crystal Structure Determination

H．Transition-Metal Alloys

5．Interatomic Interactions and Elasticity

A．The Effective Interaction

B．Elastic Constants

C．Multibody Forces

6．Ferromagnetism

A．The Exchange Energy

B．The Ferromagnetic State

16 f-Shell Metals

1．Correlated States

A．An Exact Solution

B．The Unrestricted Hartree-Fock Approximation

C．Self-Interactions

D．Generalization to d-and f-Bands

a．Local Moments in the UHF Approximation

b．Generalizing the Exact Result

2．Parameters for f-Shell Systems

A．ff-Coupling

B．General Formulae

C．Coulomb Uf

D．Spin-Orbit Coupling

E．The sd-Electrons

3．Electronic Structure of Rare Earths

A．The f-Electrons

B．The Cohesive Energy

C．The Volume-Dependent Energy

D．Interatomic Interactions

E．Crystal Structure

4．Electronic Structure of the Actinides

A．The Cohesive Energy

B．Volume-Dependent Properties

C．Interatomic Interactions

D．Crystal Strucutres

5．Criterion for Local Moments

A．Phase Shifts

B．The Friedel Sum Rule

C．Resonant States

D．The Criterion

6．Strongly Correlated Systemse

A．The Electronic Structure of Americium

B．Antiferromagnetism

C．The Kondo Effect

D．Heavy Fermion Systems

17 Transition-Metal(AB)Compounds

1．Parameters for Compounds

2．The Monoxides,Nitrides and Carbides

A．The Octet Compounds

B．Other Oxides and Nitrides

3．Quantitative Theory

A．The Essential Electronic Structure

B．Bands for the Compounds

C．Covalent and Polar Energies

D．The d-State Energy,εd

E．The pd-Bonding Energy and Cohesion

F．The Volume-Dependent Properties

4．Correlated States

A．Correlation Energy

B．The Metal-Insulator Transition

5．The Role of d-States in Semiconductors

18 Other Transition and f-Shell Compounds

1．Compounds of f-Shell Metals

A．Rare-Earth Compounds

B．Actinide Compounds

2．The Dioxides

A．TiO2,Rutile

B．RuO2

3．Trioxides,the Perovskites

A．The Perovskite Structure

B．The Electronic Structure

C．Bonding Properties

D．Madelung Energies

E．The Electron-Phonon Interaction

4．The Cuprates

A．The Electronic Structure

B．Peierls Instabilities and the Antiferromagnetic State

C．Phonons,Paramagnons,and Excitons

19 Surfaces and Interfaces

1．Surface Energies

A．Elemental Semiconductors

B．Ionic Crystals and Polar Semiconductors.

C．Metal Surfaces.

D．Interaction Between Surfaces and Giant Magnetoresistance

2．Photothresholds,Work Functions and Electron Affinities

A．Corrections to the Tight-Binding Photothreshold

B．Photothresholds in Semiconductors.

C．Work Functions in Metals

3．Reconstruction on Semiconductor Surfaces

A．The Silicon(111)2×1 and General(110)Surfaces

B．The Silicon(100)2×1

C．Polar Surfaces

D．The Silicon(111)7×7

4．Interfaces

A．Matching Wavefunctions at Heterojunctions

B．Semiconductor Band Line-Ups

C．Other Views

D．Strain-Layer Superlattices

E．Metal-Semiconductor Interfaces

F．Adsorbed Atoms on Semiconductors

20 Other Systems

1．Non-Tetrahedral Covalent Solids

A．Two Nearest Neighbors,S,Se and Te

B．Multicenter Bonds

C．Zn3P2

D．Boron

2．Inert-Gas Solids and Molecular Crystals

A．Electronic Structure of Inert-Gas Solids

B．Excitons

C．Dielectric Polarizability

D．Van-der-Waals Interaction

E．Lennard-Jones Interaction

F．Molecular Solids

3．π-Bonded Systems

A．Graphite

a．Energy Bands

b．The π-Bonding Energy

B．Fullerenes

C．The Heme Group

4．Systems with Hydrogen

A．H2

B．Central Hydrides

C．Hydrocarbons

D．Shared-Hydrogen Bonding

Author Index

Subject Index