A Matter of Density: Exploring the Electron Density Concept in the Chemical, Biological, and Materials Sciences

A MATTER OF DENSITY......Page 2
CONTENTS......Page 6
PREFACE......Page 8
CONTRIBUTORS......Page 10
1 INTRODUCTION OF PROBABILITY CONCEPTS IN PHYSICS—THE PATHTO STATISTICAL MECHANICS......Page 12
FURTHER READING......Page 25
2.1 QUANTA OF RADIATION......Page 26
2.2 ADIABATIC INVARIANTS......Page 29
2.3 PROBABILITY LAWS......Page 30
2.4 MATTER WAVES......Page 33
2.5 QUANTUM STATISTICS......Page 34
2.6 MATRIX MECHANICS AND COMMUTATION RELATIONS......Page 35
2.7 WAVE FUNCTIONS......Page 38
2.8 THE STATISTICS OF ELECTRONS......Page 40
2.9 DOES GOD PLAY DICE?......Page 42
REFERENCES......Page 47
3.1 MOLECULAR STRUCTURE......Page 52
3.2 SELF-CONSISTENT TREATMENT OF MANY-ELECTRONSYSTEMS......Page 57
3.3 DENSITY MATRICES AND ELECTRON CORRELATION......Page 61
3.4 EXPERIMENTAL DETERMINATION OF THE ELECTRON DENSITY......Page 65
3.4.1 Determination of the Unit Cell Constants and Their Use in Ascertaining the Contents of the Unit Cell......Page 69
3.5 CONCLUDING REMARKS......Page 75
REFERENCES......Page 76
4 ATOMS IN MOLECULES......Page 78
4.1 CRITICAL POINTS OF THE ELECTRON DENSITY......Page 79
4.2 VIRIAL PARTITIONING OF THE ELECTRON DENSITY......Page 82
4.3 THE BOND PATH AND THE MOLECULAR GRAPH......Page 87
4.4 CATASTROPHE POINTS IN THE CHANGE OF MOLECULAR STRUCTURE......Page 89
4.5 TOPOLOGY OF THE LAPLACIAN DISTRIBUTION......Page 91
4.6 THE FERMI HOLE AND ELECTRON DELOCALIZATION......Page 94
4.7 ELECTRON LOCALIZATION FUNCTION......Page 97
4.8 THE SOURCE FUNCTION......Page 100
4.9 STOCKHOLDER PARTITIONING OF THE ELECTRON DENSITY......Page 103
4.10 ATOMS IN MOMENTUM SPACE......Page 107
4.11 DENSITY MATRIX PARTITIONING......Page 108
4.12 CONCLUDING REMARKS......Page 113
4.13 EPILOGUE......Page 114
REFERENCES......Page 115
5.1 THE HOHENBERG–KOHN THEOREMS......Page 118
5.2 THE CHEMICAL POTENTIAL......Page 122
5.3 THE EXCHANGE-CORRELATION HOLE......Page 124
5.4 THE KOHN–SHAM EQUATION......Page 125
5.5 A MATTER OF PHASE......Page 129
REFERENCES......Page 132
6.1 THE CHALLENGE OF DENSITY-FUNCTIONAL THEORY......Page 136
6.2 EXCHANGE AND CORRELATION FUNCTIONALS......Page 138
6.3 INGREDIENTS AND TECHNIQUES FOR CONSTRUCTING DENSITY FUNCTIONAL APPROXIMATIONS......Page 141
6.4 NONEMPIRICAL DERIVATION AND LOCAL DENSITY MODELS......Page 143
6.5 SEMILOCAL FUNCTIONALS BEYOND THE LOCAL DENSITY APPROXIMATION......Page 145
6.6 CONSTRAINT SATISFACTION......Page 147
6.7 THE COMEBACK OF EXACT EXCHANGE: GLOBAL AND LOCAL HYBRIDS......Page 153
6.8 THE BEST OF BOTH WORLDS: RANGE-SEPARATED HYBRIDS......Page 155
6.9 EMPIRICAL FITS......Page 157
6.10 CORRELATION FUNCTIONALS COMPATIBLE WITH EXACT EXCHANGE......Page 159
6.11 CURRENT TRENDS AND OUTLOOK FOR THE FUTURE......Page 162
REFERENCES......Page 166
7.1 INTRODUCTION......Page 168
7.2.1 Global Reactivity Descriptors......Page 169
7.2.2 Local Reactivity Descriptors......Page 177
7.3 MOLECULAR ELECTRONIC STRUCTURE PRINCIPLES......Page 183
7.3.2 Electrophilicity Equalization Principle......Page 184
7.3.3 Hard–Soft Acid–Base (HSAB) Principle......Page 185
7.3.5 Minimum Polarizability Principle......Page 187
7.4 CONCEPTUAL DFT AS A USEFUL TOOL TOWARDS ANALYZING CHEMICAL REACTIVITY......Page 188
7.4.2 Structure, Bonding, Reactivity, and Aromaticity in Cluster Assemblies......Page 189
7.4.3 Bond-Stretch Isomerism......Page 194
7.4.4 Analysis of the Toxic Effects of Different Molecules through QSAR/QSTR-Based Model......Page 196
7.4.5 CDFT as a Novel Tool toward Designing Suitable Storage Materials for Trapping Hydrogen......Page 200
7.5 CONCLUDING REMARKS......Page 205
REFERENCES......Page 206
8.1 THE MOLECULAR SIMILARITY PRINCIPLE IN DRUG DESIGN......Page 214
8.2 ELECTRON-DENSITY-BASED ATOMIC AND MOLECULAR SIMILARITY ANALYSIS......Page 217
8.3 MOLECULAR SIMILARITY MEASURES FROM CRITICAL POINTS OF THE ELECTRON DENSITY......Page 225
8.4 ELECTRON-DENSITY-DERIVED MOLECULAR SURFACE DESCRIPTORS......Page 228
8.5 ALIGNMENT-FREE MOLECULAR SHAPE AND ELECTRONIC PROPERTY DESCRIPTORS......Page 233
8.6 NETWORK GRAPHS FROM MOLECULAR SIMILARITY......Page 235
REFERENCES......Page 238
9.1 THE ELECTRONIC DENSITY......Page 244
9.2 THE ELECTROSTATIC POTENTIAL......Page 245
9.3 THE AVERAGE LOCAL IONIZATION ENERGY......Page 248
9.4.1 Overview......Page 250
9.4.2 Noncovalent Interactions: Chemical Vapor Sensing......Page 252
9.4.3 Covalent Interactions: Graphene......Page 256
9.4.4 Carbon Nanotubes......Page 260
9.5 SUMMARY......Page 263
REFERENCES......Page 264
10.1 INTRODUCTION......Page 268
10.3 A POSTULATE AND ITS EXISTING SUPPORT......Page 271
10.4 STRUCTURE OF MOTION, TRANSFERABILITY, AND ANISOTROPY......Page 275
10.5 CONCLUSION......Page 279
REFERENCES......Page 280
11.1 INTRODUCTION......Page 282
11.2 THE PREDICTIVE CAPABILITY OF DFT......Page 283
11.3 SLAB MODELS USED IN SURFACE/INTERFACE STUDIES......Page 285
11.4 THE SURFACE ENERGY AND ISSUES WITH POLAR SURFACES......Page 287
11.5 ADSORBATE ON SURFACES—ENERGETICS AND THE WULFF CONSTRUCTION......Page 293
11.5.1 CdSe Crystallites......Page 294
11.5.3 WC crystallites......Page 297
11.6 ADSORBATES ON SURFACES—ELECTRONIC STRUCTURE......Page 300
11.7 SURFACE PHASE DIAGRAMS: FIRST PRINCIPLES THERMODYNAMICS......Page 303
11.8 INTERFACE PHASE DIAGRAMS: FIRST PRINCIPLES THERMODYNAMICS......Page 308
11.8.1 Interface Phase Diagrams Not Including Vibrational and Configurational Energies......Page 313
11.8.2 Impact of Other Factors (For Example, the Vibrational and Configurational Energy Contributions) on Interface Phase Diagrams......Page 315
REFERENCES......Page 319
INDEX......Page 324
SUPPLEMENTAL IMAGES......Page 330