Valency and Molecular Structure (eBook)

Front Cover 1
Valency and Molecular Structure 4
Copyright Page 5
Table of Contents 8
Preface to the Fourth Edition 6
CHAPTER 1. HISTORICAL INTRODUCTION 12
1.1 Electricity and Chemical Bonding 12
1.2 The Lewis–Langmuir Electron-pair Bond 14
1.3 Quantum Theory of Chemical Bonding 17
1.4 Bibliography 18
CHAPTER 2. THE EXPERIMENTAL FOUNDATION OF THE QUANTUM THEORY 19
2.1 Energy Units 19
2.2 Black Body Radiation 20
2.3 The Photoelectric Effect 22
2.4 The Bohr Theory of the Hydrogen Atom 24
2.5 Energy Level Diagrams 26
2.6 Extensions of the Bohr Theory 28
CHAPTER 3. ELEMENTARY QUANTUM THEORY 29
3.1 Particles and Waves 29
3.2 The New Quantum Theory and the 'Uncertainty Principle' 30
3.3 Waves and Wave Equations 32
3.4 The Wave Equation for Electrons 36
3.5 Operator Form of the Schrödinger Equation 38
CHAPTER 4. THE HYDROGEN ATOM 40
4.1 Introduction 40
4.2 Polar Co-ordinates 40
4.3 Acceptable Solutions – the Quantum Numbers 41
4.4 The Radial Functions R(r) 42
4.5 Radial Distribution Functions 43
4.6 The Angular Functions .(.,f) 45
4.7 Orbitals, Probability Distributions and Charge Clouds 46
4.8 Energy Levels 48
CHAPTER 5. QUANTUM THEORY AND THE PERIODIC CLASSIFICATION 49
5.1 The Wave Equation for Many-electron Atoms 49
5.2 Energy Levels 49
5.3 Electron Spin 50
5.4 The Exclusion Principle 51
5.5 Ionization Energies 53
5.6 The 'Building-up' ('Aufbau') Principle and the Periodic Classification 54
5.7 Transition Series: the 'd-block' Elements 57
CHAPTER 6. THE MOLECULAR-ORBITAL METHOD 61
6.1 Introduction 61
6.2 Relationship between Atomic and Molecular Orbitals (United Atom Approach) 62
6.3 The LCAO Method 64
6.4 Hydrogen Molecule Ion (H2 +) 65
6.5 Homonuclear Diatomic Molecules 67
6.6 Heteronuclear Diatomic Molecules 73
6.7 Bond Strength 76
6.8 Reference 77
CHAPTER 7. THE VALENCE-BOND METHOD 78
7.1 Introduction 78
7.2 The Hydrogen Molecule Ion 78
7.3 The Hydrogen Molecule 82
7.4 Comparison of the Molecular-orbital and Valence-bond Methods 83
7.5 Heteronuclear Diatomic Molecules 85
7.6 Resonance 86
7.7 Resonance: Some Misconceptions and Some Guiding Principles 89
CHAPTER 8. DIRECTED VALENCY 92
8.1 Shapes of Molecules Formed by First-row Elements 92
8.2 The Criterion of Maximum Overlapping 96
8.3 Polyatomic Molecules: VB and MO Descriptions 97
8.4 Non-equivalent Orbitals 107
8.5 p Molecular Orbitals 108
8.6 The Equivalent-orbital Description 113
8.7 Bond Energies 115
CHAPTER 9. IONIC, HYDROGEN AND METALLIC BONDS 116
9.1 Introduction 116
9.2 Ionic bonds 116
9.3 Crystal Lattice Energy 118
9.4 The Born–Haber Cycle 121
9.5 Ionic Radii 123
9.6 Ionic Structures 126
9.7 Electronegativity 130
9.8 The Hydrogen Bond 133
9.9 Metallic Bonds 138
9.10 The Molecular or van der Waals' Bond 140
9.11 Bibliography 141
CHAPTER 10. THE STRUCTURES OF SOME SIMPLE INORGANIC COMPOUNDS 142
10.1 Bond Lengths 142
10.2 Calculated Bond Lengths 143
10.3 Stereochemistry of Compounds Formed by Main-group Elements 143
10.4 Lithium and the Alkali Metals 144
10.5 Beryllium and the Alkaline Earth Metals 146
10.6 Boron and the Group IIIB Elements 149
10.7 Carbon and the Group IVB Elements 154
10.8 Nitrogen and the Group VB Elements 162
10.9 Oxygen and the Group VIB Elements 178
10.10 Fluorine and the Group VIIB Elements 190
10.11 Compounds of the Noble Gases 202
10.12 Bonding in Xenon Compounds 205
10.13 References 207
CHAPTER 11. COMPLEX COMPOUNDS 209
11.1 Introduction and Nomenclature1 , 2 209
11.2 Bonding in Complex Compounds 214
11.3 Absorption Spectra9-11 223
11.4 Magnetic Susceptibility12 226
11.5 The Stability of Complex Compounds13 232
11.6 Distortion of Octahedral Complexes 235
11.7 Co-ordination Numbers Other Than 6 238
11.8 Co-ordination Number 2 239
11.9 Co-ordination Number 3 242
11.10 Co-ordination Number 4 245
11.11 Co-ordination Number 5 253
11.12 Co-ordination Number 770 265
11.13 Co-ordination Number 873 267
74 11.14 Co-ordination Numbers 9, 10 and 1274 272
11.15 Metal–Metal Bonding: Cluster Compounds 273
11.16 Carbonyls 277
11.17 Cyclopentadiene Complexes 281
11.18 Alkene and Alkyne Complexes 285
11.19 Reactivity of Complex Compounds: Orbital Considerations3 288
11.20 The Stability and Reactivity of Four-co-ordinate Complexes: the 'trans' Influence and 'trans' Effect111 293
11.21 References 297
CHAPTER 12. ELECTRONIC SPECTRA OF TRANSITION-METAL COMPLEXES 302
12.1 Introduction 302
12.2 Electronic Spectra of d1 Ions 302
12.3 Intensity of d–d Bands 305
12.4 Configurations for Free Ions (dn) 306
12.5 Coupling of Electron Spins 307
12.6 Coupling of Orbital Angular Momenta 308
12.7 Spin Multiplicity (2S + 1) 309
12.8 Relationship Between Terms and Microstates for the p2 Configuration 310
12.9 Microstates and Terms for a d2 Configuration 313
12.10 Terms for dn Configurations 313
12.11 Coupling of Spin and Orbital Momenta 314
12.12 Free Ions: Term Energies 319
12.13 Spectra of Complex Ions 320
12.14 Weak-field Method 321
12.15 Spectra of Octahedral d2 Complexes (e.g. [VL6 ] 3 +): The Weak-field Approach 323
12.16 Orgel Diagrams 324
12.17 Strong-field Method (for Octahedral Fields) 326
12.18 Correlation of Weak-field and Strong-field Levels 327
12.19 Other Tanabe–Sugano Diagrams 332
12.20 References 333
CHAPTER 13. ELECTRON-DEFICIENT MOLECULES1 
334 
13.1 Introduction 334
13.2 The Structure and Bonding of Diborane 334
13.3 The Structures of the Higher Hydrides of Boron 339
13.4 The Structures of the Borohydrides (Tetrahydroborates) 342
13.5 The Metal Alkyls 344
13.6 References 348
INDEX 349