Table of contents : Title Page Acknowledgments Preface Contents Short Bibliography Table of Atomic and Magnetic Constants 1. Principles of Magnetic Resonance 1.1 Introduction 1.2 The NMR Experiment 1.3 The ESR Experiment 1.4 Thermal Equilibrium and Spin Relaxation 1.5 The Resonance Line Shape 1.6 Magnetic Interactions Problems Suggestions for Further Reading 2. Magnetic Resonance Spectra of the Hydrogen and Helium Atoms 2.1 Introduction 2.2 The Magnetic Hamiltonian 2.3 Perturbation Theory 2.4 The Basic Spin Functions and Zero-Order Energies 2.5 The First-Order Hyperfine Energies 2.6 The Second-Order Hyperfine Interaction 2.7 The First Order ESR Spectrum 2.8 The Second-Order ESR Spectrum - Forbidden Transitions 2.9 The Zero-Field Levels of Hydrogen 2.10 The NMR Spectrum of the Helium Atom 2.11 Chemical Shielding 2.12 Corrections to the g Factor 2.13 Anisotropic Effects Problems Suggestions for Further Reading 3. Nuclear Resonance in Solids 3.1 Introduction 3.2 The Dipolar Coupling Tensor 3.3 The NMR Spectrum of Two Coupled Protons 3.4 The Second Moment of an NMR Absorption Line 3.5 Structural Studies by the Method of Moments 3.6 Nuclear Quadrupole Resonance Problems Suggestions for Further Reading 4. The Analysis of NMR Spectra in Liquids 4.1 Introduction 4.2 The Chemical Shift 4.3 The Spin-Spin Coupling 4.4 The Analysis of Complex Spectra 4.4.1 Classification of Spectra 4.4.2 The Analysis of an AB Spectrum 4.4.3 The Analysis of an A2B2 Spectrum 4.4.4 Splitting from Magnetically Equivalent Nuclei 4.5 Practical Considerations Problems Suggestions for Further Reading 5. Interpretation of Chemical Shifts and Spin-Spin Couplings 5.1 Introduction 5.2 Origins of the Chemical Shift 5.2.1 Molecular Electronic Currents 5.2.2 Ramsey’s Formula 5.3 Proton Chemical Shifts 5.4 Shifts from Other Nuclei 5.4.1 Fluorine 19F 5.4.2 Carbon 13C 5.4.3 Nitrogen 14N and 15N 5.4.4 Other Nuclei 5.4.5 Solvent Effects 5.5 The Origin of Nuclear Spin-Spin Coupling 5.6 Proton Spin-Spin Coupling 5.7 Molecular Structure Studies by NMR Problems Suggestions for Further Reading 6. ESR Spectra of Organic Radicals in Solution 6.1 The Spin Hamiltonian: Hyperfine Splitting 6.2 Sets of Equivalent Protons 6.3 Hyperfine Patterns from Other Nuclei 6.4 Mechanism of the Hyperfine Coupling 6.4.1 The Unpaired Spin Density 6.4.2 Indirect Coupling Through a C-H Bond 6.4.3 McConnell’s Relation 6.4.4 Hyperconjugation 6.5 Spin Distributions in Alternant Hydrocarbon Ions 6.5.1 Delocalized Molecular Orbitals 6.5.2 Substituted Benzene Anions 6.5.3 The Pairing of Electronic States 6.6 Negative Spin Densities in Odd Alternant Radicals 6.7 Hyperfine Splitting from 13C and 14N Nuclei 6.7.1 Carbon 13 6.7.2 Nitrogen 14 6.8 Applications of ESR to Solution Chemistry Problems Suggestions for Further Reading 7. ESR of Trapped Organic Radicals in Solids 7.1 Introduction 7.2 The Spin Hamiltonian 7.3 The First-Order ESR Spectrum 7.4 Second-Order Effects 7.5 Experimental Determination of the Hyperfine Tensor 7.6 The Sign of the Electron-Nuclear Dipolar Coupling 7.7 α-Proton Coupling Tensor 7.8 Delocalized π-Electron Radicals 7.9 Hyperfine Coupling from β Protons 7.10 Hyperfine Tensors of Other Nuclei 7.10.1 Carbon 13 7.10.2 Nitrogen 14 7.10.3 19F Splittings 7.11 Randomly Oriented Solids Problems Suggestions for Further Reading 8. ESR of Organic Molecules in Triplet States 8.1 Introduction 8.2 Electron Spin-Spin Interaction 8.3 The Triplet Energy Levels 8.4 Transitions with Δms = 2 8.5 Hyperfine Structure 8.6 Further Studies of Excited Triplet States 8.7 Organic Molecules with Triplet Ground States 8.7.1 Methylene and Nitrene Derivatives 8.7.2 Triplets with One Localized Electron 8.7.3 π-Electron Triplets 8.8 Triplet Excitons 8.9 Radical-Ion Clusters in Solution Problems Suggestions for Further Reading 9. Theory of the g Tensor and the ESR Spectra of Inorganic Radicals 9.1 Determination of the g Tensor in Crystals 9.2 Theory of the g Tensor and the Effective Spin Hamiltonian 9.3 A Simple Example 9.4 The g Tensor in Molecules 9.5 The CO2- Radical 9.5.1 Experimental Results 9.5.2 Molecular Orbitals 9.5.3 Interpretation of the T and g tensors 9.6 Other Inorganic Radicals Problems Suggestions for Further Reading 10. ESR of Transition Metal Ions and Complexes 10.1 Introduction 10.2 Energy Levels of the d Electrons 10.2.1 The d Orbitals of a Free Ion 10.2.2 The Ligand Field Splitting 10.2.3 Regular and Distorted Complexes 10.3 General Freatures of the ESR Spectra 10.4 Kramers’ Theorem 10.5 The g Tensor in Ions with S=1/2 10.5.1 The Ti3+ Ion in a Tetrahedral Complex 10.5.2 The Ti3+ Ion in an Octahedral Complex 10.6 The Zero-Field Splitting of Triplet States 10.6.1 The Origin of the Splittings 10.6.2 Zero-Field Splitting in the V3+ Ion 10.6.3 The Spin Hamilton 10.6.4 ESR Measurements of D 10.7 Ions with Spin S Greater Than One 10.7.1 Quartet States 10.7.2 Quintet and Sextet States 10.7.3 Summary 10.8 Hyperfine Splitting from the Metal Nucleus 10.9 Covalent Bonding and Ligand Hyperfine Structure 10.10 Electron Exchange Coupling 10.11 The Rare-Earth Ions 10.12 Spin-Lattice Relaxation Problems Suggestions for Further Reading 11. Spin Relaxation 11.1 Introduction 11.2 Bloch’s Equations 11.3 The Lorentz Line Shape 11.4 The Origin of Magnetic Relaxation 11.5 Nuclear Spin Relaxation in the Water Molecule 11.5.1 Perturbation Theory 11.5.2 The Power Spectrum of a Random Force 11.5.3 The Effect of a Local Field 11.5.4 Rotational Brownian Motion 11.5.5 The Calculation of T1 and T2 11.5.6 Short and Long Correlation Times 11.6 Other Nuclear Relaxation Mechanisms 11.6.1 Introduction 11.6.2 Anisotropic Chemical Shift 11.6.3 Nuclear Spin-Rotational Coupling 11.6.4 Electric Quadrupole Couplings 11.6.5 Unpaired Electron Spins 11.7 Spin Relaxation of Radicals in Solution 11.7.1 Relaxation Mechanisms 11.7.2 Anisotropic g Tensor and Hyperfine Tensor 11.7.3 Electron Spin Exchange 11.7.4 Zero-Field Splittings Problems Suggestions for Further Reading 12. The Study of Molecular Rate Processes 12.1 The Time Scale of Magnetic Resonance Experiments 12.2 The Line Shape for a Jumping Spin 12.3 Chemical Exchange Effects in NMR Spectra 12.3.1 Hindered Internal Rotation 12.3.2 Spin Coupled to a Relaxing Nucleus 12.3.3 Proton Exchange Reactions 12.4 Rate Effects in ESR Spectra 12.4.1 Modulation of the Hyperfine Coupling 12.4.2 Ion-Pairing in Solution 12.4.3 Electron Transfer Reactions 12.4.4 Time-Dependent Changes in the Direction of Spin Quantization Problems Suggestions for Further Reading 13. Nuclear Resonance in Paramagnetic Systems - Double Resonance 13.1 Introduction 13.2 The Knight Shift 13.3 Unpaired Electron Distributions by NMR 13.4 Relaxation by Paramagnetic Ions in Solution 13.5 Electron Nuclear Double Resonance 13.5.1 The Overhauser Effect 13.5.2 The Solid-State Effect 13.5.3 ENDOR 13.6 Spin Decoupling in NMR Problems Suggestions for Further Reading Appendixes Appendix A. Matrix Elements and Eigenvalues Appendix B. Time-Independent Perturbation Theory Appendix C. Spin Angular Momentum Appendix D. Tensors and Vectors Appendix E. Time-Dependent Perturbation Theory Appendix F. Calculation of T1 and T2 for a Spin of 1/2 Appendix G. The Power Spectrum of a Random Function Appendix H. The Diffusion Equation for Brownian Motion Appendix I. Tensor Averages in a Rotating Molecule Index