Magnetochemistry

Description

This book deals with the electronic structure of transition metal complexes as revealed by their magnetic properties. Paramagnetic phenomena are reviewed, but the emphasis throughout the book lies with magnetic ordering phenomena, in both low-dimensional systems as well as with systems undergoing long-range ordering. Field dependent properties are described, and percolation phenomena are introduced. Experimental procedures are also discussed. Cover Magnetochemistry Copyright Preface Reference Contents List of symbols 1. Diamagnetism and Paramagnetism 1.1 Introduction 1.2 Diamagnetism 1.3 Atomic Term Symbols 1.4 Paramagnetism 1.5 Some Curie Law Magnets 1.6 Curie-Weiss Law 1.7 Temperature Independent Paramagnetism 1.8 References 1.9 General References 1.10 Appendix 1.10.1 Physical Constants and Units 1.10.2 Hyperbolic Functions 1.10.3 Magnetic Moment of a Magnetic Ion Subsystem 1.10.4 References 2. Paramagnetism: Zero-Field Splittings 2.1 Introduction 2.2 VanVleck's Equation 2.3 Paramagnetic Anisotropy 2.4 Spin-Orbit Coupling 2.5 Effective Spin 2.6 Direct Measurement of D 2.7 Electron Paramagnetic Resonance (EPR) 2.8 References 3. Thermodynamics 3.1 Introduction 3.2 Thermodynamic Relations 3.3 Thermal Effects 3.4 Adiabatic Demagnetization 3.5 Schottky Anomalies 3.6 Spin-Lattice Relaxation 3.7 References 4. Paramagnetism and Crystalline Fields: The Iron Series Ions 4.1 Introduction 4.2 Magnetic Properties of Free Ions 4.3 Quenching of Orbital Angular Momentum 4.4 Coordination Compounds 4.5 Jahn-Teller Behavior [13] 4.6 The Iron Series Ions 4.6.1 Titaoium(III), d 1, 2T 2 4.6.2 Vanadium(III), d2, 3A2 4.6.3 Vanadyl, V02+, d1 4.6.4 Chromium(III), d3, 4 A:z 4.6.5 Manganese(II), d5, 6 At 4.6.6 Iron(III), d5, 6 At 4.6.7 Chromium(II), d4, Manganese(III), d4, and Iron(II), d6 4.6.8 Cobalt(II), d' 4.6.9 Nickel(ll), d8, 3 A2 4.6.10 Copper(ll), d9, 2E 4.7 References 5. Introduction to Magnetic Exchange: Dimers and Clusters 5.1 Introduction 5.2 Energy Levels and Specific Heats 5.3 Magnetic Susceptibilities 5.4 Copper Acetate and Related Compounds 5.5 Some Other Dimers 5.6 EPR Measurements 5.7 Clusters 5.8 The Ising Model 5.9 References 6. Long Range Order. Ferromagnetism and Antiferromagnetism 6.1 Introduction 6.2 Molecular Field Theory of Ferromagnetism [1] 6.3 Thermal Effects 6.4 Molecular Field Theory of Antiferromagnetism [1] 6.5 Ising, XY, and Heisenberg Models [2, 11] 6.6 Dipole-Dipole Interactions 6.7 Exchange Effects on Paramagnetic Susceptibilities 6.8 Superexchange 6.9 Field Dependent Phenomena 6.9.1 Spin Flop 6.9.2 Field Induced Ordering 6.10 Ferromagnets 6.11 Ferrimagnetism 6.12 Canting and Weak Ferromagnetism 6.13 Characteristic Behavior of the 3d Ions 6.14 References 7. Lower Dimensional Magnetism 7.1 Introduction 7.2 One-Dimensional or Linear Chain Systems 7.2.1 Ising Systems 7.2.2 Heisenberg Systems 7.2.3 XY Systems 7.2.4 Some Other Aspects 7.3 Long-Range Order 7.4 Alternating Linear Chains 7.5 Spin-Peierls Systems 7.6 Two-Dimensional or Planar Systems 7.7 CaCu(OAc)4· 6H2O 7.8 Metamagnetism 7.9 Canting and Weak Ferromagnetism 7.10 Some Ferromagnetic Linear Chains 7.11 Solitons 7.12 References 8. The Heavy Transition Metals 8.1 Introduction 8.2 Molybdenum(III) 8.3 Ruthenium(III) 8.4 Rbeoium(lV) 8.5 Osmium(lll) 8.6 Iridium(lV) 8.7 References 9. The Rare Earths or Lanthanides 9.1 Introduction 9.2 Cerium 9.3 Praseodymium 9.4 Neodymium 9.5 Samarium 9.6 Europium 9.7 Gadolinium 9.8 Terbium 9.9 Dysprosium 9.10 Holmium 9.11 Erbium 9.12 Thulium 9.13 Ytterbium 9.14 Some Other Systems 9.15 References 10. Selected Examples 10.1 Introduction 10.2 Hydrated Nickel Halides 10.3 Tris(dithiocarbamates) of Iron(III) 10.4 φ =3/2 Iron(llI) 10.5 Manganous Acetate Tetrahydrate 10.6 Polymeric NiX2L2 10.7 Hydrated Nickel Nitrates 10.8 The Pyridine N-Oxide Series 10.9 The A2[FeX5(H2O)] Series of Antiferromagnets 10.10 Some Dilution Experiments 10.11 Biomagnetochemistry of Cobalt(ll) 10.12 References 11. Some Experimental Techniques 11.1 Introduction 11.2 Specific Heat Measurements 11.3 Gouy and Faraday Balances 11.4 Susceptibilities in Alternating Fields 11.5 Anisotropic Susceptibilities 11.6 References Formula Index Subject Index