| Introduction | |
| What is ESR Spectroscopy? | p. 1 |
| The ESR Experiment | p. 3 |
| Sensitivity | p. 4 |
| Saturation | p. 5 |
| Nuclear Hyperfine Interaction | p. 5 |
| Operation of an ESR Spectrometer | p. 7 |
| Optimization of Operating Parameters | p. 11 |
| Microwave Frequency | p. 11 |
| Microwave Power | p. 12 |
| Center Field, Sweep Width and Field Offset | p. 13 |
| Sweep Time | p. 14 |
| Modulation Frequency | p. 14 |
| Second Harmonic Detection | p. 15 |
| Modulation Amplitude | |
| Modulation Phase | p. 15 |
| Signal Gain | p. 16 |
| Filter Time Constant | p. 16 |
| Applications of ESR Spectroscopy | p. 17 |
| Electronic Structure Determination | p. 17 |
| Analytical Applications | p. 17 |
| Determination of Rates | p. 18 |
| References | p. 18 |
| Isotropic ESR Spectra of Organic Radicals | |
| Isotropic ESR Spectra | p. 21 |
| Line Positions in Isotropic Spectra | p. 21 |
| Hyperfine Coupling Patterns | p. 22 |
| Second-order Splittings | p. 25 |
| Spin Hamiltonian Parameters from Spectra | p. 26 |
| Interpretation of Isotropic Parameters | p. 27 |
| Line Widths in Isotropic Spectra | p. 29 |
| Incomplete Averaging of Anisotropies | p. 29 |
| Rates of Fluxionality from Line Widths | p. 30 |
| Organic Radical Reactions | p. 32 |
| Analysis of Isotropic ESR Spectra | p. 32 |
| Preliminary Examination of the Spectrum | p. 33 |
| What do you Expect to See? | p. 33 |
| Are the Gross Features of the Spectrum Consistent with the Model? | p. 34 |
| An Example | p. 34 |
| Detailed Analysis for Determination of Parameters | p. 36 |
| Computation of Multiplet Intensity Ratios | p. 37 |
| Multiplet Patterns due to Isotopomers | p. 38 |
| Second-order Shifts in Line Positions | p. 39 |
| Related Techniques (ENDOR) | p. 41 |
| References | p. 42 |
| Isotropic Spectra of Organometallic Radicals | |
| Second-order Effects on Line Positions | p. 44 |
| Understanding the Variation in Line Widths | p. 47 |
| Puzzling Line Shapes | p. 48 |
| Use of ESR Spectra to Determine Formation Constants | p. 49 |
| References | p. 51 |
| Anisotropic ESR Spectra | |
| Introduction | p. 52 |
| Solid-state ESR Spectra | p. 53 |
| Spectra of Dilute Single Crystals | p. 54 |
| Analysis of Frozen Solution Spectra | p. 55 |
| Interpretation of the g-Matrix | p. 59 |
| Interpretation of the Hyperfine Matrix | p. 60 |
| Organometallic Examples | p. 63 |
| A Low-spin Manganese(II) Complex | p. 63 |
| Some Cobalt(O) Radical Anions | p. 66 |
| Organic Examples of Solid-state ESR Spectra | p. 69 |
| Irradiated Single Crystal of Glycylgiycine | p. 69 |
| X-irradiated Single Crystal of Methylene Diphosphonic Acid | p. 70 |
| Non-coincident Matrix Axes | p. 71 |
| Symmetry Considerations | p. 71 |
| Experimental Determination of Matrix Axis Orientations | p. 72 |
| Organometallic Examples of Non-coincident Matrix Axes | p. 73 |
| A Chromium Nitrosyl Complex | p. 73 |
| Iron Pentacarbonyl Ions | p. 74 |
| Another Low-spin Manganese(II) Complex | p. 76 |
| Chromium(I) Piano-stool Complex | p. 77 |
| [(RCCR')Co2(CO)6]2+- and [SFeCo2(CO)9]2+- | p. 79 |
| (o-Xylylene)-Mn(dmpe)2 | p. 81 |
| Cobalt Dithiolene Complexes | p. 86 |
| "g-Strain" | p. 87 |
| References | p. 89 |
| ESR Kinetic Studies | |
| Bloch's Phenomenological Model | p. 92 |
| Derivation of the Bloch Equations | p. 94 |
| Steady-state Solution | p. 95 |
| Chemical Exchange - The Modified Bloch Equations | p. 98 |
| Further Discussion of Line Shapes | p. 102 |
| Applications of the Modified Bloch Equations | p. 102 |
| Alternating Line Width Effects | p. 107 |
| Spin Labels | p. 108 |
| References | p. 110 |
| ESR Spectra of Biradicals, Triplet States, and other S > 1/2 Systems | |
| Biradicals | p. 112 |
| Exchange Coupling | p. 113 |
| Organic Triplet State Molecules and the Dipolar Interaction | p. 117 |
| Organic Triplet State Molecules | p. 122 |
| Transition Metal Complexes with S > 1/2 | p. 122 |
| Spin-Orbit Coupling | p. 122 |
| High-spin Transition Metal Ions | p. 126 |
| p. 130 |
| References | p. 132 |
| Perturbation Theory Calculations | |
| Second-order Perturbation Theory Treatment of Spin Hamiltonian with Non-coincident g- and 4-axes | p. 133 |
| The Electron Zeeman Term | p. 133 |
| Nuclear Hyperfine Interaction | p. 135 |
| Perturbation Theory Treatment of Hyperfine Term | p. 138 |
| Example Application of these Results | p. 144 |
| Quadrupole Coupling | p. 145 |
| Perturbation Theory Treatment of Quadrupole Term | p. 146 |
| Example Application of Analysis Quadrupole Effects | p. 149 |
| References | p. 152 |
| Physical Constants, Conversion Factors, and Properties of Nuclei (Tables A1.1-A1.4) | |
| Example | p. 155 |
| References | p. 157 |
| Advanced ESR Methods | |
| High Frequency ESR | p. 159 |
| Double Resonance | p. 161 |
| Pulsed Methods | p. 162 |
| References | p. 164 |
| Subject Index | p. 169 |
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