Electron Paramagnetic Resonance Elementary Theory and Practical Applications
by Weil, John A.; Bolton, James R.Edition: 2nd
Format: Hardcover
Pub. Date: 2007-01-08
Publisher(s): Wiley-Interscience
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Summary
This book provides an introduction to the underlying theory, fundamentals, and applications of EPR spectroscopy, as well as new developments in the area. Knowledge of the topics presented will allow the reader to interpret of a wide range of EPR spectra, as well as help them to apply EPR techniques to problem solving in a wide range of areas: organic, inorganic, biological, and analytical chemistry; chemical physics, geophysics, and minerology. Includes updated information on high frequency and multi-frequency EPR, pulsed microwave techniques and spectra analysis, dynamic effects, relaxation phenomena, computer-based spectra simulation, biomedical aspects of EPR, and more Equips readers with sufficient knowledge of EPR techniques to go on in their specialized area of interest Provides problem sets and concise bibliographies at the end of each chapter, plus several tutorial appendices on topics like mathematical operations, quantum mechanics of angular momentum, experimental considerations.
Author Biography
JOHN A. WEIL is Professor Emeritus of Chemistry and Physics at the University of Saskatchewan and an active international researcher in the field of EPR and NMR spectroscopy and theory.
JAMES R. BOLTON is President of Bolton Photosciences, which provides specialty consulting services for the development and operation of ultraviolet (UV) technologies. He is Adjunct Professor in the Department of Civil and Environmental Engineering at the University of Alberta, and Professor Emeritus of Chemistry at the University of Western Ontario.
Table of Contents
| Preface | p. xix |
| Acknowledgments | p. xxiii |
| Basic Principles of Paramagnetic Resonance | p. 1 |
| Introduction | p. 1 |
| Historical Perspective | p. 3 |
| A Simple EPR Spectrometer | p. 4 |
| Scope of the EPR Technique | p. 7 |
| Energy Flow in Paramagnetic Systems | p. 11 |
| Quantization of Angular Momenta | p. 13 |
| Relation Between Magnetic Moments and Angular Momenta | p. 14 |
| Magnetic Field Quantities and Units | p. 15 |
| Bulk Magnetic Properties | p. 18 |
| Magnetic Energies and States | p. 20 |
| Interaction of Magnetic Dipoles with Electromagnetic Radiation | p. 21 |
| Characteristics of the Spin Systems | p. 23 |
| The g Factor | p. 23 |
| Characteristics of Dipolar Interactions | p. 27 |
| Parallel-Field EPR | p. 28 |
| Time-Resolved EPR | p. 29 |
| Computerology | p. 29 |
| EPR Imaging | p. 30 |
| References | p. 30 |
| Notes | p. 32 |
| Further Reading | p. 34 |
| Problems | p. 35 |
| Magnetic Interaction Between Particles | p. 36 |
| Introduction | p. 36 |
| Theoretical Considerations of the Hyperfine Interaction | p. 38 |
| Angular-Momentum and Energy Operators | p. 40 |
| Spin Operators and Hamiltonians | p. 41 |
| Electronic and Nuclear Zeeman Interactions | p. 43 |
| Spin Hamiltonian Including Isotropic Hyperfine Interaction | p. 46 |
| Energy Levels of a System with One Unpaired Electron and One Nucleus with I = 1/2 | p. 47 |
| Energy Levels of a System with S = 1/2 and I = 1 | p. 50 |
| Signs of Isotropic Hyperfine Coupling Constants | p. 53 |
| Dipolar Interactions Between Electrons | p. 54 |
| References | p. 54 |
| Notes | p. 55 |
| Further Reading | p. 56 |
| Problems | p. 56 |
| Isotropic Hyperfine Effects in EPR Spectra | p. 58 |
| Introduction | p. 58 |
| Hyperfine Splitting from Protons | p. 59 |
| Single Set of Equivalent Protons | p. 59 |
| Multiple Sets of Equivalent Protons | p. 62 |
| Hyperfine Splittings from Other Nuclei with I = 1/2 | p. 68 |
| Hyperfine Splittings from Nuclei with I > 1/2 | p. 69 |
| Useful Rules for the Interpretation of EPR Spectra | p. 74 |
| Higher-Order Contributions to Hyperfine Splittings | p. 75 |
| Deviations from the Simple Multinomial Scheme | p. 77 |
| Other Problems Encountered in EPR Spectra of Free Radicals | p. 77 |
| Some Interesting [Pi]-Type Free Radicals | p. 78 |
| References | p. 79 |
| Notes | p. 79 |
| Further Reading | p. 80 |
| Problems | p. 80 |
| Zeeman Energy (g) Anisotropy | p. 85 |
| Introduction | p. 85 |
| Systems with High Local Symmetry | p. 88 |
| Systems with Rhombic Local Symmetry | p. 90 |
| Construction of the g Matrix | p. 92 |
| Symmetry-Related Sites | p. 96 |
| EPR Line Intensities | p. 97 |
| Statistically Randomly Oriented Solids | p. 99 |
| Spin-Orbit Coupling and Quantum-Mechanical Modeling of g | p. 105 |
| Comparative Overview | p. 110 |
| References | p. 111 |
| Notes | p. 112 |
| Further Reading | p. 114 |
| Problems | p. 114 |
| Hyperfine (A) Anisotropy | p. 118 |
| Introduction | p. 118 |
| Origin of the Anisotropic Part of the Hyperfine Interaction | p. 120 |
| Determination and Interpretation of the Hyperfine Matrix | p. 122 |
| The Anisotropic Breit-Rabi Case | p. 122 |
| The Case of Dominant Electron Zeeman Energy | p. 124 |
| General Case | p. 126 |
| The Case of B [approximately] B[subscript hf] | p. 128 |
| The Case of B [greater than greater than] B[subscript hf] | p. 141 |
| Combined g and Hyperfine Anisotropy | p. 143 |
| Multiple Hyperfine Matrices | p. 144 |
| Systems With I > 1/2 | p. 144 |
| Hyperfine Powder Lineshapes | p. 145 |
| References | p. 150 |
| Notes | p. 151 |
| Further Reading | p. 152 |
| Problems | p. 152 |
| Systems With More Than One Unpaired Electron | p. 158 |
| Introduction | p. 158 |
| Spin Hamiltonian for Two Interacting Electrons | p. 159 |
| Electron-Exchange Interaction | p. 160 |
| Electron-Electron Dipole Interaction | p. 162 |
| Systems with S = 1 (Triplet States) | p. 164 |
| Spin Energies and Eigenfunctions | p. 165 |
| '[delta]M[subscript s] = [PlusMinus]2' Transitions | p. 172 |
| Randomly Oriented Triplet Systems | p. 173 |
| Photo-excited Triplet-State Entities | p. 177 |
| Thermally Accessible Triplet Entities | p. 182 |
| Ground-State Triplet Entities | p. 185 |
| Carbenes and Nitrenes | p. 185 |
| Dianions of Symmetric Aromatic Hydrocarbons | p. 187 |
| Inorganic Triplet Species | p. 188 |
| Interacting Radical Pairs | p. 189 |
| Biradicals | p. 190 |
| Systems with S > 1 | p. 195 |
| High-Spin and High-Field Energy Terms | p. 196 |
| The Spin Hamiltonian: A Summing up | p. 197 |
| Modeling the Spin-Hamiltonian Parameters | p. 199 |
| References | p. 200 |
| Notes | p. 203 |
| Further Reading | p. 204 |
| Problems | p. 205 |
| Paramagnetic Species in the Gas Phase | p. 208 |
| Introduction | p. 208 |
| Monatomic Gas-Phase Species | p. 209 |
| Diatomic Gas-Phase Species | p. 211 |
| Triatomic and Polyatomic Gas-Phase Molecules | p. 217 |
| Laser Electron Paramagnetic Resonance | p. 219 |
| Other Techniques | p. 219 |
| Reaction Kinetics | p. 220 |
| Astro-EPR | p. 220 |
| References | p. 221 |
| Notes | p. 222 |
| Further Reading | p. 222 |
| Problems | p. 223 |
| Transition-Group Ions | p. 225 |
| Introduction | p. 225 |
| The Electronic Ground States of d-Electron Species | p. 227 |
| The EPR Parameters of d-Electron Species | p. 232 |
| Tanabe-Sugano Diagrams and Energy-Level Crossings | p. 240 |
| Covalency Effects | p. 243 |
| A Ferroelectric System | p. 244 |
| Some f-Electron Systems | p. 245 |
| References | p. 246 |
| Notes | p. 248 |
| Further Reading | p. 249 |
| Problems | p. 249 |
| The Interpretation of EPR Parameters | p. 253 |
| Introduction | p. 253 |
| [Pi]-Type Organic Radicals | p. 254 |
| Anions and Cations of Benzene and Some of its Derivatives | p. 259 |
| Anions and Cations of Polyacenes | p. 262 |
| g Factors of [Pi] Radicals | p. 262 |
| Origin of Proton Hyperfine Splittings | p. 263 |
| Sign of the Proton Hyperfine Splitting Constant | p. 265 |
| Methyl Proton Hyperfine Splittings and Hyperconjugation | p. 268 |
| Hyperfine Splitting from Nuclei Other than Protons | p. 270 |
| One-Dimensional Chain Paramagnets | p. 272 |
| [sigma]-Type Organic Radicals | p. 274 |
| Triplet States and Biradicals | p. 275 |
| Inorganic Radicals | p. 276 |
| Electrically Conducting Systems | p. 281 |
| Metals | p. 281 |
| Metals Dissolved in Ammonia and Amine Solutions | p. 282 |
| Semiconductors | p. 283 |
| Graphitic Compounds | p. 285 |
| Techniques for Structural Estimates from EPR Data | p. 285 |
| The Newman Superposition Model | p. 285 |
| The Pseudo-cube Method | p. 286 |
| Distances from Parameter D | p. 286 |
| Eatons' Interspin-Distance Formula | p. 287 |
| Summary | p. 287 |
| References | p. 287 |
| Notes | p. 291 |
| Further Reading | p. 291 |
| Problems | p. 292 |
| Huckel Molecular-Orbital Calculations | p. 294 |
| HMO References | p. 298 |
| HMO Problems | p. 299 |
| Relaxation Times, Linewidths and Spin Kinetic Phenomena | p. 301 |
| Introduction | p. 301 |
| Spin Relaxation: General Aspects | p. 302 |
| Spin Temperature and Boltzmann Distribution | p. 302 |
| Spin Dynamics | p. 303 |
| Mechanisms for [tau subscript 1] | p. 305 |
| Spin Relaxation: Bloch Model | p. 308 |
| Magnetization in a Static Magnetic Field | p. 309 |
| Addition of an Oscillating Magnetic Field | p. 310 |
| Rotating Frame | p. 311 |
| Steady-State Solutions of Bloch Equations | p. 312 |
| Linewidths | p. 316 |
| Homogeneous Broadening | p. 316 |
| Inhomogeneous Broadening | p. 316 |
| Dynamic Lineshape Effects | p. 317 |
| Generalized Bloch Equations | p. 318 |
| Other Theoretical Models | p. 322 |
| Examples of Line-Broadening Mechanisms | p. 322 |
| Electron-Spin Exchange | p. 323 |
| Electron Transfer | p. 324 |
| Proton Transfer | p. 326 |
| Fluxional Motion | p. 326 |
| Linewidth Variation: Dynamic Hyperfine Contributions | p. 327 |
| Single Nucleus | p. 328 |
| Multiple Nuclei | p. 329 |
| Molecular Tumbling Effects | p. 333 |
| Dipolar Effects | p. 335 |
| Spin-Rotation Interaction | p. 339 |
| General Example | p. 340 |
| Longitudinal Detection | p. 342 |
| Saturation-Transfer EPR | p. 343 |
| Time Dependence of the EPR Signal Amplitude | p. 343 |
| Concentration Changes | p. 343 |
| Chemically Induced Dynamic Electron Polarization | p. 345 |
| Dynamic Nuclear Polarization | p. 347 |
| Bio-Oxygen | p. 347 |
| Summary | p. 347 |
| References | p. 348 |
| Notes | p. 351 |
| Further Reading | p. 352 |
| Problems | p. 353 |
| Noncontinuous Excitation of Spins | p. 357 |
| Introduction | p. 357 |
| The Idealized B[subscript 1] Switch-on | p. 359 |
| The Single B[subscript 1] Pulse | p. 362 |
| Fourier-Transform EPR and FID Analysis | p. 364 |
| Multiple Pulses | p. 368 |
| Electron Spin-Echo Envelope Modulation | p. 369 |
| Advanced Techniques | p. 375 |
| Spin Coherence and Correlation | p. 375 |
| References | p. 378 |
| Notes | p. 380 |
| Further Reading | p. 381 |
| Problems | p. 382 |
| Double-Resonance Techniques | p. 385 |
| Introduction | p. 385 |
| A Continuous-Wave ENDOR Experiment | p. 386 |
| Energy Levels and ENDOR Transitions | p. 388 |
| Relaxation Processes in Steady-State ENDOR[superscript 5] | p. 392 |
| CW ENDOR: Single-Crystal Examples | p. 397 |
| The F Centers in the Alkali Halides | p. 397 |
| Metal-Ion Tetraphenylporphyrins | p. 401 |
| CW ENDOR in Powders and Non-Crystalline Solids | p. 401 |
| CW ENDOR in Liquid Solutions | p. 402 |
| Pulse Double-Resonance Experiments | p. 404 |
| Electron-Electron Double Resonance (ELDOR) | p. 404 |
| Optically Detected Magnetic Resonance | p. 406 |
| Fluorescence-Detected Magnetic Resonance | p. 407 |
| References | p. 408 |
| Notes | p. 410 |
| Further Reading | p. 411 |
| Problems | p. 411 |
| Other Topics | p. 414 |
| Apologia | p. 414 |
| Biological Systems | p. 414 |
| Clusters | p. 415 |
| Charcoal, Coal, Graphite and Soot | p. 415 |
| Colloids | p. 415 |
| Electrochemical EPR | p. 415 |
| EPR Imaging | p. 416 |
| Ferromagnets, Antiferromagnets and Superparamagnets | p. 416 |
| Glasses | p. 417 |
| Geologic/Mineralogic Systems and Selected Gems | p. 417 |
| Amethyst | p. 417 |
| Beryl and Chrysoberyl | p. 417 |
| Diamond | p. 417 |
| Emerald | p. 418 |
| Opal | p. 418 |
| Rock Crystal ([alpha]-Quartz) | p. 418 |
| Ruby | p. 418 |
| Sapphire | p. 418 |
| Topaz | p. 418 |
| Tourmaline | p. 419 |
| Turquoise | p. 419 |
| Zircon | p. 419 |
| Liquid Crystals | p. 419 |
| "Point" Defects | p. 419 |
| Insulators | p. 419 |
| Alkali Halides | p. 419 |
| Oxides | p. 419 |
| Semiconductors | p. 420 |
| Polymers | p. 420 |
| Radiation Dosage and Dating | p. 420 |
| Spin Labels | p. 421 |
| Spin Traps | p. 421 |
| Trapped Atoms and Molecules | p. 421 |
| Mathematical Operations | p. 422 |
| Complex Numbers | p. 422 |
| Operator Algebra | p. 423 |
| Properties of Operators | p. 423 |
| Eigenvalues and Eigenfunctions | p. 426 |
| Determinants | p. 428 |
| Vectors: Scalar, Vector, and Outer Products | p. 430 |
| Matrices | p. 432 |
| Addition and Subtraction of Matrices | p. 434 |
| Multiplication of Matrices | p. 434 |
| Special Matrices and Matrix Properties | p. 438 |
| Dirac Notation for Eigenfunctions and Matrix Elements | p. 438 |
| Diagonalization of Matrices | p. 440 |
| Matrix Invariants | p. 446 |
| Perturbation Theory | p. 446 |
| Dirac Delta Function | p. 449 |
| Group Theory | p. 450 |
| References | p. 450 |
| Notes | p. 451 |
| Further Reading | p. 451 |
| Problems | p. 451 |
| Quantum Mechanics of Angular Momentum | p. 455 |
| Introduction | p. 455 |
| Angular-Momentum Operators | p. 457 |
| Commutation Relations for General Angular-Momentum Operators | p. 458 |
| Eigenvalues of J[superscript 2] and J[subscript z] | p. 459 |
| Superposition of States | p. 464 |
| Angular-Momentum Matrices | p. 464 |
| Addition of Angular Momenta | p. 466 |
| Notation for Atomic and Molecular States | p. 472 |
| Angular Momentum and Degeneracy of States | p. 473 |
| Time Dependence | p. 475 |
| Precession | p. 475 |
| Magnetic Flux Quantization | p. 477 |
| Summary | p. 478 |
| References | p. 479 |
| Notes | p. 480 |
| Further Reading | p. 480 |
| Problems | p. 481 |
| Notes for Problem B.12 | p. 483 |
| The Hydrogen Atom and Selected Radicals RH[subscript n] | p. 484 |
| Hydrogen Atom | p. 484 |
| Spin Hamiltonian | p. 484 |
| The Spin Eigenkets and Energy Matrix | p. 485 |
| Exact Solution for the Energy Eigenvalues | p. 487 |
| Energy Eigenstates and Allowed Transitions | p. 489 |
| Resonant Frequencies in Constant Magnetic Field | p. 493 |
| Resonant Magnetic Fields at Constant Excitation Frequency | p. 493 |
| Calculation of Spin Energy Levels by Perturbation Theory | p. 495 |
| RH Radicals | p. 497 |
| RH[subscript 2] Radicals | p. 498 |
| Spin Hamiltonian and Energy Levels | p. 499 |
| EPR Transitions | p. 499 |
| References | p. 501 |
| Notes | p. 501 |
| Further Reading | p. 502 |
| Problems | p. 502 |
| Photons | p. 505 |
| Introduction | p. 505 |
| The Physical Aspects of Photons | p. 505 |
| Magnetic-Resonance Aspects | p. 508 |
| References | p. 510 |
| Notes | p. 510 |
| Instrumentation and Technical Performance | p. 512 |
| Instrumental: Background | p. 512 |
| CW EPR Spectrometers | p. 515 |
| Magnet System | p. 516 |
| Radiation Source | p. 517 |
| Microwave Transmission | p. 518 |
| Coupling of the Source to the Resonator | p. 519 |
| Resonator System | p. 520 |
| Field Modulation System | p. 525 |
| Coupling of the Resonator to the Detector | p. 525 |
| Detection System | p. 526 |
| Pulsed EPR Spectrometers | p. 529 |
| Computer Interfacing with EPR Spectrometers | p. 530 |
| Techniques for Temperature Variation and Control | p. 531 |
| Techniques for Pressure Variation | p. 532 |
| References | p. 533 |
| Notes | p. 535 |
| Further Reading | p. 535 |
| Problems | p. 536 |
| Experimental Considerations | p. 537 |
| Techniques for Generation of Paramagnetic Species | p. 537 |
| Lineshapes and Intensities | p. 539 |
| Lineshapes | p. 539 |
| Signal Intensities and Spin-Concentration Standards | p. 545 |
| Sensitivity and Resolution | p. 548 |
| Optimum Sensitivity | p. 548 |
| Sample Temperature | p. 550 |
| Microwave Frequency | p. 550 |
| Q Factor of the Resonator | p. 551 |
| Microwave Power Level and Measurements of B[subscript 1] | p. 553 |
| Modulation Amplitude | p. 554 |
| Modulation Frequency | p. 557 |
| Measurements | p. 557 |
| g Factors and Hyperfine Splittings | p. 557 |
| Relaxation Time | p. 559 |
| Spin-Number Determinations | p. 561 |
| References | p. 561 |
| Notes | p. 564 |
| Further Reading | p. 565 |
| Problems | p. 565 |
| EPR-Related Books and Selected Chapters | p. 567 |
| Fundamental Constants, Conversion Factors, and Key Data | p. 577 |
| Miscellaneous Guidelines | p. 588 |
| Notation for Symbols | p. 588 |
| Glossary of Symbols | p. 590 |
| Abbreviations | p. 600 |
| Exponent Nomenclature | p. 602 |
| Journal Reference Style | p. 602 |
| Author Index | p. 603 |
| Subject Index | p. 624 |
| Table of Contents provided by Ingram. All Rights Reserved. |
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