Electron Paramagnetic Resonance

Name: Electron Paramagnetic Resonance | Elementary Theory and Practical Applications
Brand: Wiley
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Elementary Theory and Practical Applications

John A. Weil James R. Bolton(Autor*in)

Wiley (Verlag)

2. Auflage

Erschienen am 20. August 2007

688 Seiten

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Inhalt

Intro
ELECTRON PARAMAGNETIC RESONANCE
CONTENTS
PREFACE
ACKNOWLEDGMENTS
1 BASIC PRINCIPLES OF PARAMAGNETIC RESONANCE
1.1 Introduction
1.2 Historical Perspective
1.3 A Simple EPR Spectrometer
1.4 Scope of the EPR Technique
1.5 Energy Flow in Paramagnetic Systems
1.6 Quantization of Angular Momenta
1.7 Relation Between Magnetic Moments and Angular Momenta
1.8 Magnetic Field Quantities and Units
1.9 Bulk Magnetic Properties
1.10 Magnetic Energies and States
1.11 Interaction of Magnetic Dipoles with Electromagnetic Radiation
1.12 Characteristics of the Spin Systems
1.12.1 The g Factor
1.12.2 Characteristics of Dipolar Interactions
1.13 Parallel-Field EPR
1.14 Time-Resolved EPR
1.15 Computerology
1.16 EPR Imaging
References
Notes
Further Reading
Problems
2 MAGNETIC INTERACTION BETWEEN PARTICLES
2.1 Introduction
2.2 Theoretical Considerations of the Hyperfine Interaction
2.3 Angular-Momentum and Energy Operators
2.3.1 Spin Operators and Hamiltonians
2.3.2 Electronic and Nuclear Zeeman Interactions
2.3.3 Spin Hamiltonian Including Isotropic Hyperfine Interaction
2.4 Energy Levels of a System with One Unpaired Electron and One Nucleus with I = ½
2.5 Energy Levels of a System with S = ½ and I = 1
2.6 Signs of Isotropic Hyperfine Coupling Constants
2.7 Dipolar Interactions Between Electrons
References
Notes
Further Reading
Problems
3 ISOTROPIC HYPERFINE EFFECTS IN EPR SPECTRA
3.1 Introduction
3.2 Hyperfine Splitting from Protons
3.2.1 Single Set of Equivalent Protons
3.2.2 Multiple Sets of Equivalent Protons
3.3 Hyperfine Splittings from Other Nuclei with I = ½
3.4 Hyperfine Splittings from Nuclei with I & ½
3.5 Useful Rules for the Interpretation of EPR Spectra
3.6 Higher-Order Contributions to Hyperfine Splittings
3.7 Deviations from the Simple Multinomial Scheme
3.8 Other Problems Encountered in EPR Spectra of Free Radicals
3.9 Some Interesting p-Type Free Radicals
References
Notes
Further Reading
Problems
4 ZEEMAN ENERGY (g) ANISOTROPY
4.1 Introduction
4.2 Systems with High Local Symmetry
4.3 Systems with Rhombic Local Symmetry
4.4 Construction of the g Matrix
4.5 Symmetry-Related Sites
4.6 EPR Line Intensities
4.7 Statistically Randomly Oriented Solids
4.8 Spin-Orbit Coupling and Quantum-Mechanical Modeling of g
4.9 Comparative Overview
References
Notes
Further Reading
Problems
5 HYPERFINE (A) ANISOTROPY
5.1 Introduction
5.2 Origin of the Anisotropic Part of the Hyperfine Interaction
5.3 Determination and Interpretation of the Hyperfine Matrix
5.3.1 The Anisotropic Breit-Rabi Case
5.3.2 The Case of Dominant Electron Zeeman Energy
5.3.2.1 General Case
5.3.2.2 The Case of B ~ B(hf)
5.3.2.3 The Case of B » B(hf)
5.4 Combined g and Hyperfine Anisotropy
5.5 Multiple Hyperfine Matrices
5.6 Systems With I & ½
5.7 Hyperfine Powder Lineshapes
References
Notes
Further Reading
Problems
6 SYSTEMS WITH MORE THAN ONE UNPAIRED ELECTRON
6.1 Introduction
6.2 Spin Hamiltonian for Two Interacting Electrons
6.2.1 Electron-Exchange Interaction
6.2.2 Electron-Electron Dipole Interaction
6.3 Systems with S = 1 (Triplet States)
6.3.1 Spin Energies and Eigenfunctions
6.3.2 '?M(S) = ±2' Transitions
6.3.3 Randomly Oriented Triplet Systems
6.3.4 Photo-excited Triplet-State Entities
6.3.5 Thermally Accessible Triplet Entities
6.3.6 Ground-State Triplet Entities
6.3.6.1 Carbenes and Nitrenes
6.3.6.2 Dianions of Symmetric Aromatic Hydrocarbons
6.3.6.3 Inorganic Triplet Species
6.4 Interacting Radical Pairs
6.5 Biradicals
6.6 Systems with S &1
6.7 High-Spin and High-Field Energy Terms
6.8 The Spin Hamiltonian: A Summing up
6.9 Modeling the Spin-Hamiltonian Parameters
References
Notes
Further Reading
Problems
7 PARAMAGNETIC SPECIES IN THE GAS PHASE
7.1 Introduction
7.2 Monatomic Gas-Phase Species
7.3 Diatomic Gas-Phase Species
7.4 Triatomic and Polyatomic Gas-Phase Molecules
7.5 Laser Electron Paramagnetic Resonance
7.6 Other Techniques
7.7 Reaction Kinetics
7.8 Astro-EPR
References
Notes
Further Reading
Problems
8 TRANSITION-GROUP IONS
8.1 Introduction
8.2 The Electronic Ground States of d-Electron Species
8.3 The EPR Parameters of d-Electron Species
8.4 Tanabe-Sugano Diagrams and Energy-Level Crossings
8.5 Covalency Effects
8.6 A Ferroelectric System
8.7 Some f-Electron Systems
References
Notes
Further Reading
Problems
9 THE INTERPRETATION OF EPR PARAMETERS
9.1 Introduction
9.2 p-Type Organic Radicals
9.2.1 Anions and Cations of Benzene and Some of its Derivatives
9.2.2 Anions and Cations of Polyacenes
9.2.3 g Factors of p Radicals
9.2.4 Origin of Proton Hyperfine Splittings
9.2.5 Sign of the Proton Hyperfine Splitting Constant
9.2.6 Methyl Proton Hyperfine Splittings and Hyperconjugation
9.2.7 Hyperfine Splitting from Nuclei Other than Protons
9.2.8 One-Dimensional Chain Paramagnets
9.3 s-Type Organic Radicals
9.4 Triplet States and Biradicals
9.5 Inorganic Radicals
9.6 Electrically Conducting Systems
9.6.1 Metals
9.6.2 Metals Dissolved in Ammonia and Amine Solutions
9.6.3 Semiconductors
9.6.4 Graphitic Compounds
9.7 Techniques for Structural Estimates from EPR Data
9.7.1 The Newman Superposition Model
9.7.2 The Pseudo-cube Method
9.7.3 Distances from Parameter D
9.7.4 Eatons' Interspin-Distance Formula
9.7.5 Summary
References
Notes
Further Reading
Problems
Appendix 9A Hückel Molecular-Orbital Calculations
HMO References
HMO Problems
10 RELAXATION TIMES, LINEWIDTHS AND SPIN KINETIC PHENOMENA
10.1 Introduction
10.2 Spin Relaxation: General Aspects
10.2.1 Spin Temperature and Boltzmann Distribution
10.2.2 Spin Dynamics
10.2.3 Mechanisms for t(1)
10.3 Spin Relaxation: Bloch Model
10.3.1 Magnetization in a Static Magnetic Field
10.3.2 Addition of an Oscillating Magnetic Field
10.3.3 Rotating Frame
10.3.4 Steady-State Solutions of Bloch Equations
10.4 Linewidths
10.4.1 Homogeneous Broadening
10.4.2 Inhomogeneous Broadening
10.5 Dynamic Lineshape Effects
10.5.1 Generalized Bloch Equations
10.5.2 Other Theoretical Models
10.5.3 Examples of Line-Broadening Mechanisms
10.5.3.1 Electron-Spin Exchange
10.5.3.2 Electron Transfer
10.5.3.3 Proton Transfer
10.5.3.4 Fluxional Motion
10.5.4 Linewidth Variation: Dynamic Hyperfine Contributions
10.5.4.1 Single Nucleus
10.5.4.2 Multiple Nuclei
10.5.5 Molecular Tumbling Effects
10.5.5.1 Dipolar Effects
10.5.5.2 Spin-Rotation Interaction
10.5.6 General Example
10.6 Longitudinal Detection
10.7 Saturation-Transfer EPR
10.8 Time Dependence of the EPR Signal Amplitude
10.8.1 Concentration Changes
10.8.2 Chemically Induced Dynamic Electron Polarization
10.9 Dynamic Nuclear Polarization
10.10 Bio-Oxygen
10.11 Summary
References
Notes
Further Reading
Problems
11 NONCONTINUOUS EXCITATION OF SPINS
11.1 Introduction
11.2 The Idealized B(1) Switch-on
11.3 The Single B(1) Pulse
11.4 Fourier-Transform EPR and FID Analysis
11.5 Multiple Pulses
11.6 Electron Spin-Echo Envelope Modulation
11.7 Advanced Techniques
11.8 Spin Coherence and Correlation
References
Notes
Further Reading
Problems
12 DOUBLE-RESONANCE TECHNIQUES
12.1 Introduction
12.2 A Continuous-Wave ENDOR Experiment
12.3 Energy Levels and ENDOR Transitions
12.4 Relaxation Processes in Steady-State ENDOR(5)
12.5 CW ENDOR: Single-Crystal Examples
12.5.1 The F Centers in the Alkali Halides
12.5.2 Metal-Ion Tetraphenylporphyrins
12.6 CW ENDOR in Powders and Non-Crystalline Solids
12.7 CW ENDOR in Liquid Solutions
12.8 Pulse Double-Resonance Experiments
12.9 Electron-Electron Double Resonance (ELDOR)
12.10 Optically Detected Magnetic Resonance
12.11 Fluorescence-Detected Magnetic Resonance
References
Notes
Further Reading
Problems
13 OTHER TOPICS
13.1 Apologia
13.2 Biological Systems
13.3 Clusters
13.4 Charcoal, Coal, Graphite and Soot
13.5 Colloids
13.6 Electrochemical EPR
13.7 EPR Imaging
13.8 Ferromagnets, Antiferromagnets and Superparamagnets
13.9 Glasses
13.10 Geologic/Mineralogic Systems and Selected Gems
13.10.1 Amethyst
13.10.2 Beryl and Chrysoberyl
13.10.3 Diamond
13.10.4 Emerald
13.10.5 Opal
13.10.6 Rock Crystal (a-Quartz)
13.10.7 Ruby
13.10.8 Sapphire
13.10.9 Topaz
13.10.10 Tourmaline
13.10.11 Turquoise
13.10.12 Zircon
13.11 Liquid Crystals
13.12 "Point" Defects
13.12.1 Insulators
13.12.1.1 Alkali Halides
13.12.1.2 Oxides
13.12.2 Semiconductors
13.13 Polymers
13.14 Radiation Dosage and Dating
13.15 Spin Labels
13.16 Spin Traps
13.17 Trapped Atoms and Molecules
APPENDIX A MATHEMATICAL OPERATIONS
A.1 Complex Numbers
A.2 Operator Algebra
A.2.1 Properties of Operators
A.2.2 Eigenvalues and Eigenfunctions
A.3 Determinants
A.4 Vectors: Scalar, Vector, and Outer Products
A.5 Matrices
A.5.1 Addition and Subtraction of Matrices
A.5.2 Multiplication of Matrices
A.5.3 Special Matrices and Matrix Properties
A.5.4 Dirac Notation for Eigenfunctions and Matrix Elements
A.5.5 Diagonalization of Matrices
A.5.6 Matrix Invariants
A.6 Perturbation Theory
A.7 Dirac Delta Function
A.8 Group Theory
References
Notes
Further Reading
Problems
APPENDIX B QUANTUM MECHANICS OF ANGULAR MOMENTUM
B.1 Introduction
B.2 Angular-Momentum Operators
B.3 Commutation Relations for General Angular-Momentum Operators
B.4 Eigenvalues of J(2) and J(z)
B.5 Superposition of States
B.6 Angular-Momentum Matrices
B.7 Addition of Angular Momenta
B.8 Notation for Atomic and Molecular States
B.9 Angular Momentum and Degeneracy of States
B.10 Time Dependence
B.11 Precession
B.12 Magnetic Flux Quantization
B.13 Summary
References
Notes
Further Reading
Problems
Notes for Problem B.12
APPENDIX C THE HYDROGEN ATOM AND SELECTED RADICALS RH(n)
C.1 Hydrogen Atom
C.1.1 Spin Hamiltonian
C.1.2 The Spin Eigenkets and Energy Matrix
C.1.3 Exact Solution for the Energy Eigenvalues
C.1.4 Energy Eigenstates and Allowed Transitions
C.1.5 Resonant Frequencies in Constant Magnetic Field
C.1.6 Resonant Magnetic Fields at Constant Excitation Frequency
C.1.7 Calculation of Spin Energy Levels by Perturbation Theory
C.2 RH Radicals
C.3 RH(2) Radicals
C.3.1 Spin Hamiltonian and Energy Levels
C.3.2 EPR Transitions
References
Notes
Further Reading
Problems
APPENDIX D PHOTONS
D.1 Introduction
D.2 The Physical Aspects of Photons
D.3 Magnetic-Resonance Aspects
References
Notes
APPENDIX E INSTRUMENTATION AND TECHNICAL PERFORMANCE
E.1 Instrumental: Background
E.2 CW EPR Spectrometers
E.2.1 Magnet System
E.2.2 Radiation Source
E.2.3 Microwave Transmission
E.2.4 Coupling of the Source to the Resonator
E.2.5 Resonator System
E.2.6 Field-Modulation System
E.2.7 Coupling of the Resonator to the Detector
E.2.8 Detection System
E.3 Pulsed EPR Spectrometers
E.4 Computer Interfacing with EPR Spectrometers
E.5 Techniques for Temperature Variation and Control
E.6 Techniques for Pressure Variation
References
Notes
Further Reading
Problems
APPENDIX F EXPERIMENTAL CONSIDERATIONS
F.1 Techniques for Generation of Paramagnetic Species
F.2 Lineshapes and Intensities
F.2.1 Lineshapes
F.2.2 Signal Intensities and Spin-Concentration Standards
F.3 Sensitivity and Resolution
F.3.1 Optimum Sensitivity
F.3.2 Sample Temperature
F.3.3 Microwave Frequency
F.3.4 Q Factor of the Resonator
F.3.5 Microwave Power Level and Measurements of B(1)
F.3.6 Modulation Amplitude
F.3.7 Modulation Frequency
F.4 Measurements
F.4.1 g Factors and Hyperfine Splittings
F.4.2 Relaxation Time
F.4.3 Spin-Number Determinations
References
Notes
Further Reading
Problems
APPENDIX G EPR-RELATED BOOKS AND SELECTED CHAPTERS
APPENDIX H FUNDAMENTAL CONSTANTS, CONVERSION FACTORS, AND KEY DATA
APPENDIX I MISCELLANEOUS GUIDELINES
I.1 Notation for Symbols
I.2 Glossary of Symbols
I.3 Abbreviations
I.4 Exponent Nomenclature
I.5 Journal Reference Style
Author Index
Subject Index

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