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Cover image for Electron paramagnetic resonance : elementary theory and practical applications
Title:
Electron paramagnetic resonance : elementary theory and practical applications
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Publication Information:
New York : John Wiley & Sons, 1994
ISBN:
9780471572343

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30000003090192 QC763.W44 1994 Open Access Book Book
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Summary

Summary

Focusing primarily on isolated paramagnetic species, Electron Paramagnetic Resonance is designed to provide senior undergraduate and graduate students as well as professionals with the essential understanding needed to use this technique and be active in various specialized fields of interest.

Electron Paramagnetic Resonance enables those with no previous background in quantum mechanics to gain a fundamental grasp of EPR. It helps those with moderate training to acquire more sophisticated mathematical and quantum-mechanical skills and a knowledge of powerful theoretical and experimental techniques--tools that will allow them to interpret a wide range of EPR spectra.

This important work also introduces many exciting new EPR developments in progress, including time-resolved spectroscopy, which involves the acquisition of EPR data for short-lived species. In addition, it highlights the increasing complexity of the experimental equipment currently used, including spectrometers that operate both in the classical continuous-wave mode and in pulsed mode. This book also discusses how computers can direct spectrometer control and data acquisition, analyze data to yield to underlying parameters, and produce accurate simulated spectra.

Readers will acquire a heightened historical appreciation of the EPR technique, discovering how EPR studies have:

confirmed the existence of triplet states, establishing that new adsorption bands observed in optical spectra following excitation by light of certain molecules arise from the unpairing of electron spins identified chlorophyll radicals as the primary donor in the photosynthesis process, as well as other key intermediates in this reaction clarified the structure and function of systems of biomedical interest, including oxygen carriers and various enzymes uncovered paramagnetic species in insulators and semiconductors and described their environment facilitated chemists' investigation of reaction mechanisms

Complete with problem sets and concise bibliographies at the end of each chapter, as well as tutorial mathematical and quantum-mechanical appendices, this book is must reading for aspiring scientists in the field of physical chemistry and spectroscopy.

Using this book, you will be able to gain a fundamental grasp of EPR--even if you have no previous background in quantum mechanics. This important work also helps those with some training to acquire more sophisticated mathematical and quantum-mechanical skills and a knowledge of powerful theoretical and experimental techniques--tools that will allow them to interpret a wide range of EPR spectra.

You'll find out about many exciting new EPR developments in progress, including time-resolved spectroscopy, which involves the acquisition of EPR data for short-lived species. This book also discusses computers that direct spectrometer control and data acquisition, analyze data to yield to underlying parameters and produce accurate simulated spectra.

Complete with problem sets and concise bibliographies at the end of each chapter, this book is must reading for aspiring scientists in the field of physical chemistry and spectroscopy.


Author Notes

John A. Weil is professor Emeritus of Chemistry and Physics at the University of Saskatchewan
James R. Bolton 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


Reviews 1

Choice Review

Weil, Bolton, and Wertz provide all the basic background for an advanced student or professional using electron paramagnetic resonance (EPR) characterization techniques. Yet, the book goes far beyond a primary introduction to EPR. "Hyperfine" structures in the spectra are discussed in great detail and the latest experimental techniques (e.g., time-resolved EPR) are described. Quantum mechanical principles are applied frequently throughout and for readers who do not have a profound understanding of these techniques, the attached appendixes (about 150 pages) will provide the necessary information. The authors discuss every topic in great detail and always provide the basic underlying physical and theoretical principles. Each chapter is followed by a concise list of further readings as well as a list of special notes and a set of problem-questions. Despite the complexity of the subject, the book is very well written, illustrated, and produced. Recommended for faculty, professionals, or graduate students. H. Giesche; Alfred University


Table of 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
1.13 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
2.4 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
3.3 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
5.4 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
6.3 Systems with S = 1Triplet States
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 ¿-Type Organic Radicals
9.3 ¿-Type Organic Radicals
9.4 Triplet States and Biradicals
9.5 Inorganic Radicals
9.6 Electrically Conducting Systems
9.7 Techniques for Structural Estimates from EPR Data
References
Notes
Further Reading
Problems
Appendix 9A Hu¨ckel Molecular-Orbital Calculations
HMO References
HMO Problems
10 Relaxation Times, Linewidths And Spin Kinetic Phenomena
10.1 Introduction
10.2 Spin Relaxation: General Aspects
10.3 Spin Relaxation: Bloch Model
10.4 Linewidths
10.5 Dynamic Lineshape Effects
10.6 Longitudinal Detection
10.7 Saturation-Transfer EPR
10.8 Time Dependence of the EPR Signal Amplitude
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 ENDOR5
12.5 CW ENDOR: Single-Crystal Examples
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
13.11 Liquid Crystals
13.12 "Point" Defects
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.3 Determinants
A.4 Vectors: Scalar, Vector, and Outer Products
A.5 Matrices
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≪Sub≫N≪/Sub≫
C.1 Hydrogen Atom
C.2 RH Radicals
C.3 RH2 Radicals
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.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.3 Sensitivity and Resolution
F.4 Measurements
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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