Electron spin resonance analysis and interpretation.

This book is an introductory level textbook which presents the fundamental concepts of the subject in a simple pedagogical manner. It therefore offers an ideal starting point for any student wishing to understand and analyze ESR spectra in solution and solid state. The book is concise and clearly wr...

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Main Author Rieger, Philip H
Format eBook Book
LanguageEnglish
Published Cambridge NBN International 2007
Royal Society of Chemistry (RSC)
RSC Publishing
Royal Society of Chemistry
Royal Society of Chemistry, The
Edition1
Subjects
Chemistry
Chemistry & Chemical Engineering
Electron paramagnetic resonance
Physical & Theoretical
Physical Chemistry
SCIENCE
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Abstract This book is an introductory level textbook which presents the fundamental concepts of the subject in a simple pedagogical manner. It therefore offers an ideal starting point for any student wishing to understand and analyze ESR spectra in solution and solid state. The book is concise and clearly written with the beginner in mind, since the extensive use of complex and difficult theory is kept to a minimum. It contains numerous illustrative and worked examples throughout, covering the fundamental core ideas in continuous wave ESR and also providing an excellent overview on the many applications of this technique. The book has a strong 'chemistry feel', reflecting the author's life-long interests in organometallic species, so at all times the theory and analyses are constantly related back to solving real chemical problems. Furthermore, the numerous subtle perturbations that determine the final appearance of an ESR spectrum are emphasized and explained, enabling the reader to approach an interpretation armed with the best possible advice and guidance.
AbstractList This book describes in mathematical terms the extraction of useful information from ESR spectra.
This book describes in mathematical terms the extraction of useful information from ESR spectra as applied to paramagnetic organic, inorganic and organometalic molecules. It lays a firm groundwork for understanding more sophisticated experiments, which the availability of newer commercial instruments has made possible. It takes the reader step by step through obtaining and interpretating ESR spectra of paramagnetic molecules. The mathematical basis of each observed phenomena are detailed and examples given. In particular there is a detailed discussion of 2nd order pertubation theory treatment of the Spin Hamiltonian for non-coincident G and A axes.
This book is an introductory level textbook which presents the fundamental concepts of the subject in a simple pedagogical manner. It therefore offers an ideal starting point for any student wishing to understand and analyze ESR spectra in solution and solid state. The book is concise and clearly written with the beginner in mind, since the extensive use of complex and difficult theory is kept to a minimum. It contains numerous illustrative and worked examples throughout, covering the fundamental core ideas in continuous wave ESR and also providing an excellent overview on the many applications of this technique. The book has a strong 'chemistry feel', reflecting the author's life-long interests in organometallic species, so at all times the theory and analyses are constantly related back to solving real chemical problems. Furthermore, the numerous subtle perturbations that determine the final appearance of an ESR spectrum are emphasized and explained, enabling the reader to approach an interpretation armed with the best possible advice and guidance.
Author Rieger, Philip H
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Snippet This book is an introductory level textbook which presents the fundamental concepts of the subject in a simple pedagogical manner. It therefore offers an ideal...
This book describes in mathematical terms the extraction of useful information from ESR spectra as applied to paramagnetic organic, inorganic and organometalic...
This book describes in mathematical terms the extraction of useful information from ESR spectra.
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SubjectTerms Chemistry
Chemistry & Chemical Engineering
Electron paramagnetic resonance
Physical & Theoretical
Physical Chemistry
SCIENCE
SubjectTermsDisplay Chemistry
Physical & Theoretical
SCIENCE
Subtitle analysis and interpretation.
TableOfContents Electron spin resonance: analysis and interpretation -- Preface -- Contents -- Chapter 1. Introduction -- Chapter 2. Isotropic ESR Spectra of Organic Radicals -- Chapter 3. Isotropic Spectra of Organometallic Radicals -- Chapter 4. Anisotropic ESR Spectra -- Chapter 5. ESR Kinetic Studies -- Chapter 6. ESR Spectra of Biradicals, Triplet States, and other S>1/2 Systems -- Chapter 7. Perturbation Theory Calculations -- Appendix 1. Physical Constants, Conversion Factors, and Properties of Nuclei (Tables A1.1–A1.4) -- Appendix 2. Advanced ESR Methods -- Subject Index
Title Page Preface Table of Contents 1. Introduction 2. Isotropic ESR Spectra of Organic Radicals 3. Isotropic Spectra of Organometallic Radicals 4. Anisotropic ESR Spectra 5. ESR Kinetic Studies 6. ESR Spectra of Biradicals, Triplet States, and other S>1/2 Systems 7. Perturbation Theory Calculations Appendices Subject Index
References -- Chapter 7 Perturbation Theory Calculations -- 7.1 Second-order Perturbation Theory Treatment of Spin Hamiltonian with Non-coincident g- and A-axes -- 7.1.1 The Electron Zeeman Term -- 7.1.2 Nuclear Hyperfine Interaction -- 7.1.3 Perturbation Theory Treatment of Hyperfine Term -- 7.1.4 Example Application of these Results -- 7.2 Quadrupole Coupling -- 7.2.1 Perturbation Theory Treatment of Quadrupole Term -- 7.2.2 Example Application of Analysis Quadrupole Effects -- References -- Appendix 1 Physical Constants, Conversion Factors, and Properties of Nuclei (Tables A1.1-A1.4) -- Example -- References -- Appendix 2 Advanced ESR Methods -- A2.1 High Frequency ESR -- A2.2 Double Resonance -- A2.3 Pulsed Methods -- References -- Subject Index
3.4 Use of ESR Spectra to Determine Formation Constants -- References -- Chapter 4 Anisotropic ESR Spectra -- 4.1 Introduction -- 4.2 Solid-state ESR Spectra -- 4.2.1 Spectra of Dilute Single Crystals -- 4.2.2 Analysis of Frozen Solution Spectra -- 4.3 Interpretation of the g-Matrix -- 4.4 Interpretation of the Hyperfine Matrix -- 4.5 Organometallic Examples -- 4.5.1 A Low-spin Manganese(II) Complex -- 4.5.2 Some Cobalt(0) Radical Anions -- 4.6 Organic Examples of Solid-state ESR Spectra -- 4.6.1 Irradiated Single Crystal of Glycylglycine -- 4.6.2 X-irradiated Single Crystal of Methylene Diphosphonic Acid -- 4.7 Non-coincident Matrix Axes -- 4.7.1 Symmetry Considerations -- 4.7.2 Experimental Determination of Matrix Axis Orientations -- 4.8 Organometallic Examples of Non-coincident Matrix Axes -- 4.8.1 A Chromium Nitrosyl Complex -- 4.8.2 Iron Pentacarbonyl Ions -- 4.8.3 Another Low-spin Manganese(II) Complex -- 4.8.4 Chromium(I) Piano-stool Complex -- 4.8.5 [(RCCR0)Co2(CO)6]‾ and [SFeCo2(CO)9]‾ -- 4.8.6 (o-Xylylene)-Mn(dmpe)2 -- 4.8.7 Cobalt Dithiolene Complexes -- 4.9 "g-Strain -- References -- Chapter 5 ESR Kinetic Studies -- 5.1 Bloch's Phenomenological Model -- 5.1.1 Derivation of the Bloch Equations -- 5.1.2 Steady-state Solution -- 5.2 Chemical Exchange - The Modified Bloch Equations -- 5.3 Further Discussion of Line Shapes -- 5.4 Applications of the Modified Bloch Equations -- 5.5 Alternating Line Width Effects -- 5.6 Spin Labels -- References -- Chapter 6 ESR Spectra of Biradicals, Triplet States, and other S&gt -- 1/2 Systems -- 6.1 Biradicals -- 6.1.1 Exchange Coupling -- 6.2 Organic Triplet State Molecules and the Dipolar Interaction -- 6.2.1 Organic Triplet State Molecules -- 6.3 Transition Metal Complexes with S&gt -- 1/2 -- 6.3.1 Spin-Orbit Coupling -- 6.3.2 High-spin Transition Metal Ions -- 6.3.3 Examples: K3Cr(CN)6 and K4V(CN)6
Electron Spin Resonance -- Contents -- Chapter 1 Introduction -- 1.1 What is ESR Spectroscopy? -- 1.2 The ESR Experiment -- 1.2.1 Sensitivity -- 1.2.2 Saturation -- 1.2.3 Nuclear Hyperfine Interaction -- 1.3 Operation of an ESR Spectrometer -- 1.4 Optimization of Operating Parameters -- 1.4.1 Microwave Frequency -- 1.4.2 Microwave Power -- 1.4.3 Center Field, Sweep Width and Field Offset -- 1.4.4 Sweep Time -- 1.4.5 Modulation Frequency -- 1.4.6 Second Harmonic Detection -- 1.4.7 Modulation Amplitude -- 1.4.8 Modulation Phase -- 1.4.9 Signal Gain -- 1.4.10 Filter Time Constant -- 1.5 Applications of ESR Spectroscopy -- 1.5.1 Electronic Structure Determination -- 1.5.2 Analytical Applications -- 1.5.3 Determination of Rates -- References -- Chapter 2 Isotropic ESR Spectra of Organic Radicals -- 2.1 Isotropic ESR Spectra -- 2.1.1 Line Positions in Isotropic Spectra -- 2.1.2 Hyperfine Coupling Patterns -- 2.1.3 Second-order Splittings -- 2.1.4 Spin Hamiltonian Parameters from Spectra -- 2.2 Interpretation of Isotropic Parameters -- 2.3 Line Widths in Isotropic Spectra -- 2.3.1 Incomplete Averaging of Anisotropies -- 2.3.2 Rates of Fluxionality from Line Widths -- 2.4 Organic Radical Reactions -- 2.5 Analysis of Isotropic ESR Spectra -- 2.5.1 Preliminary Examination of the Spectrum -- 2.5.2 What do you Expect to See? -- 2.5.3 Are the Gross Features of the Spectrum Consistent with the Model? -- 2.5.4 An Example -- 2.5.5 Detailed Analysis for Determination of Parameters -- 2.5.6 Computation of Multiplet Intensity Ratios -- 2.5.7 Multiplet Patterns due to Isotopomers -- 2.5.8 Second-order Shifts in Line Positions -- 2.6 Related Techniques (ENDOR) -- References -- Chapter 3 Isotropic Spectra of Organometallic Radicals -- 3.1 Second-order Effects on Line Positions -- 3.2 Understanding the Variation in Line Widths -- 3.3 Puzzling Line Shapes
Title Electron spin resonance
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