Electron spin resonance analysis and interpretation.

• Main Author: Rieger, Philip H
• Format: eBook Book
• Language: English
• Published: Cambridge NBN International 2007; Royal Society of Chemistry (RSC); RSC Publishing; Royal Society of Chemistry; Royal Society of Chemistry, The
• Edition: 1
• Subjects: Chemistry; Chemistry & Chemical Engineering; Electron paramagnetic resonance; Physical & Theoretical; Physical Chemistry; SCIENCE

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...

Table of Contents:

• 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