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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.…mehr
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.
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Inhaltsangabe
Chapter 1: What is ESR Spectroscopy The ESR Experiment Sensitivity Saturation Nuclear Hyperfine Interaction Operation of an ESR Spectrometer Optimization of Operating Parameters Applications of ESR Spectroscopy Electronic Structure Determination Analytical Applications Determination of Rates References Chapter 2: Isotropic ESR Spectra Line Positions in Isotropic Spectra Hyperfine Coupling Parameters Second-order Splittings Spin Hamiltonian Parameters from Spectra Interpretation of Isotropic Parameters Linewidths in Isotropic Spectra Incomplete Averaging of Anisotropies Rates of Fluxionality from Linewidths Organic Radical Reactions Analysis of Isotropic ESR Spectra Preliminary Examination of the Spectrum What do you expect to see? Are the Gross Features of the Spectrum Consistent with the Model? An Example Detailed Analysis for Determination of Parameters Computation of Multiplet Intensity Ratios Multiplet Patterns Due to Isotopomers Second-order Shifts in Line Positions Related Techniques (ENDOR) References Chapter 3: Second-order Effects on Line Positions Understanding the Variation in Line Widths Puzzling Line Shapes Use of ESR Spectra to Determine Formation Constants References Chapter 4: Introduction: Solid-State ESR Spectra Spectra of Dilute Single Crystals Analysis of Frozen Solution Spectra Interpretation of the g-Matrix Interpretation of the Hyperfine Matrix Organometallic Examples A Low-spin Manganese(II) Complex Some Cobalt(0) Radical Anions Organic Examples of Solid-State ESR Spectra Irradiated Single Crystal Of Glycylglycine X-irradiated Single Crystal of Methylene Diphosphonic Acid Non-Coincident Matrix Axes Symmetry Considerations Experimental Determination of Matrix Axis Orientations Organometallic Examples of Non-Coincident Matrix Axes A Chromium Nitrosyl Complex Iron Pentacarbonyl Ions Another Low-Spin Manganese(II) Complex Chromium(I) Piano-Stool Complex [(RCCR')Co2(CO)6]- and [SFeCo2(CO)9]- (o-xylylene)-Mn(dmpe)2 Cobalt Dithiolene Complexes "g-Strain" References Chapter 5: Bloch's Phenomenological Model Derivation of the Bloch Equations Steady-State Solution Chemical Exchange-The Modified Bloch Equations Further Discussion of Line Shapes Applications of the Modified Bloch Equations Alternating Linewidth Effects Spin Labels References Chapter 6: Biradicals Exchange Coupling Organic Triplet-State Molecules and the Dipolar Interaction Organic Triplet-State Molecules Transition Metal Complexes with S>1/2 Spin-Orbit Coupling High-Spin Transition Metal Ions Examples: K3Cr(CN)6 and K4V(CN)6 References Chapter 7 Second-order Perturbation Theory Treatment of Spin Hamiltonian with Non-Coincident g- and A-Axes The Electron Zeeman Term Nuclear Hyperfine Interaction Perturbation Theory Treatment of Hyperfine Term Example of Application of These Results Quadrupole Coupling Perturbation Theory Treatment of Quadrupole Term Example of Application of Analysis of Quadrupole Effects References
Chapter 1: What is ESR Spectroscopy The ESR Experiment Sensitivity Saturation Nuclear Hyperfine Interaction Operation of an ESR Spectrometer Optimization of Operating Parameters Applications of ESR Spectroscopy Electronic Structure Determination Analytical Applications Determination of Rates References Chapter 2: Isotropic ESR Spectra Line Positions in Isotropic Spectra Hyperfine Coupling Parameters Second-order Splittings Spin Hamiltonian Parameters from Spectra Interpretation of Isotropic Parameters Linewidths in Isotropic Spectra Incomplete Averaging of Anisotropies Rates of Fluxionality from Linewidths Organic Radical Reactions Analysis of Isotropic ESR Spectra Preliminary Examination of the Spectrum What do you expect to see? Are the Gross Features of the Spectrum Consistent with the Model? An Example Detailed Analysis for Determination of Parameters Computation of Multiplet Intensity Ratios Multiplet Patterns Due to Isotopomers Second-order Shifts in Line Positions Related Techniques (ENDOR) References Chapter 3: Second-order Effects on Line Positions Understanding the Variation in Line Widths Puzzling Line Shapes Use of ESR Spectra to Determine Formation Constants References Chapter 4: Introduction: Solid-State ESR Spectra Spectra of Dilute Single Crystals Analysis of Frozen Solution Spectra Interpretation of the g-Matrix Interpretation of the Hyperfine Matrix Organometallic Examples A Low-spin Manganese(II) Complex Some Cobalt(0) Radical Anions Organic Examples of Solid-State ESR Spectra Irradiated Single Crystal Of Glycylglycine X-irradiated Single Crystal of Methylene Diphosphonic Acid Non-Coincident Matrix Axes Symmetry Considerations Experimental Determination of Matrix Axis Orientations Organometallic Examples of Non-Coincident Matrix Axes A Chromium Nitrosyl Complex Iron Pentacarbonyl Ions Another Low-Spin Manganese(II) Complex Chromium(I) Piano-Stool Complex [(RCCR')Co2(CO)6]- and [SFeCo2(CO)9]- (o-xylylene)-Mn(dmpe)2 Cobalt Dithiolene Complexes "g-Strain" References Chapter 5: Bloch's Phenomenological Model Derivation of the Bloch Equations Steady-State Solution Chemical Exchange-The Modified Bloch Equations Further Discussion of Line Shapes Applications of the Modified Bloch Equations Alternating Linewidth Effects Spin Labels References Chapter 6: Biradicals Exchange Coupling Organic Triplet-State Molecules and the Dipolar Interaction Organic Triplet-State Molecules Transition Metal Complexes with S>1/2 Spin-Orbit Coupling High-Spin Transition Metal Ions Examples: K3Cr(CN)6 and K4V(CN)6 References Chapter 7 Second-order Perturbation Theory Treatment of Spin Hamiltonian with Non-Coincident g- and A-Axes The Electron Zeeman Term Nuclear Hyperfine Interaction Perturbation Theory Treatment of Hyperfine Term Example of Application of These Results Quadrupole Coupling Perturbation Theory Treatment of Quadrupole Term Example of Application of Analysis of Quadrupole Effects References
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