Electron Spin Resonance

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ISBN: 9780854043552 | 0854043551
Cover: Hardcover
Copyright: 9/30/2007

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Electron spin resonance (ESR) is a technique which can be used to detect substances containing unpaired electrons and to investigate their electronic structure as well as to study the reactions of these substances. This book provides a reader, already familiar with quantum mechanics, with an understanding of the origins of the physical phenomena which make ESR possible.

Introduction
What is ESR Spectroscopy?	p. 1
The ESR Experiment	p. 3
Sensitivity	p. 4
Saturation	p. 5
Nuclear Hyperfine Interaction	p. 5
Operation of an ESR Spectrometer	p. 7
Optimization of Operating Parameters	p. 11
Microwave Frequency	p. 11
Microwave Power	p. 12
Center Field, Sweep Width and Field Offset	p. 13
Sweep Time	p. 14
Modulation Frequency	p. 14
Second Harmonic Detection	p. 15
Modulation Amplitude
Modulation Phase	p. 15
Signal Gain	p. 16
Filter Time Constant	p. 16
Applications of ESR Spectroscopy	p. 17
Electronic Structure Determination	p. 17
Analytical Applications	p. 17
Determination of Rates	p. 18
References	p. 18
Isotropic ESR Spectra of Organic Radicals
Isotropic ESR Spectra	p. 21
Line Positions in Isotropic Spectra	p. 21
Hyperfine Coupling Patterns	p. 22
Second-order Splittings	p. 25
Spin Hamiltonian Parameters from Spectra	p. 26
Interpretation of Isotropic Parameters	p. 27
Line Widths in Isotropic Spectra	p. 29
Incomplete Averaging of Anisotropies	p. 29
Rates of Fluxionality from Line Widths	p. 30
Organic Radical Reactions	p. 32
Analysis of Isotropic ESR Spectra	p. 32
Preliminary Examination of the Spectrum	p. 33
What do you Expect to See?	p. 33
Are the Gross Features of the Spectrum Consistent with the Model?	p. 34
An Example	p. 34
Detailed Analysis for Determination of Parameters	p. 36
Computation of Multiplet Intensity Ratios	p. 37
Multiplet Patterns due to Isotopomers	p. 38
Second-order Shifts in Line Positions	p. 39
Related Techniques (ENDOR)	p. 41
References	p. 42
Isotropic Spectra of Organometallic Radicals
Second-order Effects on Line Positions	p. 44
Understanding the Variation in Line Widths	p. 47
Puzzling Line Shapes	p. 48
Use of ESR Spectra to Determine Formation Constants	p. 49
References	p. 51
Anisotropic ESR Spectra
Introduction	p. 52
Solid-state ESR Spectra	p. 53
Spectra of Dilute Single Crystals	p. 54
Analysis of Frozen Solution Spectra	p. 55
Interpretation of the g-Matrix	p. 59
Interpretation of the Hyperfine Matrix	p. 60
Organometallic Examples	p. 63
A Low-spin Manganese(II) Complex	p. 63
Some Cobalt(O) Radical Anions	p. 66
Organic Examples of Solid-state ESR Spectra	p. 69
Irradiated Single Crystal of Glycylgiycine	p. 69
X-irradiated Single Crystal of Methylene Diphosphonic Acid	p. 70
Non-coincident Matrix Axes	p. 71
Symmetry Considerations	p. 71
Experimental Determination of Matrix Axis Orientations	p. 72
Organometallic Examples of Non-coincident Matrix Axes	p. 73
A Chromium Nitrosyl Complex	p. 73
Iron Pentacarbonyl Ions	p. 74
Another Low-spin Manganese(II) Complex	p. 76
Chromium(I) Piano-stool Complex	p. 77
[(RCCR')Co₂(CO)₆]^2+- and [SFeCo₂(CO)₉]^2+-	p. 79
(o-Xylylene)-Mn(dmpe)₂	p. 81
Cobalt Dithiolene Complexes	p. 86
"g-Strain"	p. 87
References	p. 89
ESR Kinetic Studies
Bloch's Phenomenological Model	p. 92
Derivation of the Bloch Equations	p. 94
Steady-state Solution	p. 95
Chemical Exchange - The Modified Bloch Equations	p. 98
Further Discussion of Line Shapes	p. 102
Applications of the Modified Bloch Equations	p. 102
Alternating Line Width Effects	p. 107
Spin Labels	p. 108
References	p. 110
ESR Spectra of Biradicals, Triplet States, and other S > 1/2 Systems
Biradicals	p. 112
Exchange Coupling	p. 113
Organic Triplet State Molecules and the Dipolar Interaction	p. 117
Organic Triplet State Molecules	p. 122
Transition Metal Complexes with S > 1/2	p. 122
Spin-Orbit Coupling	p. 122
High-spin Transition Metal Ions	p. 126
	p. 130
References	p. 132
Perturbation Theory Calculations
Second-order Perturbation Theory Treatment of Spin Hamiltonian with Non-coincident g- and 4-axes	p. 133
The Electron Zeeman Term	p. 133
Nuclear Hyperfine Interaction	p. 135
Perturbation Theory Treatment of Hyperfine Term	p. 138
Example Application of these Results	p. 144
Quadrupole Coupling	p. 145
Perturbation Theory Treatment of Quadrupole Term	p. 146
Example Application of Analysis Quadrupole Effects	p. 149
References	p. 152
Physical Constants, Conversion Factors, and Properties of Nuclei (Tables A1.1-A1.4)
Example	p. 155
References	p. 157
Advanced ESR Methods
High Frequency ESR	p. 159
Double Resonance	p. 161
Pulsed Methods	p. 162
References	p. 164
Subject Index	p. 169
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Electron Spin Resonance

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