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Electron Spin Resonance : Analysis and Interpretation - Philip H. Rieger

Electron Spin Resonance

Analysis and Interpretation

Hardcover Published: 1st August 2007
ISBN: 9780854043552
Number Of Pages: 173

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From reviews: 'an excellent textbook, presenting the subject of ESR in a straightforward manner and unraveling the complexities of spectral analyses and interpretation.'

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.

Industry Reviews

"It is a very welcome addition to the literature in the field of EPR spectroscopy....its approach is fresh and didactically sound. The book is accessible to a broader readership than existing textbooks.The selection of topics is well balanced. A student who reads through this book will acquire a solid repertoire of methods for interpreting even complicated EPR spectra....For experienced researchers the book is well suited as a dictionary of spectrum analysis....clear and simple figures are well suited for illustrating lectures. There are not many books that I could recommend with such a good conscience as this one. Personally, I now regard it as an essential item on my bookshelf." * Angewandte Chemie, International Edition, 2008, 47 2913-2914 (Gunnar Jeschke) *
"I would also like to compliment you on the very fine production of the monograph." * University of Manchester, 10th September 2007 (Prof David Collison) *

What is ESR Spectroscopy?p. 1
The ESR Experimentp. 3
Sensitivityp. 4
Saturationp. 5
Nuclear Hyperfine Interactionp. 5
Operation of an ESR Spectrometerp. 7
Optimization of Operating Parametersp. 11
Microwave Frequencyp. 11
Microwave Powerp. 12
Center Field, Sweep Width and Field Offsetp. 13
Sweep Timep. 14
Modulation Frequencyp. 14
Second Harmonic Detectionp. 15
Modulation Amplitude
Modulation Phasep. 15
Signal Gainp. 16
Filter Time Constantp. 16
Applications of ESR Spectroscopyp. 17
Electronic Structure Determinationp. 17
Analytical Applicationsp. 17
Determination of Ratesp. 18
Referencesp. 18
Isotropic ESR Spectra of Organic Radicals
Isotropic ESR Spectrap. 21
Line Positions in Isotropic Spectrap. 21
Hyperfine Coupling Patternsp. 22
Second-order Splittingsp. 25
Spin Hamiltonian Parameters from Spectrap. 26
Interpretation of Isotropic Parametersp. 27
Line Widths in Isotropic Spectrap. 29
Incomplete Averaging of Anisotropiesp. 29
Rates of Fluxionality from Line Widthsp. 30
Organic Radical Reactionsp. 32
Analysis of Isotropic ESR Spectrap. 32
Preliminary Examination of the Spectrump. 33
What do you Expect to See?p. 33
Are the Gross Features of the Spectrum Consistent with the Model?p. 34
An Examplep. 34
Detailed Analysis for Determination of Parametersp. 36
Computation of Multiplet Intensity Ratiosp. 37
Multiplet Patterns due to Isotopomersp. 38
Second-order Shifts in Line Positionsp. 39
Related Techniques (ENDOR)p. 41
Referencesp. 42
Isotropic Spectra of Organometallic Radicals
Second-order Effects on Line Positionsp. 44
Understanding the Variation in Line Widthsp. 47
Puzzling Line Shapesp. 48
Use of ESR Spectra to Determine Formation Constantsp. 49
Referencesp. 51
Anisotropic ESR Spectra
Introductionp. 52
Solid-state ESR Spectrap. 53
Spectra of Dilute Single Crystalsp. 54
Analysis of Frozen Solution Spectrap. 55
Interpretation of the g-Matrixp. 59
Interpretation of the Hyperfine Matrixp. 60
Organometallic Examplesp. 63
A Low-spin Manganese(II) Complexp. 63
Some Cobalt(O) Radical Anionsp. 66
Organic Examples of Solid-state ESR Spectrap. 69
Irradiated Single Crystal of Glycylgiycinep. 69
X-irradiated Single Crystal of Methylene Diphosphonic Acidp. 70
Non-coincident Matrix Axesp. 71
Symmetry Considerationsp. 71
Experimental Determination of Matrix Axis Orientationsp. 72
Organometallic Examples of Non-coincident Matrix Axesp. 73
A Chromium Nitrosyl Complexp. 73
Iron Pentacarbonyl Ionsp. 74
Another Low-spin Manganese(II) Complexp. 76
Chromium(I) Piano-stool Complexp. 77
[(RCCR')Co2(CO)6]2+- and [SFeCo2(CO)9]2+-p. 79
(o-Xylylene)-Mn(dmpe)2p. 81
Cobalt Dithiolene Complexesp. 86
"g-Strain"p. 87
Referencesp. 89
ESR Kinetic Studies
Bloch's Phenomenological Modelp. 92
Derivation of the Bloch Equationsp. 94
Steady-state Solutionp. 95
Chemical Exchange - The Modified Bloch Equationsp. 98
Further Discussion of Line Shapesp. 102
Applications of the Modified Bloch Equationsp. 102
Alternating Line Width Effectsp. 107
Spin Labelsp. 108
Referencesp. 110
ESR Spectra of Biradicals, Triplet States, and other S > 1/2 Systems
Biradicalsp. 112
Exchange Couplingp. 113
Organic Triplet State Molecules and the Dipolar Interactionp. 117
Organic Triplet State Moleculesp. 122
Transition Metal Complexes with S > 1/2p. 122
Spin-Orbit Couplingp. 122
High-spin Transition Metal Ionsp. 126
p. 130
Referencesp. 132
Perturbation Theory Calculations
Second-order Perturbation Theory Treatment of Spin Hamiltonian with Non-coincident g- and 4-axesp. 133
The Electron Zeeman Termp. 133
Nuclear Hyperfine Interactionp. 135
Perturbation Theory Treatment of Hyperfine Termp. 138
Example Application of these Resultsp. 144
Quadrupole Couplingp. 145
Perturbation Theory Treatment of Quadrupole Termp. 146
Example Application of Analysis Quadrupole Effectsp. 149
Referencesp. 152
Physical Constants, Conversion Factors, and Properties of Nuclei (Tables A1.1-A1.4)
Examplep. 155
Referencesp. 157
Advanced ESR Methods
High Frequency ESRp. 159
Double Resonancep. 161
Pulsed Methodsp. 162
Referencesp. 164
Subject Indexp. 169
Table of Contents provided by Ingram. All Rights Reserved.

ISBN: 9780854043552
ISBN-10: 0854043551
Audience: Professional
Format: Hardcover
Language: English
Number Of Pages: 173
Published: 1st August 2007
Country of Publication: GB
Dimensions (cm): 23.62 x 15.49  x 1.78
Weight (kg): 0.44

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