The structure of inorganic radicals: An application of electron spin resonance to the study of molecular structure. With 74 illustr. and 57 tables
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| Main Authors: | , |
|---|---|
| Format: | Book |
| Language: | English |
| Published: |
Amsterdam [u.a.]
Elsevier
1967
|
| Subjects: | |
| Online Access: | Inhaltsverzeichnis |
| Physical Description: | X, 280 S. Ill., graph. Darst. |
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| 245 | 1 | 0 | |a The structure of inorganic radicals |b An application of electron spin resonance to the study of molecular structure. With 74 illustr. and 57 tables |c by P. W. Atkins and M. C. R. Symons |
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Record in the Search Index
| _version_ | 1804119875293020160 |
|---|---|
| adam_text | THE STRUCTURE OF
INORGANIC RADICALS
An Application of Electron Spin Resonance
to the Study of Molecular Structure
B Y
P W ATKINS
Fellow of Lincoln College, Oxford
A N D
MCR SYMONS
Professor of Physical Chemistry, The University of Leicester
t
I
ELSEVIER PUBLISHING COMPANY
AMSTERDAM-LONDON-NEWYORK
Contents
PREFACE V
Chapter 1 INTRODUCTION 1
1 1 Survey 1
(a) Details of chapters 2
1 2 Historical Review 3
(a) Electron spin resonance 3
(b) Radical formation and trapping 5
1 3 Other Techniques 6
(a) Ultraviolet spectroscopy 6
(b) Infrared and Raman spectroscopy 6
(c) Nuclear magnetic resonance 7
(d) Microwave spectroscopy 7
References 7
Chapter 2 AN INTRODUCTION TO ELECTRON SPIN RESONANCE 9
2 1 Basic Principles 9
2 2 Value Variation 11
2 3 Hyperfine Interaction 14
(a) Multiplet spectrum from one nucleus 15
(b) Multiplet spectrum from several nuclei 15
(c) Anisotropic (dipolar) interaction 17
(d) Isotropic (contact) interaction 18
(e) Inner shell polarisation 19
2 4 Molecular Parameters 20
(a) Spin density distribution 20
(b) Bond angles 22
2 5 Hyperfine Coupling to a-Atoms 23
(a) Anisotropic hyperfine coupling to a-atoms % 23
(b) Isotropic hyperfine coupling to a-atoms 23
(c) Isotropic hyperfine coupling to /?-atoms (hyperconjugation) 27
2 6 Radicals in the Liquid and Solid State 28
(a) Radicals in single crystals 28
(b) Radicals in glasses 28
(c) Radicals in solution 29
2 7 Line-Widths and Relaxation 29
(a) Spin-lattice relaxation 29
(b) Spin-spin relaxation 30
(c) Line-widths and correlation times 31
References 33
VIII CONTENTS
Chapter 3 FORMATION AND TRAPPING OF RADICALS 35
3 1 Radicals in the Gas Phase 35
3 2 Matrix Isolation Methods 36
(a) Formation prior to trapping 36
(b) Formation by photolysis in situ 36
(c) Formation by reaction in situ 37
3 3 Irradiation of Solids 37
(a) Pure materials 37
(b) Solid solutions 40
3 4 Transient Radicals in Solution 41
(a) Photolysis and radiolysis 41
(b) Flow techniques 41
References 42
Chapter 4 TRAPPED AND SOLVATED ELECTRONS 43
4 1 F-Centres 43
(a) Information from hyperfine coupling 43
(b) Information from the ^-tensor 48
(c) Other electron-excess centres 49
(d) Other ionic crystals 50
4 2 Metal Solutions 51
(a) Equilibria and species 52
(b) Information from electron spin resonance 53
(c) Information from nuclear magnetic resonance 63
(d) Theories 67
4 3 Electrons in Glasses 73
(a) Rigid ammoniacal solutions 73
(b) Electrons in water 74
(c) Electrons in organic solvents 76
References 77
Chapter 5 ATOMS AND MONATOMIC IONS 80
5 1 Matrix Effects 80
(a) Long range interaction 81
(b) Short range interaction 82
5 2 Hydrogen Atoms 84
5 3 Metal Atoms 90
(a) Alkali metals 90
(b) Silver atoms 90
5 4 Atoms of Group V-Elements 93
5 5 Oxygen Atoms and 0~-Ions 95
5 6 Halogen Atoms 96
(a) The ion F2 97
References 97
Chapter 6 DIATOMIC RADICALS 99
6 1 Structural Aspects 99
(a) AB 7r-radicals 99
(b) AH rc-radicals 102
(c) AB (j-radicals 102
(d) Order of levels 103
CONTENTSIX
(e) Contribution from A and B 103
6 2 Results for Diatomic Radicals 104
(a) AH rc-radicals 104
(b) AB ^-radicals 108
(c) AB (7i*)3-radicals 110
(d) AB cr-radicals 113
References 117
Chapter 7 TRIATOMIC RADICALS 119
7 1 Structural Aspects 119
(a) Linear molecules v 119
(b) Bent AB2 molecules 119
(c) Electronegativity and bond angle 122
(d) Expected electron spin resonance spectra 124
7 2 Results for Triatomic Radicals 127
(a) Seventeen electron radicals 127
(b) Nineteen electron radicals 142
(c) Twenty-one electron radicals 158
References 160
Chapter 8 TETRA-ATOMIC RADICALS 162
8 1 Structural Aspects 162
(a) Planar molecules 162
(b) Pyramidal molecules 162
(c) Electronegativity effects 164
(d) Expected electron spin resonance spectra 164
8 2 Experimental Results 166
(a) Twenty-three electron radicals 166
(b) Twenty-five electron radicals 170
(c) Reactivity 176
(d) Related species 178
References 185
Chapter 9 PENTA-ATOMIC RADICALS 187
9 1 Structural Aspects 187
(a) Tetrahedral molecules 187
(b) Distortions 188
(c) Expected electron spin resonance spectra 190
9 2 Experimental Results 193
(a) Thirty-one electron radicals » 194
(b) Thirty-three electron radicals 200
References)207
Chapter 10 SUMMARY AND CONCLUSIONS 208
10 1 Some Generalisations 208
(a) The applicability of simple theory 208
(b) Trends in isoelectronic series 210
(c) Identification of radicals in irradiated solids 212
10 2 Some Unresolved Problems 213
(a) Radicals in irradiated borates 213
(b) Radicals in irradiated silicon 214
X CONTENTS
(c) Sulphur radicals 215
References 218
Appendix 1 THE LANGUAGE OF GROUP THEORY 219
1A 1 Definitions 219
1A 2 Symbols 224
(a) The operations 224
(b) The representations 224
(c) The groups 225
1A 3 Applications 226
(a) To label an orbital 226
(b) To label a state • 227
(c) Selection rules 228
References 229
Appendix 2 THE SPIN HAMILTONIAN 230
2A 1 The spin Hamiltonian 230
2A 2 Application of Perturbation Theory 232
2A 3 Solution of-the Eigenvalue Equation 235
(a) No magnetic nuclei present 235
(b) One spin-i nucleus present 236
(c) The Breit-Rabi equation 238
References 240
Appendix 3 CALCULATION OE ^-VALUES 241
3A 1 General Theory 241
3A 2 Examples 244
(a) o-*-Radicals 244
(b) rc-Radicals 247
(c) ABn-Radicals 251
References 254
Appendix 4 DETERMINATION OF SPIN-DENSITY DISTRIBUTK IN AND BOND ANGLES 255
4A 1 Population Analysis 255
(a) Determination of (r~ J)np 255
(b) Calculation of | pns (0)|2 257
4A 2 Determination of Bond Angles 257
4A 3 Neighbouring Atom Interactions 258
References 260
Appendix 5 ANALYSIS OF ELECTRON SPIN RESONANCE SPECTRA 261
5A 1 Solution Spectra 264
5A 2 Crystal Spectra 265
5A 3 Powder Spectra 268
References 272
INDEX OF DATA 273
SUBJECT INDEX 275
|
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| spelling | Atkins, Peter W. 1940- Verfasser (DE-588)128437782 aut The structure of inorganic radicals An application of electron spin resonance to the study of molecular structure. With 74 illustr. and 57 tables by P. W. Atkins and M. C. R. Symons Amsterdam [u.a.] Elsevier 1967 X, 280 S. Ill., graph. Darst. txt rdacontent n rdamedia nc rdacarrier Anorganische Chemie (DE-588)4002145-2 gnd rswk-swf Anorganische Verbindungen (DE-588)4002147-6 gnd rswk-swf Elektronenstruktur (DE-588)4129531-6 gnd rswk-swf Radikal Chemie (DE-588)4076475-8 gnd rswk-swf Anorganische Verbindungen (DE-588)4002147-6 s Radikal Chemie (DE-588)4076475-8 s DE-604 Elektronenstruktur (DE-588)4129531-6 s Anorganische Chemie (DE-588)4002145-2 s Symons, Martyn C. R. 1925- Verfasser (DE-588)124745016 aut HEBIS Datenaustausch application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=003552049&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis |
| spellingShingle | Atkins, Peter W. 1940- Symons, Martyn C. R. 1925- The structure of inorganic radicals An application of electron spin resonance to the study of molecular structure. With 74 illustr. and 57 tables Anorganische Chemie (DE-588)4002145-2 gnd Anorganische Verbindungen (DE-588)4002147-6 gnd Elektronenstruktur (DE-588)4129531-6 gnd Radikal Chemie (DE-588)4076475-8 gnd |
| subject_GND | (DE-588)4002145-2 (DE-588)4002147-6 (DE-588)4129531-6 (DE-588)4076475-8 |
| title | The structure of inorganic radicals An application of electron spin resonance to the study of molecular structure. With 74 illustr. and 57 tables |
| title_auth | The structure of inorganic radicals An application of electron spin resonance to the study of molecular structure. With 74 illustr. and 57 tables |
| title_exact_search | The structure of inorganic radicals An application of electron spin resonance to the study of molecular structure. With 74 illustr. and 57 tables |
| title_full | The structure of inorganic radicals An application of electron spin resonance to the study of molecular structure. With 74 illustr. and 57 tables by P. W. Atkins and M. C. R. Symons |
| title_fullStr | The structure of inorganic radicals An application of electron spin resonance to the study of molecular structure. With 74 illustr. and 57 tables by P. W. Atkins and M. C. R. Symons |
| title_full_unstemmed | The structure of inorganic radicals An application of electron spin resonance to the study of molecular structure. With 74 illustr. and 57 tables by P. W. Atkins and M. C. R. Symons |
| title_short | The structure of inorganic radicals |
| title_sort | the structure of inorganic radicals an application of electron spin resonance to the study of molecular structure with 74 illustr and 57 tables |
| title_sub | An application of electron spin resonance to the study of molecular structure. With 74 illustr. and 57 tables |
| topic | Anorganische Chemie (DE-588)4002145-2 gnd Anorganische Verbindungen (DE-588)4002147-6 gnd Elektronenstruktur (DE-588)4129531-6 gnd Radikal Chemie (DE-588)4076475-8 gnd |
| topic_facet | Anorganische Chemie Anorganische Verbindungen Elektronenstruktur Radikal Chemie |
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