Magnetism and Transition Metal Complexes

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ISBN: 9780486462844 | 0486462846
Cover: Paperback
Copyright: 1/11/2008

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This text presents a detailed view of the calculation methods involved in the magnetic properties of transition metal complexes. Starting at an elementary level, it proceeds gradually through theory and calculations to offer sufficient background for original work in the field.

Preface	p. ix
Preface by Dante Gatteschi	p. xi
Preface to the First Edition	p. xiii
Symbols and useful constants	p. xvii
Magnetic units in the c.g.s. and SI systems	p. xxi
General considerations	p. 1
Introduction	p. 1
Definitions	p. 2
Types of magnetic behaviour	p. 4
Diamagnetism	p. 4
Paramagnetism	p. 6
Magnetic interactions	p. 8
The origin of paramagnetism	p. 10
Generalizations about the magnetic behaviour of transition metal complexes	p. 12
Simplification of Van Vleck's equation	p. 12
The magnitudes of magnetic moments	p. 16
References	p. 23
Free ions and crystal field theory	p. 24
Introduction	p. 24
Free ions	p. 25
Interelectron repulsion and free ion terms	p. 25
Spin-orbit coupling in free ions	p. 28
Cubic crystal fields	p. 31
The strength of crystal fields	p. 31
The weak field approximation	p. 32
Strong crystal fields	p. 34
Intermediate strength crystal fields	p. 39
Nephelauxetic and spectrochemical series	p. 39
Spin-orbit coupling in crystal field terms	p. 40
Wave-functions and energy levels in cubic and axially distorted cubic complexes	p. 40
Cubic symmetry	p. 41
Axially distorted cubic symmetries	p. 43
References	p. 46
Perturbation theory and its applications	p. 47
Perturbation theory	p. 47
The non-degenerate case	p. 49
The degenerate case	p. 51
Some remarks on the evaluation of matrix elements	p. 54
Orders of perturbation: first and second order Zeeman effects	p. 57
The relationship between g values from electron spin resonance and the wavefunctions of a system	p. 58
Simultaneous perturbations	p. 60
References	p. 62
The magnetic properties of transition metal ions in cubic crystal fields	p. 63
Introduction	p. 63
The quenching of the orbital contribution to the magnetic susceptibility	p. 63
The magnetic properties of transition metal ions in weak octahedral and tetrahedral crystal fields	p. 67
The [superscript 2]T[subscript 2] term arising from a free ion [superscript 2]D term	p. 68
The [superscript 5]T[subscript 2] term arising from a free ion [superscript 5]D term	p. 82
The [superscript 3]T[subscript 1] term arising from a free ion [superscript 3]F term	p. 84
The [superscript 4]T[subscript 1] term arising from a free ion [superscript 4]F term	p. 87
A[subscript 2] terms arising from free ion F terms	p. 89
E terms arising from free ion D terms	p. 94
The [superscript 6]A[subscript 1] term arising from a free ion [superscript 6]S term	p. 96
The magnetic properties of transition metal ions in medium and strong octahedral and tetrahedral crystal fields	p. 97
Medium crystal field T[subscript 1] terms arising from free ion F terms	p. 97
The calculation of the magnetic properties of transition metal ions with T ground terms from a consideration of t[superscript n subscript 2] e[superscript m] configurations	p. 100
The magnetic properties of spin-paired transition metal complexes in cubic crystal fields	p. 104
References	p. 106
The magnetic properties of transition metal ions in axially symmetric crystal fields	p. 107
The reduction of orbital angular momentum	p. 107
The magnetic properties of T terms in axially symmetric crystal fields	p. 110
The [superscript 2]T[subscript 2] term arising from a free ion [superscript 2]D term	p. 110
The [superscript 3]T[subscript 1] term arising from a free ion [superscript 3]F term	p. 121
The [superscript 5]T[subscript 2] term arising from a free ion [superscript 5]D term	p. 128
The [superscript 4]T[subscript 1] term arising from a free ion [superscript 4]F term	p. 132
The magnetic properties of A[subscript 2] and E terms in axially symmetric crystal fields	p. 137
The [superscript 2]E[subscript g] term from the d[superscript 9] configuration in a tetragonally distorted octahedral environment	p. 138
The [superscript 4]A[subscript 2g] term from the d[superscript 7] configuration in a tetragonally distorted tetrahedral environment	p. 143
References	p. 149
A comparison of experimental and calculated data	p. 150
The d[superscript 9] configuration	p. 150
The d[superscript 8] configuration	p. 156
The d[superscript 7] configuration	p. 158
The d[superscript 6] configuration	p. 159
The d[superscript 2] configuration	p. 161
The d[superscript 1] configuration	p. 165
References	p. 168
The magnetic properties of polynuclear transition metal complexes	p. 170
Introduction	p. 170
Mechanisms of antiferromagnetic exchange interactions	p. 172
Direct Interaction	p. 172
Superexchange	p. 174
Antiferromagnetism in polynuclear transition metal complexes	p. 175
Binuclear complexes	p. 178
Triangular trinuclear complexes	p. 190
Linear trinuclear complexes	p. 196
References	p. 202
Index	p. 204
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Magnetism and Transition Metal Complexes

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