3 Perturbation Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
3.1 Interelectronic Repulsion Perturbation . . . . . . . . . . . . . . . . . . . . 40
3.2 Spin–Orbit Coupling Perturbation . . . . . . . . . . . . . . . . . . . . . . . 43
3.3 Crystal Field Perturbation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
3.3.1 Use of the Group Theory to Predict the Orbital
Spitting in a Given Symmetry . . . . . . . . . . . . . . . . . . . . 47
3.4 Examples of Attribution of the Absorption Bands . . . . . . . . . . . . 55
3.5 Crystal Field Limits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
3.6 Effect of Distortion from Cubic Symmetry . . . . . . . . . . . . . . . . . 59
4 Magnetism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
4.1 Interaction Between Electrons and Magnetic Field . . . . . . . . . . . 65
4.2 Magnetic Susceptibility Expression for S = 1/2 . . . . . . . . . . . . . 69
4.3 Electron Spin Resonance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
4.3.1 Hyperfine Nuclear Interaction . . . . . . . . . . . . . . . . . . . . 75
4.3.2 Hyperfine Interaction by Quantum Mechanical
Approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
4.3.3 The Electronic Interaction with the Magnetic
Field in Oriented Systems . . . . . . . . . . . . . . . . . . . . . . . 77
4.3.4 The Electronic Interaction with the Magnetic
Field in Oriented Systems . . . . . . . . . . . . . . . . . . . . . . . 77
4.3.5 The Origin of the g Anisotropic Behavior . . . . . . . . . . . 79
4.3.6 g Expressions for a d
1 Electronic Configuration
in Tetragonal Symmetry Field . . . . . . . . . . . . . . . . . . . . 80
4.3.7 g Tensor Dependence on the Energy Level Trend
of the Paramagnetic Centers . . . . . . . . . . . . . . . . . . . . . 81
5 The Symmetry Properties Describe the Electronic Structure
of Inorganic and Coordination Compounds . . . . . . . . . . . . . . . . . . . 85
5.1 The Case of [Fe 3 Pt 3 (CO) 15 ]
n− n = 2, 1,
and of [Fe 3 Pt 3 (CO) 15 ]
2-n . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
85
5.2 Discussion of the Case . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
5.2.1 X-Ray Diffraction Studies . . . . . . . . . . . . . . . . . . . . . . . 86
5.2.2 Diffuse Reflectance Spectra . . . . . . . . . . . . . . . . . . . . . . 87
5.2.3 Electron Spin Resonance (ESR) Spectra . . . . . . . . . . . . 87
5.3 Chemical Message . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
5.4 The Case of Adducts of NN′Ethylenebis (acetylacetoneiminato)
Cobalt (II) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
5.5 Discussion of the Case . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
5.6 Chemical Message . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
5.7 The Case of Phthalocyaninato Co(II) . . . . . . . . . . . . . . . . . . . . . 93
5.8 Discussion of the Case . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
5.8.1 Electron Spin Resonance (ESR) Spectra . . . . . . . . . . . . 94
5.8.2 Diffuse Reflectance Spectra . . . . . . . . . . . . . . . . . . . . . . 96
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3.1 Interelectronic Repulsion Perturbation . . . . . . . . . . . . . . . . . . . . 40
3.2 Spin–Orbit Coupling Perturbation . . . . . . . . . . . . . . . . . . . . . . . 43
3.3 Crystal Field Perturbation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
3.3.1 Use of the Group Theory to Predict the Orbital
Spitting in a Given Symmetry . . . . . . . . . . . . . . . . . . . . 47
3.4 Examples of Attribution of the Absorption Bands . . . . . . . . . . . . 55
3.5 Crystal Field Limits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58
3.6 Effect of Distortion from Cubic Symmetry . . . . . . . . . . . . . . . . . 59
4 Magnetism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63
4.1 Interaction Between Electrons and Magnetic Field . . . . . . . . . . . 65
4.2 Magnetic Susceptibility Expression for S = 1/2 . . . . . . . . . . . . . 69
4.3 Electron Spin Resonance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
4.3.1 Hyperfine Nuclear Interaction . . . . . . . . . . . . . . . . . . . . 75
4.3.2 Hyperfine Interaction by Quantum Mechanical
Approach . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
4.3.3 The Electronic Interaction with the Magnetic
Field in Oriented Systems . . . . . . . . . . . . . . . . . . . . . . . 77
4.3.4 The Electronic Interaction with the Magnetic
Field in Oriented Systems . . . . . . . . . . . . . . . . . . . . . . . 77
4.3.5 The Origin of the g Anisotropic Behavior . . . . . . . . . . . 79
4.3.6 g Expressions for a d
1 Electronic Configuration
in Tetragonal Symmetry Field . . . . . . . . . . . . . . . . . . . . 80
4.3.7 g Tensor Dependence on the Energy Level Trend
of the Paramagnetic Centers . . . . . . . . . . . . . . . . . . . . . 81
5 The Symmetry Properties Describe the Electronic Structure
of Inorganic and Coordination Compounds . . . . . . . . . . . . . . . . . . . 85
5.1 The Case of [Fe 3 Pt 3 (CO) 15 ]
n− n = 2, 1,
and of [Fe 3 Pt 3 (CO) 15 ]
2-n . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
85
5.2 Discussion of the Case . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
5.2.1 X-Ray Diffraction Studies . . . . . . . . . . . . . . . . . . . . . . . 86
5.2.2 Diffuse Reflectance Spectra . . . . . . . . . . . . . . . . . . . . . . 87
5.2.3 Electron Spin Resonance (ESR) Spectra . . . . . . . . . . . . 87
5.3 Chemical Message . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
5.4 The Case of Adducts of NN′Ethylenebis (acetylacetoneiminato)
Cobalt (II) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
5.5 Discussion of the Case . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
5.6 Chemical Message . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
5.7 The Case of Phthalocyaninato Co(II) . . . . . . . . . . . . . . . . . . . . . 93
5.8 Discussion of the Case . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
5.8.1 Electron Spin Resonance (ESR) Spectra . . . . . . . . . . . . 94
5.8.2 Diffuse Reflectance Spectra . . . . . . . . . . . . . . . . . . . . . . 96
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