Ligand Field Theory and Its Applications Book

	Preface	xv
1	Introduction	1
1.1	The Concept of a Ligand Field	1
1.2	The Scope of Ligand Field Theory	4
1.3	The d and Other Orbitals	5
1.4	The Symmetry Properties of Molecules and Wavefunctions	14
1.5	Qualitative Demonstration of the Ligand Field Effect	17
1.6	The Physical Properties Affected by Ligand Field Theory	21
1.7	Crystal Fields and Ligand Fields	24
2	Quantitative Basis of Crystal Fields	27
2.1	Crystal Field Theory	27
2.2	The Octahedral Crystal Field Potential	30
2.3	The Effect of V[subscript oct] on the d Wavefunctions	33
2.4	The Evaluation of [Delta]	38
2.5	The Tetrahedral and Cubic Potentials	40
2.6	Naming the Real d Orbitals	41
2.7	Potentials for Lower Symmetries	41
2.8	Other Parameterization Schemes	45
2.9	Limitations of Crystal Field Theory: Ligand Field Theory	48
2.10	f Orbitals and the Crystal Field Potential	50
3	The Angular Overlap Model	53
3.1	Basis of the Angular Overlap Model (AOM)	53
3.2	AOM Expressions for Complexes of Various Symmetries	61
3.3	Extensions of the AOM for Some Polyatomic Ligands	73
3.4	Approximations in the Derivation of Bonding Parameters	76
3.5	Advantages of the AOM Compared to the Electrostatic Crystal Field Theory	78
3.6	Calculations of Electronic Spectra and Magnetic Properties Using Computer Programs Based on the AOM	80
4	The Origin and Calculation of [Delta]	83
4.1	Calculations Based on Electrostatic Interactions	83
4.2	One-Electron Molecular Orbital Calculations	84
4.3	All-Electron Molecular Orbital Calculations	87
4.4	Symmetries Lower Than Cubic	89
4.5	f Electron Systems	89
4.6	Real Electron Density Distribution	90
5	Energy Levels of Transition Metal Ions	92
5.1	Introduction	92
5.2	Free Transition Ions	93
5.3	Free Ion Terms	95
5.4	Term Wavefunctions	103
5.5	Spin--Orbit Coupling	107
6	Effect of Ligand Fields on the Energy Levels of Transition Ions	112
6.1	The Effect of a Cubic Ligand Field on S and P Terms	112
6.2	The Effect of a Cubic Ligand Field on D Terms	115
6.3	The Effect of a Cubic Ligand Field on F Terms	117
6.4	The Effect of a Cubic Ligand Field on G, H, and I Terms	121
6.5	Strong-Field Configurations	121
6.6	Transition from Weak to Strong Ligand Fields	122
6.7	Correlation Diagrams	126
6.8	Tanabe--Sugano Diagrams	131
6.9	Spin-Pairing Energies	141
7	Influence of the d Configuration on the Geometry and Stability of Complexes	145
7.1	Dependence of the Geometry of a Complex on Its d Configuration	146
7.2	Dependence of the Stability of a Complex on Its d Configuration	166
8	The Electronic Spectra of Complexes	179
8.1	Important Features of Electronic Spectra	179
8.2	Characteristic Spectra of Complexes of First-Row Transition Ions	204
8.3	Typical Spectra of Second- and Third-Row Transition Ions	214
8.4	The Spectrochemical and Nephelauxetic Series	215
8.5	Charge Transfer Spectra	221
8.6	Luminescence Spectra	224
9	Magnetic Properties of Complexions	228
9.1	The Theory of Magnetic Susceptibility	228
9.2	The Magnetic Properties of Free Ions	237
9.3	Quenching of Orbital Angular Momentum by Ligand Fields	241
9.4	The Magnetic Properties of A and E Terms	244
9.5	The Magnetic Properties of T Terms	248
9.6	t[subscript 2(g)] Electron Delocalization	256
9.7	The Magnetic Properties of Complexes with A and E Ground Terms	259
9.8	The Magnetic Properties of Complexes with T Ground Terms	264
9.9	Summary	268
9.10	Spin-Free-Spin-Paired Equilibria	269
9.11	Magnetic Exchange	272
10	Electron Paramagnetic Resonance Spectra of Complexes	282
10.1	Nature of the EPR Experiment	282
10.2	The Spin Hamiltonian	294
10.3	Interpretation of the Spin Hamiltonian Parameters	296
10.4	Electron Nuclear Double Resonance	308
11	Actinide Element Compounds	311
11.1	Ligand Fields and f Electron Systems	311
11.2	Actinide Element Compounds	314
11.3	f Electrons and V[subscript oct]	315
11.4	Uv/vis Spectra of Actinide Complexes	317
11.5	Magnetic Properties of Actinide Complexes	319
	Appendix A1	325
A1.1	The Spherical Harmonics Y[superscript m subscript l]	325
A1.2	Integration of Products of Spherical Harmonics	325
	Appendix A2	328
A2.1	The Associated Legendre Polynomials [Xi superscript m subscript l] to Order 6	328
	Appendix A3	330
A3.1	The Energies Resulting from the Application of V[subscript trig]	330
	Appendix A4	331
A4.1	Relationships Between Some of the Coefficients in the Operators Defined in Section 2.8.1	331
	Appendix A5	332
A5.1	Matrix Elements of the Crystal Field Potential V[subscript cf] from a General Distribution of Effective Point Charges	332
	Appendix A6	334
A6.1	Energies of the Terms of d[superscript n] using Condon-Shortley Parameters	334
	Appendix A7	336
A7.1	The Curie Law for Magnetic Behavior	336
	Appendix A8	337
A8.1	The Operators L[subscript x], L[subscript y], S[subscript x], and S[subscript y]	337
	Appendix A9	339
A9.1	Expressions for the Magnetic Moments of [superscript 4]T[subscript 1(g)], [superscript 2]T[subscript 2(g)], and [superscript 5]T[subscript 2(g)] Terms in Cubic Symmetry	339
	List of Commonly Used Symbols	340
	Fundamental Constants	342
	Index	345