9780471317760

Ligand Field Theory and Its Applications

by ;
  • ISBN13:

    9780471317760

  • ISBN10:

    0471317764

  • Format: Hardcover
  • Copyright: 1999-12-28
  • Publisher: Wiley-VCH
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Summary

A complete, up-to-date treatment of ligand field theory and its applications Ligand Field Theory and Its Applications presents an up-to-date account of ligand field theory, the model currently used to describe the metal-ligand interactions in transition metal compounds, and the way it is used to interpret the physical properties of the complexes. It examines the traditional electrostatic crystal field model, still widely used by physicists, as well as covalent approaches such as the angular overlap model, which interprets the metal ligand interactions using parameters relating directly to chemical behavior. Written by internationally recognized experts in the field, this book provides a comparison between ligand field theory and more sophisticated treatments as well as an account of the methods used to calculate the energy levels in compounds of the transition metals. It also covers physical properties such as stereochemistry, light absorption, and magnetic behavior. An emphasis on the interpretation of experimental results broadens the book's field of interest beyond transition metal chemistry into the many other areas where these metal ions play an important role. As clear and accessible as Brian Figgis's 1966 classic Introduction to Ligand Fields, this new book provides inorganic and bioinorganic chemists as well as physical chemists, chemical physicists, and spectroscopists with a much-needed overview of the many significant changes that have taken place in ligand field theory over the past 30 years.

Author Biography

BRIAN N. FIGGIS, DSc, is Professor of Inorganic Chemistry at the University of Western Australia. <p> L A. HITCHMAN, DSc, is Reader in Chemistry at the University of Tasmania.

Table of Contents

Preface xv
Introduction
1(26)
The Concept of a Ligand Field
1(3)
The Scope of Ligand Field Theory
4(1)
The d and Other Orbitals
5(9)
The Symmetry Properties of Molecules and Wavefunctions
14(3)
The Molecular Point Groups
14(1)
The Representations of Wavefunctions
15(1)
Typical Applications in Ligand Field Theory
16(1)
Qualitative Demonstration of the Ligand Field Effect
17(4)
The Physical Properties Affected by Ligand Field Theory
21(3)
Thermochemical Properties and Geometric Distortions
21(1)
Spectral Properties
22(1)
Magnetic Properties
23(1)
Crystal Fields and Ligand Fields
24(3)
Quantitative Basis Of Crystal Fields
27(26)
Crystal Field Theory
27(3)
The Octahedral Crystal Field Potential
30(3)
The Effect of Voct on the d Wavefunctions
33(5)
The Evaluation of δ
38(2)
The Tetrahedral and Cubic Potentials
40(1)
Naming the Real d Orbitals
41(1)
Potentials for Lower Symmetries
41(4)
Tetragonally Distorted Octahedron
41(3)
Trigonally Distorted Octahedron
44(1)
Other Parameterization Schemes
45(3)
The A and B Coefficients
46(1)
The Parameters Ds and Dt
47(1)
Limitations of Crystal Field Theory: Ligand Field Theory
48(2)
f Orbitals and the Crystal Field Potential
50(3)
The Angular Overlap Model
53(30)
Basis of the Angular Overlap Model (AOM)
53(8)
Simple MO Picture of the Bonding in Transition-Metal Complexes
54(4)
Derivation of AOM Parameters Using the Wolfsberg--Helmholtz Approximation
58(2)
Derivation of the d Orbital Energies and Wavefunctions in a Complex Using the AOM
60(1)
AOM Expressions for Complexes of Various Symmetries
61(12)
Octahedral Complexes
61(3)
Tetragonally Distorted Octahedral, Planar, and Linear Complexes: The Importance of d-s Mixing
64(3)
Tetrahedral, Distorted Tetrahedral, and Square-Based Pyramidal Complexes
67(1)
Trigonal Bipyramidal Complexes
68(1)
Variation of AOM Parameters with Bond Distance
69(1)
Typical AOM Parameters
70(3)
Extensions of the AOM for Some Polyatomic Ligands
73(3)
Phase-Coupled Ligators
73(1)
Off-Axis Bonds and Interactions with Nonbonding Electron Pairs
74(2)
Approximations in the Derivation of Bonding Parameters
76(2)
Advantages of the AOM Compared to the Electrostatic Crystal Field Theory
78(2)
Calculations of Electronic Spectra and Magnetic Properties Using Computer Programs Based on the AOM
80(3)
The Origin And Calculation of δ
83(9)
Calculations Based on Electrostatic Interactions
83(1)
One-Electron Molecular Orbital Calculations
84(3)
All-Electron Molecular Orbital Calculations
87(2)
Symmetries Lower Than Cubic
89(1)
f Electron Systems
89(1)
Real Electron Density Distribution
90(2)
Energy Levels Of Transition Metalions
92(20)
Introduction
92(1)
Free Transition Ions
93(2)
Free Ion Terms
95(8)
Term Wavefunctions
103(4)
Spin-Orbit Coupling
107(5)
Effect Of Ligand Fields On The Energy Levels Of Transition Ions
112(33)
The Effect of a Cubic Ligand Field on S and P Terms
112(3)
S Terms
113(1)
P Terms
113(2)
The Effect of a Cubic Ligand Field on D Terms
115(2)
The Effect of a Cubic Ligand Field on F Terms
117(4)
The Effect of a Cubic Ligand Field on G, H, and I Terms
121(1)
Strong-Field Configurations
121(1)
Transition from Weak to Strong Ligand Fields
122(4)
Correlation Diagrams
126(5)
Tanabe-Sugano Diagrams
131(10)
Spin-Pairing Energies
141(4)
Influence Of the d Configuration On The Geometry And Stability Of Complexes
145(34)
Dependence of the Geometry of a Complex on Its d Configuration
146(20)
Nondegenerate Electronic States
146(2)
Degenerate States: The Jahn-Teller Effect
148(12)
Bond Length Differences Between High-and Low-spin Complexes
160(3)
Variation of Bond Lengths on Crossing the Transition Series
163(3)
Dependence of the Stability of a Complex on Its d Configuration
166(13)
Thermodynamic Effects
167(9)
Kinetic Effects
176(3)
The Electronic Spectra Of Complexes
179(49)
Important Features of Electronic Spectra
179(25)
Band Intensities
179(10)
Band Energies
189(6)
Band Widths and Shapes
195(6)
Effect of Temperature on Electronic Bands
201(3)
Characteristic Spectra of Complexes of First-Row Transition Ions
204(10)
Hexaaqua Complexes of First-Row Ions
204(7)
Tetrahedral and Planar Complexes of First-Row Transition Ions
211(3)
Typical Spectra of Second-and Third-Row Transition Ions
214(1)
The Spectrochemical and Nephelauxetic Series
215(6)
The Spectrochemical Series
215(3)
The Nephelauxetic Series
218(3)
Charge Transfer Spectra
221(3)
Luminescence Spectra
224(4)
Magnetic Properties Of Complex Ions
228(54)
The Theory of Magnetic Susceptibility
228(9)
General
228(4)
Paramagnetism
232(1)
Quantum Mechanical Treatment of Paramagnetic Susceptibilities
233(4)
The Magnetic Properties of Free Ions
237(4)
The First-Order Zeeman Effect
237(1)
The Second-Order Zeeman Effect
238(1)
States kT
239(2)
States kT
241(1)
Quenching of Orbital Angular Momentum by Ligand Fields
241(3)
The Magnetic Properties of A and E Terms
244(4)
The Magnetic Properties of T Terms
248(8)
Splitting by Spin-Orbit Coupling
248(3)
The Calculation of µeff
251(3)
Departure from Cubic Symmetry
254(2)
t2(g) Electron Delocalization
256(3)
General
256(1)
A and E Terms
257(2)
T Terms
259(1)
The Magnetic Properties of Complexes with A and E Ground Terms
259(5)
Octahedral Complexes
259(2)
Tetrahedral Complexes
261(3)
The Magnetic Properties of Complexes with T Ground Terms
264(4)
Summary
268(1)
Spin-Free-Spin-Paired Equilibria
269(3)
Magnetic Exchange
272(10)
The Heisenberg Hamiltonian
272(1)
Mechanism of Magnetic Exchange: Superexchange
273(4)
Some Examples of Superexchange in Clusters
277(5)
Electron Paramagnetic Resonance Spectra Of Complexes
282(29)
Nature of the EPR Experiment
282(12)
Introduction
282(2)
Features of EPR Spectra
284(10)
The Spin Hamiltonian
294(2)
Interpretation of the Spin Hamiltonian Parameters
296(12)
The g Tensor
296(5)
The Hyperfine Tensor
301(7)
The Zero-Field Splitting Tensor
308(1)
Electron Nuclear Double Resonance
308(3)
Actinide Element Compounds
311(14)
Ligand Fields and f Electron Systems
311(3)
Actinide Element Compounds
314(1)
f Electrons and Voct
315(2)
Uv/vis Spectra of Actinide Complexes
317(2)
Magnetic Properties of Actinide Complexes
319(6)
Appendix A1 325(3)
A1.1 The Spherical Harmonics
325(1)
A1.2 Integration of Products of Spherical Harmonics
325(3)
Appendix A2 328(2)
A2.1 The Associated Legendre Polynomials to Order 6
328(2)
Appendix A3 330(1)
A3.1 The Energies Resulting from the Application of Vtrig
330(1)
Appendix A4 331(1)
A4.1 Relationships Between Some of the Coefficients in the Operators Defined in Section 2.8.1
331(1)
Appendix A5 332(2)
A5.1 Matrix Elements of the Crystal Field Potential Vcf from a General Distribution of Effective Point Charges
332(2)
Appendix A6 334(2)
A6.1 Energies of the Terms of dn using Condon-Shortley Parameters
334(2)
Appendix A7 336(1)
A7.1 The Curie Law for Magnetic Behavior
336(1)
Appendix A8 337(2)
A8.1 The Operators Lx, Ly, Sx, and Sy
337(2)
Appendix A9 339(1)
A9.1 Expressions for the Magnetic Moments of Terms in Cubic Symmetry
339(1)
List Of Commonly Used Symbols 340(2)
Fundamental Constants 342(3)
Index 345

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