Electron Paramagnetic Resonance of Transition Ions

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  • Edition: Reprint
  • Format: Paperback
  • Copyright: 2012-07-26
  • Publisher: Oxford University Press

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This book is a reissue of a classic Oxford text, and provides a comprehensive treatment of electron paramagnetic resonance of ions of the transition groups. The emphasis is on basic principles, with numerous references to publications containing further experimental results and more detailed developments of the theory. An introductory survey gives a general understanding, and a general survey presents such topics as the classical and quantum resonance equations, thespin-Hamiltonian, Endor, spin-spin and spin-lattice interactions, together with an outline of the known behaviour of ions of each of the five transition groups, at the experimentalist's level. Finally a theoretical survey, using group theory and symmetry properties, discusses the fundamentals of the theory ofparamagnetism.

Table of Contents

Preliminary Survey
Introduction to Electron Paramagnetic Resonance
Electronic and nuclear magnetic dipole momentsp. 1
Hyperfine structure in a free atom or ionp. 5
Magnetic resonancep. 9
Effective spin and anisotropyp. 10
'Initial splittings' or 'fine structure'p. 16
Magnetic hyperfine structurep. 25
Hyperfine structure including nuclear electric quadrupole interactionp. 31
A simple examplep. 33
Transition group ions and ligand fieldsp. 39
Spin-spin interactionp. 52
Spin-lattice interactionp. 60
Dynamic nuclear orientationp. 74
Endorp. 87
Experimental aspectsp. 92
General Survey
The Resonance Phenomenon
Use of rotating coordinatesp. 95
Magnetic resonancep. 96
Quantum-mechanical analysisp. 98
Magnetic resonance in aggregated systemsp. 102
Adiabatic rapid passagep. 104
Relaxation effectsp. 108
Radio-frequency pulses and spin-echoesp. 113
Solution of the macroscopic equations for slow passagep. 115
Intensity and line widthp. 119
Spectrometer sensitivityp. 125
The Spin Hamiltonian and the Spectrum
The spin Hamiltonianp. 133
The effect of anisotropy in the g-factorp. 135
Multipole fine structurep. 139
Fine structure in cubic fields (S = &frac52;, &frac72;)p. 142
Electronic 'quadrupole' fine structure (S = 1, &frac32;)p. 151
Electronic 'quadrupole' fine structure in a strong magnetic fieldp. 156
Hyperfine structure I-introductory remarksp. 163
Hyperfine structure II-strong external fieldp. 167
Hyperfine structure III-nuclear electric quadrupole interactionp. 178
'Forbidden' hyperfine transitionsp. 186
Ligand hyperfine structurep. 192
The spectrum of a powderp. 200
Effects of crystal imperfectionsp. 205
Weak-field Zeeman interaction for non-Kramers ionsp. 209
Electron-Nuclear Double Resonance (Endor)
Introductionp. 217
The Endor spectrump. 223
Enhancement of the nuclear transition probabilityp. 228
Endor on donors in siliconp. 234
Endor on donors in silicon-relaxation effectsp. 239
Relaxation effects in Endor-generalp. 243
The hyperfine structure of europiump. 251
The Endor spectrum of Nd3+ in LaCl3p. 255
Endor measurements of ligand hyperfine structurep. 259
Endor line widthsp. 264
'Indirect' observation of Endor transitionsp. 272
Summaryp. 274
The Lanthanide (4f) Group
Lanthanide compoundsp. 271
The free ionsp. 282
Crystalline field theory-C3h symmetryp. 285
Magnetic hyperfine structurep. 296
Nuclear electric quadrupole interactionp. 301
Experimental results for ethylsulphates and anhydrous chloridesp. 303
Experimental results for the double nitrates, Ln2Mg3(NO3)12 24H2Op. 320
Lanthanide ions in cubic symmetryp. 325
Ions with a half-filled 4f-shell, 4f7, 8S7\2, Eu2, Gd3+ Tb4+p. 335
Higher-order terms in the spin Hamiltonianp. 341
The Actinide (5f) Group
Ions and compounds of the actinide groupp. 346
Tripositive actinide ionsp. 348
Actinide ions in CaF2p. 350
Actinide ions in octahedral symmetryp. 354
Neptunyl and plutonyl ionsp. 359
Ions of the 3d Group in Intermediate Ligand Fields
Introductionp. 365
The intermediate crystal field approachp. 372
The strong crystal field approachp. 377
The effects of bondingp. 392
The electronic spin Hamiltonianp. 398
Magnetic hyperfine interactionp. 406
Nuclear electric quadrupole and nuclear Zeeman interactionp. 414
3d1. Ti3+ in an octahedral field. 2D, L = 2, S = ½p. 417
3d2. V3+, Cr4+ in an octahedral field. 43F, L = 3, S = 1p. 426
3d3. V2+, Cr3+ Mn4+ in an octahedral field. 4F, L = 3, S = &frac32;p. 430
3d4. Cr2+ in an octahedral field. 5D, L = 2, S = 2p. 434
3d5. Cr+, Mn2+ Fe3+ in an octahedral field. 6S, L = 0, S = &frac52;p. 436
3d6. Fe2+ in an octahedral field. 5D, L = 2, S = 2p. 443
3d7. Fe+ Co2+, Ni3+ in an octahedral field. 4F, L = 3, S = &frac32;p. 446
3d8. Co+, Ni2+, Cu3+ in an octahedral field. 3F, L = 3, S = 1p. 449
3d9. Ni+, Cu2+ in an octahedral field. 2D, L = 2, S = ½p. 455
3d ions in tetrahedral symmetryp. 467
Ions of the d-Groups in Strong Ligand Fields
The ions and their compoundsp. 472
The strong ligand field octahedral complexp. 476
Hyperfine interactionp. 478
d1 in strong octahedral field; (d¿)1, (t2), S = ½p. 478
d2 in strong octahedral field; (d¿) 2, (t2)2 S = 1p. 479
d3 in strong octahedral field; (d¿)3, (t2)3, S = &frac32;p. 479
d4 in strong octahedral field; (d¿)4, (t2)4, S = 1p. 480
d5 in strong octahedral field; (d¿)5, (t2)5, S = ½p. 481
d6 in strong octahedral field; (d¿) 6, (t2)6, S = 0p. 486
d7 in strong octahedral field; (d¿)6 (d¿), (t2)6e, S = ½p. 486
d8 in strong octahedral field; (d¿)6 (d¿)2, (t2)2e2, S = 1p. 487
d9 in strong octahedral field; (d¿)6 (d¿)3, (t2)6e3, S = ½p. 487
d1 in cubic (eightfold) coordinationp. 490
Spin-Spin Interaction
Introductionp. 491
Magnetic dipole-dipole interactionp. 492
Exchange interactionp. 495
Multipole interactionsp. 499
Interaction between a pair of similar ionsp. 502
Interaction between a pair of dissimilar ionsp. 509
Line broadening by spin-spin interactionp. 514
Line shape due to dipolar spin-spin interactionp. 521
Effect of exchange interaction on line shapep. 527
Magnetic dilution, and the spectra of pairsp. 529
Temperature-dependent effectsp. 535
Spin-Phonon Interaction
The attainment of thermal equilibriump. 541
The phonon radiation bathp. 547
Spin-lattice relaxation by phonons-Waller processesp. 551
Spin-lattice relaxation by modulation of the ligand fieldp. 557
Summary and comparison with experimentp. 565
The phonon 'bottle-neck' and phonon 'avalanche'p. 574
Theoretical Survey
The Electronic Zeeman Interaction
The interaction between electrons and a magnetic fieldp. 585
The Zeeman effect in a free atom (or ion)p. 586
LS-coupling and the Landé formulap. 587
Self-consistent field configurationsp. 589
Spin-orbit couplingp. 592
Matrix elements between Slater determinantsp. 593
Introduction of the crystal fieldp. 595
Gboup Theory-An Outline
In variance and degeneracyp. 601
Linear representations, equivalence, and irreducibilityp. 602
Orthogonality relations, characters, and classesp. 603
Reduction of a representation and calculation of the charactersp. 605
Splitting of a degenerate level by a perturbation of lower symmetryp. 607
The direct product of two representationsp. 611
Group Theory-The Rotation Group
Angular momentump. 615
The irreducible representationsp. 617
The coupling of angular momentap. 620
Multiple vector coupling and Racah symbolsp. 622
Irreducible tensor operators, the Wigner-Eckart theorem, and equivalent operatorsp. 624
The Cubic Group and Some Other Groups
The cubic groupp. 629
The fictitious angular momentump. 632
The multiplets ¿4 and ¿5 in trigonal axesp. 633
The double cubic groupp. 634
Groups of lower symmetryp. 638
Improper rotationsp. 640
Time Reversal and Kramers Degeneracy
Operations involving the timep. 643
Complex conjugationp. 644
Determination of the time reversal operatorp. 646
Kramers degeneracyp. 647
Time-reversal operator in the J, M> representationp. 649
The 'Spin Hamiltonian' for a Kramers doubletp. 650
The rhombic groupp. 654
Threefold symmetryp. 654
Selection rules related to time-reversalp. 656
The effect of an applied electric field on a paramagnetic ionp. 659
Elementary Theory of the Crystal Field
The crystal field (or crystal potential)p. 665
Equivalent operatorsp. 670
Off-diagonal matrix elements of the crystal fieldp. 676
The electronic Zeeman interactionp. 677
Electron spin-spin interactionsp. 678
Hyperfine Structure
Electrostatic hyperfine interactionsp. 680
Magnetic hyperfine interactionsp. 687
Alternative derivation of the magnetic hyperfine interactionp. 690
Equivalent operators for the magnetic hyperfine interactionp. 692
The effect of s-electrons: configuration interactionp. 695
The effect of s-electrons: core polarizationp. 702
Finer effects in the theory of hyperfine structurep. 706
Ions in a Weak Crystal Field (f Electrons)
Kramers ions in a weak crystal fieldp. 713
Rare-earth ions in cubic symmetryp. 719
The quadruplet ¿8p. 721
Representation of an irreducible tensor within the quadruplet ¿8-quadrupole couplingp. 731
Non-Kramers ions in the rare-earth groupp. 732
Non-Kramers rare-earth ions in cubic surroundingsp. 739
Intermediate Crystal Fields (The Iron Group)
Effect of the cubic crystal potentialp. 742
'Singlet' orbital ground state (ions of type A)p. 745
Triplet orbital ground state (ions of type B)p. 751
Departures from cubic symmetryp. 755
The influence of excited termsp. 758
The Effects Of Covalent Bonding
Summary of the foregoing theoryp. 761
The molecular orbitals model for covalent bondingp. 762
Bonding and anti-bonding orbitals, overlap, and covalencyp. 764
The ground states in weakly covalent compoundsp. 767
Orbital momentum and spin-orbit coupling in the presence of covalent bondingp. 773
Ligand hyperfine structure for ions of type Ap. 777
Orbital singlets: correction terms for the ligand hyperfine structurep. 781
Ligand hyperfine structure for ions of type Bp. 784
Ligand quadrupole hyperfine structurep. 788
The Jahn-Teller Effect in Paramagnetic Resonance
Introductionp. 79$
The Born-Oppenheimer approximation and the Jahn-Teller theoremp. 79$
The magnetic properties of a 2E levelp. 79$
The static Jahn-Teller effect in a 2E statep. 80$
Dynamic features of the static Jahn-Teller effectp. 80$
The dynamic Jahn-Teller effect in a 2E statep. 80$
Motional narrowing of the Jahn-Teller spectrump. 82$
Comparison with experimentp. 832
The Jahn-Teller effect in a triplet statep. 835
The Jahn-Teller effect in an orbital triplet with ¿3 couplingp. 835
The Jahn-Teller effect in an orbital triplet with ¿5 couplingp. 841
Comparison with experimentp. 846
Thermal and magnetic properties of a paramagnetic substancep. 848
Tables 1 to 26p. 856
Bibliographyp. 879
Author Indexp. 893
Subject Indexp. 898
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