Ligand field theory and its applications:
Saved in:
| Main Authors: | , |
|---|---|
| Format: | Book |
| Language: | English |
| Published: |
New York [u.a.]
Wiley-VCH
2000
|
| Series: | Special topics in inorganic chemistry
|
| Subjects: | |
| Online Access: | Inhaltsverzeichnis |
| Physical Description: | XVIII, 354 S. Ill., graph. Darst. |
| ISBN: | 0471317764 |
Staff View
MARC
| LEADER | 00000nam a2200000 c 4500 | ||
|---|---|---|---|
| 001 | BV012999050 | ||
| 003 | DE-604 | ||
| 005 | 20050831 | ||
| 007 | t | ||
| 008 | 000222s2000 ad|| |||| 00||| eng d | ||
| 020 | |a 0471317764 |9 0-471-31776-4 | ||
| 035 | |a (OCoLC)246125379 | ||
| 035 | |a (DE-599)BVBBV012999050 | ||
| 040 | |a DE-604 |b ger |e rakwb | ||
| 041 | 0 | |a eng | |
| 049 | |a DE-355 |a DE-20 |a DE-703 |a DE-384 |a DE-11 | ||
| 050 | 0 | |a QD475 | |
| 082 | 0 | |a 541.2242 | |
| 084 | |a UP 3500 |0 (DE-625)146383: |2 rvk | ||
| 084 | |a VE 5720 |0 (DE-625)147120:253 |2 rvk | ||
| 100 | 1 | |a Figgis, Brian N. |e Verfasser |4 aut | |
| 245 | 1 | 0 | |a Ligand field theory and its applications |c Brian N. Figgis ; Michael A. Hitchman |
| 264 | 1 | |a New York [u.a.] |b Wiley-VCH |c 2000 | |
| 300 | |a XVIII, 354 S. |b Ill., graph. Darst. | ||
| 336 | |b txt |2 rdacontent | ||
| 337 | |b n |2 rdamedia | ||
| 338 | |b nc |2 rdacarrier | ||
| 490 | 0 | |a Special topics in inorganic chemistry | |
| 650 | 7 | |a Química de coordenação |2 larpcal | |
| 650 | 0 | 7 | |a Ligandenfeldtheorie |0 (DE-588)4167657-9 |2 gnd |9 rswk-swf |
| 689 | 0 | 0 | |a Ligandenfeldtheorie |0 (DE-588)4167657-9 |D s |
| 689 | 0 | |5 DE-604 | |
| 700 | 1 | |a Hitchman, Michael A. |e Verfasser |4 aut | |
| 856 | 4 | 2 | |m HBZ Datenaustausch |q application/pdf |u http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=008858447&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA |3 Inhaltsverzeichnis |
| 999 | |a oai:aleph.bib-bvb.de:BVB01-008858447 | ||
Record in the Search Index
| _version_ | 1804127699104432128 |
|---|---|
| adam_text | Titel: Ligand field theory and its applications
Autor: Figgis, Brian N
Jahr: 2000
CONTENTS
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
1.4.1 The Molecular Point Groups / 14
1.4.2 The Representations of Wavefunctions / 15
1.4.3 Typical Applications in Ligand Field Theory / 16
1.5 Qualitative Demonstration of the Ligand Field Effect / 17
1.6 The Physical Properties Affected by Ligand Field Theory / 21
1.6.1 Thermochemical Properties and Geometric
Distortions / 21
1.6.2 Spectral Properties / 22
1.6.3 Magnetic Properties / 23
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
K CONTENTS
2.3 The Effect of Voct on the d Wavefunctions / 33
2.4 The Evaluation of A / 38
2.5 The Tetrahedral and Cubic Potentials / 40
2.6 Naming the Real d Orbitals / 41
2.7 Potentials for Lower Symmetries / 41
2.7.1 Tetragonally Distorted Octahedron / 41
2.7.2 Trigonally Distorted Octahedron / 44
2.8 Other Parameterization Schemes / 45
2.8.1 The A and B Coefficients / 46
2.8.2 The Parameters Ds and Dt / 47
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
3.1.1 Simple MO Picture of the Bonding in
Transition-Metal Complexes / 54
3.1.2 Derivation of AOM Parameters Using the
Wolfsberg-Helmholtz Approximation / 58
3.1.3 Derivation of the d Orbital Energies and Wavefunctions
in a Complex Using the AOM / 60
3.2 AOM Expressions for Complexes of Various Symmetries / 61
3.2.1 Octahedral Complexes / 61
3.2.2 Tetragonally Distorted Octahedral, Planar, and Linear
Complexes: The Importance of d-s Mixing / 64
3.2.3 Tetrahedral, Distorted Tetrahedral, and Square-Based
Pyramidal Complexes / 67
3.2.4 Trigonal Bipyramidal Complexes / 68
3.2.5 Variation of AOM Parameters with Bond Distance / 69
3.2.6 Typical AOM Parameters / 70
3.3 Extensions of the AOM for Some Polyatomic Ligands / 73
3.3.1 Phase-Coupled Ligators / 73
3.3.2 Off-Axis Bonds and Interactions with Nonbonding
Electron Pairs / 74
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
CONTENTS XI
4 THE ORIGIN AND CALCULATION OF A 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
5.3.1 d1 / 98
5.3.2 d2 / 99
5.3.3 d3-d9 / 101
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
6.1.1 S Terms / 113
6.1.2 P Terms / 113
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
6.7.1 d1, d9: Any Stereochemistry / 127
6.7.2 d2 (Oh), d8 (Td) / 127
6.7.3 d2(Td),d8(Oh) / 127
6.7.4 d3 (Oh), d7 (Td) / 127
6.7.5 d3 (Td). d7 (Oh) / 127
6.7.6 d4 (Oh), d6 (Td) / 128
6.7.7 d4 (Td), d6 (Oh) / 129
6.7.8 d5(OhandTd) / 130
XÜ CONTENTS
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
7.1.1 Nondegenerate Electronic States / 146
7.1.2 Degenerate States: The Jahn-Teller Effect / 148
7.1.3 Bond Length Differences Between High- and
Low-spin Complexes / 160
7.1.4 Variation of Bond Lengths on Crossing the Transition
Series / 163
7.2 Dependence of the Stability of a Complex on Its
d Configuration / 166
7.2.1 Thermodynamic Effects / 167
7.2.2 Kinetic Effects / 176
8 THE ELECTRONIC SPECTRA OF COMPLEXES 179
8.1 Important Features of Electronic Spectra / 179
8.1.1 Band Intensities / 179
8.1.2 Band Energies / 189
8.1.3 Band Widths and Shapes / 195
8.1.4 Effect of Temperature on Electronic Bands / 201
8.2 Characteristic Spectra of Complexes of First-Row Transition
Ions / 204
8.2.1 Hexaaqua Complexes of First-Row Ions / 204
8.2.2 Tetrahedral and Planar Complexes of First-Row
Transition Ions / 211
8.3 Typical Spectra of Second- and Third-Row Transition Ions / 214
8.4 The Spectrochemical and Nephelauxetic Series / 215
8.4.1 The Spectrochemical Series / 215
8.4.2 The Nephelauxetic Series / 218
8.5 Charge Transfer Spectra / 221
8.6 Luminescence Spectra / 224
9 MAGNETIC PROPERTIES OF COMPLEX IONS 228
9.1 The Theory of Magnetic Susceptibility / 228
9.1.1 General / 228
contents xiii
9.1.2 Paramagnetism / 232
9.1.3 Quantum Mechanical Treatment of Paramagnetic
Susceptibilities / 233
9.2 The Magnetic Properties of Free Ions / 237
9.2.1 The First-Order Zeeman Effect / 237
9.2.2 The Second-Order Zeeman Effect / 238
9.2.3 States ~*T / 239
9.2.4 States £T / 241
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
9.5.1 Splitting by Spin-Orbit Coupling / 248
9.5.2 The Calculation of/ieff / 251
9.5.3 Departure from Cubic Symmetry / 254
9.6 t2(g) Electron Derealization / 256
9.6.1 General / 256
9.6.2 A and E Terms / 257
9.6.3 T Terms / 259
9.7 The Magnetic Properties of Complexes with A and E Ground
Terms / 259
9.7.1 Octahedral Complexes / 259
9.7.2 Tetrahedral Complexes / 261
9.8 The Magnetic Properties of Complexes with T Ground
Terms / 264
9.8.1 d 2T2g/264
9.8.2 d2,3T,g / 265
9.8.3 d4, 3Tig / 266
9.8.4 d5,2T2g / 267
9.8.5 d6,5T2g / 268
9.8.6 d7, 4T2g / 268
9.8.7 d8,3T, / 268
9.9 Summary / 268
9.10 Spin-Free-Spin-Paired Equilibria / 269
9.11 Magnetic Exchange / 272
9.11.1 The Heisenberg Hamiltonian / 272
9.11.2 Mechanism of Magnetic Exchange:
Superexchange / 273
9.11.3 Some Examples of Superexchange in Clusters / 277
XIV contents
10 ELECTRON PARAMAGNETIC RESONANCE SPECTRA OF
COMPLEXES 282
10.1 Nature of the EPR Experiment / 282
10.1.1 Introduction / 282
10.1.2 Features of EPR Spectra / 284
10.2 The Spin Hamiltonian / 294
10.3 Interpretation of the Spin Hamiltonian Parameters / 296
10.3.1 The g Tensor / 296
10.3.2 The Hyperfine Tensor / 301
10.3.3. The Zero-Field Splitting Tensor / 308
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^ / 315
11.4 Uv/vis Spectra of Actinide Complexes / 317
11.5 Magnetic Properties of Actinide Complexes / 319
11.5.1 f ,2F2i / 319
11.5.2 f2, 3H4 / 322
11.5.3 f3, 5I4i / 323
11.5.4 f4tof7 / 323
APPENDIX A1 325
Al.l The Spherical Harmonics Yf I 325
A1.2 Integration of Products of Spherical Harmonics / 325
APPENDIX A2 328
A2.1 The Associated Legendre Polynomials S™ to
Order 6 / 328
APPENDIX A3 330
A3.1 The Energies Resulting from the Application of Vtrig / 330
APPENDIX A4 331
A4.1 Relationships Between Some of the Coefficients in the
Operators Defined in Section 2.8.1 / 331
contents xv
APPENDIX A5 332
A5.1 Matrix Elements of the Crystal Field Potential Vcf from a
General Distribution of Effective Point Charges / 332
APPENDIX A6 334
A6.1 Energies of the Terms of d using Condon-Shortley
Parameters / 334
APPENDIX A7 336
A7.1 The Curie Law for Magnetic Behavior / 336
APPENDIX A8 337
A8.1 The Operators Lx, Ly, Sx, and Sv / 337
APPENDIX A9 339
A9.1 Expressions for the Magnetic Moments of 4T,(g), 2T2(g), and 5T2(g)
Terms in Cubic Symmetry / 339
LIST OF COMMONLY USED SYMBOLS 340
FUNDAMENTAL CONSTANTS 342
INDEX 345
|
| any_adam_object | 1 |
| author | Figgis, Brian N. Hitchman, Michael A. |
| author_facet | Figgis, Brian N. Hitchman, Michael A. |
| author_role | aut aut |
| author_sort | Figgis, Brian N. |
| author_variant | b n f bn bnf m a h ma mah |
| building | Verbundindex |
| bvnumber | BV012999050 |
| callnumber-first | Q - Science |
| callnumber-label | QD475 |
| callnumber-raw | QD475 |
| callnumber-search | QD475 |
| callnumber-sort | QD 3475 |
| callnumber-subject | QD - Chemistry |
| classification_rvk | UP 3500 VE 5720 |
| ctrlnum | (OCoLC)246125379 (DE-599)BVBBV012999050 |
| dewey-full | 541.2242 |
| dewey-hundreds | 500 - Natural sciences and mathematics |
| dewey-ones | 541 - Physical chemistry |
| dewey-raw | 541.2242 |
| dewey-search | 541.2242 |
| dewey-sort | 3541.2242 |
| dewey-tens | 540 - Chemistry and allied sciences |
| discipline | Chemie / Pharmazie Physik |
| format | Book |
| fullrecord | <?xml version="1.0" encoding="UTF-8"?><collection xmlns="http://www.loc.gov/MARC21/slim"><record><leader>01472nam a2200385 c 4500</leader><controlfield tag="001">BV012999050</controlfield><controlfield tag="003">DE-604</controlfield><controlfield tag="005">20050831 </controlfield><controlfield tag="007">t</controlfield><controlfield tag="008">000222s2000 ad|| |||| 00||| eng d</controlfield><datafield tag="020" ind1=" " ind2=" "><subfield code="a">0471317764</subfield><subfield code="9">0-471-31776-4</subfield></datafield><datafield tag="035" ind1=" " ind2=" "><subfield code="a">(OCoLC)246125379</subfield></datafield><datafield tag="035" ind1=" " ind2=" "><subfield code="a">(DE-599)BVBBV012999050</subfield></datafield><datafield tag="040" ind1=" " ind2=" "><subfield code="a">DE-604</subfield><subfield code="b">ger</subfield><subfield code="e">rakwb</subfield></datafield><datafield tag="041" ind1="0" ind2=" "><subfield code="a">eng</subfield></datafield><datafield tag="049" ind1=" " ind2=" "><subfield code="a">DE-355</subfield><subfield code="a">DE-20</subfield><subfield code="a">DE-703</subfield><subfield code="a">DE-384</subfield><subfield code="a">DE-11</subfield></datafield><datafield tag="050" ind1=" " ind2="0"><subfield code="a">QD475</subfield></datafield><datafield tag="082" ind1="0" ind2=" "><subfield code="a">541.2242</subfield></datafield><datafield tag="084" ind1=" " ind2=" "><subfield code="a">UP 3500</subfield><subfield code="0">(DE-625)146383:</subfield><subfield code="2">rvk</subfield></datafield><datafield tag="084" ind1=" " ind2=" "><subfield code="a">VE 5720</subfield><subfield code="0">(DE-625)147120:253</subfield><subfield code="2">rvk</subfield></datafield><datafield tag="100" ind1="1" ind2=" "><subfield code="a">Figgis, Brian N.</subfield><subfield code="e">Verfasser</subfield><subfield code="4">aut</subfield></datafield><datafield tag="245" ind1="1" ind2="0"><subfield code="a">Ligand field theory and its applications</subfield><subfield code="c">Brian N. Figgis ; Michael A. Hitchman</subfield></datafield><datafield tag="264" ind1=" " ind2="1"><subfield code="a">New York [u.a.]</subfield><subfield code="b">Wiley-VCH</subfield><subfield code="c">2000</subfield></datafield><datafield tag="300" ind1=" " ind2=" "><subfield code="a">XVIII, 354 S.</subfield><subfield code="b">Ill., graph. Darst.</subfield></datafield><datafield tag="336" ind1=" " ind2=" "><subfield code="b">txt</subfield><subfield code="2">rdacontent</subfield></datafield><datafield tag="337" ind1=" " ind2=" "><subfield code="b">n</subfield><subfield code="2">rdamedia</subfield></datafield><datafield tag="338" ind1=" " ind2=" "><subfield code="b">nc</subfield><subfield code="2">rdacarrier</subfield></datafield><datafield tag="490" ind1="0" ind2=" "><subfield code="a">Special topics in inorganic chemistry</subfield></datafield><datafield tag="650" ind1=" " ind2="7"><subfield code="a">Química de coordenação</subfield><subfield code="2">larpcal</subfield></datafield><datafield tag="650" ind1="0" ind2="7"><subfield code="a">Ligandenfeldtheorie</subfield><subfield code="0">(DE-588)4167657-9</subfield><subfield code="2">gnd</subfield><subfield code="9">rswk-swf</subfield></datafield><datafield tag="689" ind1="0" ind2="0"><subfield code="a">Ligandenfeldtheorie</subfield><subfield code="0">(DE-588)4167657-9</subfield><subfield code="D">s</subfield></datafield><datafield tag="689" ind1="0" ind2=" "><subfield code="5">DE-604</subfield></datafield><datafield tag="700" ind1="1" ind2=" "><subfield code="a">Hitchman, Michael A.</subfield><subfield code="e">Verfasser</subfield><subfield code="4">aut</subfield></datafield><datafield tag="856" ind1="4" ind2="2"><subfield code="m">HBZ Datenaustausch</subfield><subfield code="q">application/pdf</subfield><subfield code="u">http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=008858447&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA</subfield><subfield code="3">Inhaltsverzeichnis</subfield></datafield><datafield tag="999" ind1=" " ind2=" "><subfield code="a">oai:aleph.bib-bvb.de:BVB01-008858447</subfield></datafield></record></collection> |
| id | DE-604.BV012999050 |
| illustrated | Illustrated |
| indexdate | 2024-07-09T18:37:30Z |
| institution | BVB |
| isbn | 0471317764 |
| language | English |
| oai_aleph_id | oai:aleph.bib-bvb.de:BVB01-008858447 |
| oclc_num | 246125379 |
| open_access_boolean | |
| owner | DE-355 DE-BY-UBR DE-20 DE-703 DE-384 DE-11 |
| owner_facet | DE-355 DE-BY-UBR DE-20 DE-703 DE-384 DE-11 |
| physical | XVIII, 354 S. Ill., graph. Darst. |
| publishDate | 2000 |
| publishDateSearch | 2000 |
| publishDateSort | 2000 |
| publisher | Wiley-VCH |
| record_format | marc |
| series2 | Special topics in inorganic chemistry |
| spelling | Figgis, Brian N. Verfasser aut Ligand field theory and its applications Brian N. Figgis ; Michael A. Hitchman New York [u.a.] Wiley-VCH 2000 XVIII, 354 S. Ill., graph. Darst. txt rdacontent n rdamedia nc rdacarrier Special topics in inorganic chemistry Química de coordenação larpcal Ligandenfeldtheorie (DE-588)4167657-9 gnd rswk-swf Ligandenfeldtheorie (DE-588)4167657-9 s DE-604 Hitchman, Michael A. Verfasser aut HBZ Datenaustausch application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=008858447&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis |
| spellingShingle | Figgis, Brian N. Hitchman, Michael A. Ligand field theory and its applications Química de coordenação larpcal Ligandenfeldtheorie (DE-588)4167657-9 gnd |
| subject_GND | (DE-588)4167657-9 |
| title | Ligand field theory and its applications |
| title_auth | Ligand field theory and its applications |
| title_exact_search | Ligand field theory and its applications |
| title_full | Ligand field theory and its applications Brian N. Figgis ; Michael A. Hitchman |
| title_fullStr | Ligand field theory and its applications Brian N. Figgis ; Michael A. Hitchman |
| title_full_unstemmed | Ligand field theory and its applications Brian N. Figgis ; Michael A. Hitchman |
| title_short | Ligand field theory and its applications |
| title_sort | ligand field theory and its applications |
| topic | Química de coordenação larpcal Ligandenfeldtheorie (DE-588)4167657-9 gnd |
| topic_facet | Química de coordenação Ligandenfeldtheorie |
| url | http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=008858447&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA |
| work_keys_str_mv | AT figgisbriann ligandfieldtheoryanditsapplications AT hitchmanmichaela ligandfieldtheoryanditsapplications |