Mossbauer Spectroscopy
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VIRENDER K. SHARMA received his Ph.D. in?Marine and Atmospheric Chemistry at the Florida Insitute of Technology after graduating from the Indian Institute of Technology in New Delhi, India with the Master in Technology.?He?is?currently?Professor of Chemistry at F.I.T. He was a visiting research scholar at Stanford University under the advisory of Professor Ed Solomon and won both the?ACS Faculty of the Year award in 2008 and the?Orlando Section Outstanding Chemist Award.?His research interests include the study of kinetics and mechanisms of oxidations by transition metals in higher oxidation states in aqueous solution, development of innovative and effective methods for reducing the level of contaminants in the aquatic environment, and the physical chemistry of natural waters.
GOESTER KLINGELHOEFER is a professor?of inorganic and analytical chemistry and the University of Mainz, Germany.
TETSUAKI NISHIDA is professor of chemistry at?Kinki University, Japan.
Content
Preface xix
Contributors xxi Chapter 1 In-Situ Mössbauer Spectroscopy with Synchrotron Radiation on Thin Films 3 S Stankov, T Slezak, M Zajac, M Slezak, M Sladecek, R Röhlsberger, B. Sepiol, G Vogl, N Spiridis, J Lazewski, K Parlinski, and J Korecki
1 1 Introduction 3
1.2 Instrumentation 4
1.3 Synchrotron radiation-based Mössbauer techniques 10
References 39
Chapter 2 Mössbauer Spectroscopy in Studying Electronic Spin and Valence States of Ironin the Earth's Lower Mantle 43 Jung-Fu Lin, Zhu Mao, and Ercan E Alp
2.1 Introduction 43
2.2 Synchrotron Mössbauer Spectroscopy at High Pressures and Temperatures 44
2.3 Crystal Field Theory on the 3d Electronic States 46
2.4 Conclusion 54
Acknowledgments 55
References 55
Chapter 3 In-beam Mössbauer Spectroscopy Using a Radioisotope Beam and a Neutron Capture Reaction 58 Yoshio Kobayashi
3.1 Introduction 58
3.2 57Mn (¿ 57Fe) Implantation Mössbauer Spectroscopy 61
3.3 Neutron in-beam Mössbauer Spectroscopy 66
3 .4 Summary 66
References 67
Part II Radionuclides 71
Chapter 4 Lanthanides(151Eu and 155Gd)-Mössbauer Spectroscopic Study of Defect-FluoriteOxides Coupled with New Defect-Crystal-Chemistry Model 73 Nakamura, N Igawa, Y Okamoto, Y Hinatsu, J, Wang, M Takahashi and M. Takeda
4.1 Introduction 73
4.2 Defect-crystal-Chemistry (DCC) Lattice-parameter Model 76
4.3 Lns Mössbauer and Lattice-parameter Data of DF Oxides 79
4.4 DCC-Model Lattice-parameter and Lns-Mössbauer Data Analysis 84
Conclusion 92
References 93
Chapter 5 Mössbauer and Magnetic Study of Neptunyl(+1) Complexes 95 T Nakamoto, A Nakamura and M Takeda
5.1 Introduction 95
5.2 237Np Mössbauer Spectroscopy 96
5.3 Magnetic Property of Neptunyl Monocation (NpO2+) 97
5.4 Mössbauer and Magnetic Study of Neptunyl(+1) Complexes 98
5.5 Discussion 106
Conclusion 113
Acknowledgment 113
References 113
Chapter 6 Mössbauer Spectroscopy of 161Dy in Dysprosium Dicarboxylates 116 M Takahashi, C I Wynter, B R Hillery, Virender K Sharma, D Quarless, Leopold May, T Misu, S G Sobel, M Takeda, and E Brown
6.1 Introduction 116
6.2 Experimental Methods 117
6.3 Results and Discussion 117
Acknowledgment 122
References 122
Chapter 7 Study of Exotic Uranium Compounds using 238U Mössbauer Spectroscopy 123 Satoshi Tsutsui1,2and Masami Nakada2
7.1 Introduction 123
7.2 Determination of Nuclear g-factor in the Excited State of 238U Nuclei 125
7.3 Application of 238U Mössbauer Spectroscopy to Heavy Fermion 127
7.4 Application to Two-dimensional (2D) Fermi Surface System of Uranium Dipnictides 134
Summary 137
Acknowledgment 138
References 138
Part III Spin Dynamics 141
Chapter 8 Reversible Spin-state Switching Involving a Structural Change 143 Satoru Nakashima
8.1 Introduction 143
8.2 Three Assembled Structures of Fe(NCX)2(bpa)2 (X=S, Se) and Their Structural Change by Desorption of Propanol Molecules 144
8.3 Occurrence of Spin-crossover Phenomenon in Assembled Complexes Fe(NCX)2(bpa)2 (X=S, Se, BH3) by Enclathrating Guest Molecules 145
8.4 Reversible Structural Change of Host Framework of Fe(NCS)2(bpp)2.2(benzene) Triggered By Sorption of Benzene Molecules 147
8.5 Reversible Spin-state Switching Involving a Structural Change of Fe(NCX)2(bpp)2.2(benzene) (X=Se, BH3) Triggered By Sorption of Benzene Molecules 149
8.6 Conclusion 150
References 151
Chapter 9 Spin- Crossover and Related Phenomena Coupled with Spin, Photon and Charge 152 N Kokima and A Sugahara
9.1 Introduction 152
9.2 Photo-induced Spin-crossover Phenomena 153
9 3 Charge Transfer Phase Transition 161
9 4 Spin Equilibrium and Succeeding Phenomena 168
References 175
Chapter 10 Spin Crossover in Iron(III) Porphyrins Involving the Intermediate-Spin State 177 Mikio Nakamura and Masashi Takahashi
10.1 Introduction 177
10.2 Methodology to Obtain Pure Intermediate-Spin Complexes 178
10.3 Spin Crossover Involving the Intermediate-Spin State 189
10.4 Spin Crossover Triangle in Iron(III) Porphyrins 195
10.5 Conclusion 198
Acknowledgments 198
References 199
Chapter 11 Tin(II) Lone Pair Stereoactivity: Influence on Structures and Properties, and Mössbauer Spectroscopic Properties 202 Georges Dénès, M Cecilia Madamba, Hocine Merazigand Abdualhafed Muntasar
11.1 Introduction 202
11.2 Experimental 203
11.3 Crystal Structures 204
11.4 Tin Electronic Structure and Mössbauer Spectroscopy 208
11.5 Application to the Structural Determination of a-SnF2 213
11.6 Application to the Structural Determination of the Highly Layered Structures of a-PbSnF4 and BaSnF4 216
11.7 Application to the Structural Study of Disordered Phases 226
11.8 Lone Pair Stereoactivity and Material Properties 241
11.9 Conclusion 242
Acknowledgments 243
References 243
Part IV Biological Applications 247
Chapter 12 Synchrotron Radiation Based Nuclear Resonant Scattering: Applications to Bioinorganic Chemistry 249 Yisong Guo, Yoshitaka Yoda, Xiaowei Zhang, Yuming Xiao, Stephen P Cram
12.1 Introduction 249
12.2 Technical Background 250
12.3 Applications in Bioinorganic Chemistry 258
12.4 Summary and Prospects 269
Acknowledgment 269
References 269
Chapter 13 Mössbauer Spectroscopy in Biological and Biomedical Research 272 Alexander A Kamnev1,*, Krisztina Kovács2, Irina V Alenkina3, and Michael I. Oshtrakh
13.1 Introduction 272
13.2 Microorganisms-related studies 273
13.3 Plants 276
13.4 Enzymes 280
13.5 Hemogoblin 281
13.6 Ferritin and Hemosiderin 283
13.7 Tissues 284
13.8 Pharmaceutical Products 286
13.9 Conclusions 286
Acknowledgments 287
References 287
Chapter 14 Controlled Spontaneous Decay of Mossbauer Nuclei (Theory and Experiments) 292 Vladimir I Vysotskii and Alla A Kornilova
14.1 Introduction to the Problem of Controlled Spontaneous Gamma-decay 292
14.2 General Consideration 293
14.3 Controlled Spontaneous Gamma-decay of Excited Nucleus in the System of Mutually Uncorrelated Modes of Electromagnetic Vacuum 295
14.4 Spontaneous Gamma-decay in the System of Synchronized Modes of Electromagnetic Vacuum 302
14.5 Experimental Study of the Phenomenon of Controlled Gamma-decay of Mossbauer Nuclei 303
14.6 Experimental Study of the Phenomenon of Controlled Gamma-decay by Investigation of Space Anisotropy and Self-focusing of Mossbauer Radiation 309
14.7 Direct Experimental Observation and Study of the Process of Controlled Radioactive and Excited Nuclei Radiative Gamma-decay by the Delayed Gamma-gamma Coincidence Method 311
14.8 Conclusion 314
References 314
Chapter 15 Natural's Strategy to Oxidize Tryptophan: EPR and Mossbauer Characterization of High-Valent Fe Intermediates 315 Kednerlin Dornevil and Aimin Liu
15.1 Two Oxidizing Equivalents Stored at a Ferric Heme 315
15.2 Oxidation of L-Tryptophan by Heme-Based Enzymes 316
15.3 The Chemical Reaction Catalyzed by MauG 318
15.4 A High-Valent bis-Fe(IV) Intermediate in MauG 319
15.5 High-Valent Fe Intermediate of Tryptophan 2,3-Dioxygenase 319
15.6 Concluding Remarks 321
References 322
Chapter 16 Iron in Neurodegeneration 324 Jolanta Galazka-Friedman, Erika R Bauminger, and Andrzej Friedman
16.1 Introduction 324
16.2 Neurodegeneration and Oxidative Stress 324
16.3 Mössbauer Studies of Healthy Brain Tissue 325
16.4 Properties of Ferritin and Hemosiderin Present in Healthy Brain Tissue 327
16.5 Concentration of Iron Present in Healthy and Diseased Brain Issue 328
16.6 Asymmetry of the Mössbauer Spectra of Healthy and Diseased Brain Tissue 330
16.7 Conclusion - the Possible Role of Iron in Neurodegeneration 331
References 331
Chapter 17 Emission (57Co) Mössbauer Spectroscopy: Biology-related Applications, Potentials and Prospects 333 Alexander A Kamnev
17.1 Introduction 333
17.2 Methodology 334
17.3 Microbiological Applications 336
17.4 Enzymological Applications 340
17.5 Conclusions and Outlook 345
Acknowledgments 345
References 346
Part V Iron Oxides 349
Chapter 18 Mossbauer Spectroscopy in Study of Nanocrystalline Iron Oxides from Thermal Processes 351 Jirí Tucek, Libor Machala, Jirí Frydrych, Jirí PechouSek, and Radek Zboril
18.1 Introduction 351
18.2 Polymorphs of Iron (III) Oxide, Their Crystal Structures, Magnetic Properties, and Polymorphous Phase Transformations 352
18.3 Use of 57Fe Mössbauer Spectroscopy in Monitoring Solid State Reaction Mechanisms towards Iron Oxides 371
18.4 Various Mössbauer Spectroscopy Techniques in Study of Applications Related to Nanocrystalline Iron Oxides 378
18.5 Conclusion 389
Acknowledgment 389
References 389
Chapter 19 Transmission and Emission 57Fe Mössbauer Studies on Perovskites and Related Oxide Systems 393 Zoltán Homonnay and Zoltán Németh
19.1 Introduction 393
19.2 Study of high-Tc superconductors 394
19.3 Study of Strontium ferrate and its substituted analogues 401
19.4 Pursuing Colossal Magnetoresistance in Doped Lanthanum Cobaltates 407
References 413
Chapter 20 Enhancing the Possibilities of 57Fe Mössbauer Spectrometry to Study the Inherent Properties of Rust Layers 415 Karen E García, César A Barrero, Alvaro L Morales, and Jean-Marc Greneche
20.1 Introduction 415
20.2 Mössbauer Characterization of Some Iron Phases Presented in the Rust Layers 416
20.3 Determining Inherent Properties of Rust Layers by Mössbauer Spectrometry 421
20.4 Final Remarks 426
Acknowledgments 426
References 426
Chapter 21 Application of Mössbauer Spectroscopy in Nanomagnetics 429 Lakshmi Nambakkat
21.1 Introduction 429
21.2 Spinel Ferrites 430
21.3 Nano Sized Fe-Al Alloys Synthesized by High Energy Ball Milling 441
21.4 Magnetic Thin Films/Multilayer Systems: 57Fe/Al MLS 446
Conclusion 452
Acknowledgment 453
References 453
Chapter 22 Mössbauer Spectroscopy and Surface Analysis 455 José F Marco, J Ramón Gancedo, Matteo Monti and Juan de la Figuera
22.1 Introduction 455
22.2 The Physical Basis: How and Why Electrons Appear in Mössbauer Spectroscopy 456
22.3 Increasing Surface Sensitivity in Electron Mössbauer Spectroscopy 458
22.4 The Practical Way: Experimental Low Energy Electron Mössbauer Spectroscopy 460
22.5 Mössbauer Surface Imaging Techniques 465
22.6 Recent Surface Mössbauer Studies in an "ancient" Material: Fe3O4 466
Acknowledgments 468
References 468
Chapter 23 57Fe Mössbauer Spectroscopy in the Investigation of the Precipitation of Iron Oxides 470 Svetozar Music, Mira Ristic, and Stjepko Krehula
23.1 Introduction 470
23.2 Complexation of Iron Ions by Hydrolysis 470
23.3 Precipitation of Iron Oxides by Hydrolysis Reactions 472
23.4 Precipitation of Iron Oxides from Dense -FeOOH Suspensions 480
23.5 Precipitation and Properties of Some Other Iron Oxides 483
23.6 Influence of Cations on the Precipitation of Iron Oxides 490
Acknowledgment 496
References 497
Chapter 24 Ferrates (IV, V, and VI): Mössbauer Spectroscopy Characterization 505 Virender K Sharma, Yurii Perfiliev, Radek Zboril, Libor Machala, and Clive Wynter
24.1 Introduction 505
24.2 Spectroscopic Characterization 506
24.3 Mössbauer Spectroscopy Characterization 508
Acknowledgments 517
References 517
Chapter 25 Characterization of Dilute Iron-Doped Yttrium Aluminum Garnets by Mössbauer Spectrometry 521 Kiyoshi Nomura and Zoltán Németh
25.1 Introduction 521
25.2 Sample Preparations by sol-gel Method 523
25.3 X-ray Diffraction and EXAFS Analysis 523
25.4 Magnetic Properties 525
25.5 Mössbauer Analysis of YAG Doped with Dilute Iron 526
25.6 Micro-discharge Treatment of Iron Doped YAG 528
Conclusion 531
Acknowledgment 532
References 532
Part VI Industrial Applications 533
Chapter 26 Some Mössbauer Studies of Fe-As Based High Temperature Superconductors 535 Amar Nath and Airat Khasanov
26.1 Introduction 535
26.2 Experimental 535
26.3 Where Do the Injected Electrons Go? 537
26.4 New Electron-rich Species in Ni-doped Single Crystals: Is it Superconducting? 538
26.5 Can O2 play an Important Role? 539
Acknowledgment 541
References 541
Chapter 27 Mossbauer Study of New Electrically Conductive Glass 542 Tetsuaki Nishida and Shiro Kubuki
27.1 Introduction 542
27.2 Structural Relaxation of Electrically Conductive Vanadate Glass 544
Acknowledgments 551
References 551
Chapter 28 Applications of Mössbauer Spectroscopy in the Study of Lithium Battery Materials 552 Ricardo Alcántara, Pedro Lavela, Carlos Pérez Vicente, José L Tirado
28.1 Introduction 552
28.2 Cathode Materials for Li-ion Batteries 554
28.3 Anode Materials for Li-ion Batteries 556
Conclusions 561
Acknowledgment 561
References 562
Chapter 29 Mössbauer Spectroscopic Investigations of Novel Bimetal Catalysts for Preferential CO Oxidation in H2 564 Wansheng Zhang, Junhu Wang, Kuo Liu, Jie Jin, and Tao Zhang
29.1 Introduction 564
29.2 Experimental Section 564
29.3 Results and Discussion 565
Conclusion 574
Acknowledgments 574
References 575
Chapter 30 The use of Mossbauer Spectroscopy in Coal Research-Is it Relevant or Not? 576 F B Waanders
30.1 Introduction 576
30.2 Experimental Procedures 577
30.3 Results and Discussion 578
Conclusions 590
References 591
Part VII Environmental Applications 593
Chapter 31 Water Purification and Characterization of Recycled Iron-Silicate Glass 595 Shiro Kubuki and Tetsuaki Nishida
31.1 Introduction 595
31.2 Property and Structure of Recycled Silicate Glasses 596
31.3 Summary 605
Reference 606
Chapter 32 Mössbauer Spectroscopy in the Study of Laterite Mineral Processing 608 Eamonn Devlin, Michail Samouhos, Charalabos Zografidis
32.1 Introduction 608
32.2 Conventional Processing 609
32.3 Microwave Processing 612
Reference 619 Index 621
