Mössbauer Spectroscopy
Applications in Chemistry, Biology, and Nanotechnology

Preface xix

Contributors xxi

Chapter 1In-Situ Mössbauer Spectroscopy with Synchrotron Radiation on Thin Films 3
S Stankov, T Ślęzak, M Zając, M Ślęzak, M Sladecek, R Röhlsberger, B. Sepiol, G Vogl, N Spiridis, J Łażewski, K Parliński, 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 6Mössbauer 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 Tsutsui^1,2and 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 IIISpin 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 α−SnF₂ 213     

11.6 Application to the Structural Determination of the Highly Layered Structures of α−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 Kamnev^1,*, 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 Gałązka-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
Jiří Tuček, Libor Machala, Jiří Frydrych, Jiří Pechoušek, and Radek Zbořil

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-T_c 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 Musić, Mira Ristić, 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 Applications593

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

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.