Mössbauer Spectroscopy

VIRENDER K. SHARMA received his Ph.D. in Marine and Atmospheric Chemistry at the Florida Institute 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.

• Preface xixContributors xxiChapter 1 In-Situ Mössbauer Spectroscopy with Synchrotron Radiation on Thin Films 3S Stankov, T Ślęzak, M Zając, M Ślęzak, M Sladecek, R Röhlsberger, B. Sepiol, G Vogl, N Spiridis, J Łażewski, K Parliński, and J Korecki1 1 Introduction 31.2 Instrumentation 41.3 Synchrotron radiation-based Mössbauer techniques 10References 39Chapter 2 Mössbauer Spectroscopy in Studying Electronic Spin and Valence States of Ironin the Earth’s Lower Mantle 43Jung-Fu Lin, Zhu Mao, and Ercan E Alp2.1 Introduction 432.2 Synchrotron Mössbauer Spectroscopy at High Pressures and Temperatures 442.3 Crystal Field Theory on the 3d Electronic States 462.4 Conclusion 54Acknowledgments 55References 55Chapter 3 In-beam Mössbauer Spectroscopy Using a Radioisotope Beam and a Neutron Capture Reaction 58Yoshio Kobayashi3.1 Introduction 583.2 57Mn (→ 57Fe) Implantation Mössbauer Spectroscopy 613.3 Neutron in-beam Mössbauer Spectroscopy 663 .4 Summary 66References 67Part II Radionuclides 71Chapter 4 Lanthanides(151Eu and 155Gd)-Mössbauer Spectroscopic Study of Defect-FluoriteOxides Coupled with New Defect-Crystal-Chemistry Model 73Nakamura, N Igawa, Y Okamoto, Y Hinatsu, J, Wang, M Takahashi and M. Takeda4.1 Introduction 734.2 Defect-crystal-Chemistry (DCC) Lattice-parameter Model 764.3 Lns Mössbauer and Lattice-parameter Data of DF Oxides 794.4 DCC-Model Lattice-parameter and Lns-Mössbauer Data Analysis 84Conclusion 92References 93Chapter 5 Mössbauer and Magnetic Study of Neptunyl(+1) Complexes 95T Nakamoto, A Nakamura and M Takeda5.1 Introduction 955.2 237Np Mössbauer Spectroscopy 965.3 Magnetic Property of Neptunyl Monocation (NpO2+) 975.4 Mössbauer and Magnetic Study of Neptunyl(+1) Complexes 985.5 Discussion 106Conclusion 113Acknowledgment 113References 113Chapter 6 Mössbauer Spectroscopy of 161 Dy in Dysprosium Dicarboxylates 116M Takahashi, C I Wynter, B R Hillery, Virender K Sharma, D Quarless, Leopold May, T Misu, S G Sobel, M Takeda, and E Brown6.1 Introduction 1166.2 Experimental Methods 1176.3 Results and Discussion 117Acknowledgment 122References 122Chapter 7 Study of Exotic Uranium Compounds using 238U Mössbauer Spectroscopy 123Satoshi Tsutsui 1,2 and Masami Nakada 27.1 Introduction 1237.2 Determination of Nuclear g-factor in the Excited State of 238U Nuclei 1257.3 Application of 238U Mössbauer Spectroscopy to Heavy Fermion 1277.4 Application to Two-dimensional (2D) Fermi Surface System of Uranium Dipnictides 134Summary 137Acknowledgment 138References 138Part III Spin Dynamics 141Chapter 8 Reversible Spin-state Switching Involving a Structural Change 143Satoru Nakashima8.1 Introduction 1438.2 Three Assembled Structures of Fe(NCX)2(bpa)2 (X=S, Se) and Their Structural Change by Desorption of Propanol Molecules 1448.3 Occurrence of Spin-crossover Phenomenon in Assembled Complexes Fe(NCX)2(bpa)2 (X=S, Se, BH3) by Enclathrating Guest Molecules 1458.4 Reversible Structural Change of Host Framework of Fe(NCS)2(bpp)2•2(benzene) Triggered By Sorption of Benzene Molecules 1478.5 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 1498.6 Conclusion 150References 151Chapter 9 Spin- Crossover and Related Phenomena Coupled with Spin, Photon and Charge152N Kokima and A Sugahara9.1 Introduction 1529.2 Photo-induced Spin-crossover Phenomena 1539 3 Charge Transfer Phase Transition 1619 4 Spin Equilibrium and Succeeding Phenomena 168References 175Chapter 10 Spin Crossover in Iron(III) Porphyrins Involving the Intermediate-Spin State 177Mikio Nakamura and Masashi Takahashi10.1 Introduction 17710.2 Methodology to Obtain Pure Intermediate-Spin Complexes 17810.3 Spin Crossover Involving the Intermediate-Spin State 18910.4 Spin Crossover Triangle in Iron(III) Porphyrins 19510.5 Conclusion 198Acknowledgments 198References 199Chapter 11 Tin(II) Lone Pair Stereoactivity: Influence on Structures and Properties, and Mössbauer Spectroscopic Properties 202Georges Dénès, M Cecilia Madamba, Hocine Merazigand Abdualhafed Muntasar11.1 Introduction  20211.2 Experimental 20311.3 Crystal Structures 20411.4 Tin Electronic Structure and Mössbauer Spectroscopy 20811.5 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 BaSnF421611.7 Application to the Structural Study of Disordered Phases 22611.8 Lone Pair Stereoactivity and Material Properties 24111.9 Conclusion 242Acknowledgments 243References 243Part IV Biological Applications 247Chapter 12 Synchrotron Radiation Based Nuclear Resonant Scattering: Applications to Bioinorganic Chemistry 249Yisong Guo, Yoshitaka Yoda, Xiaowei Zhang, Yuming Xiao, Stephen P Cram12.1 Introduction 24912.2 Technical Background 25012.3 Applications in Bioinorganic Chemistry 25812.4 Summary and Prospects 269Acknowledgment 269References 269Chapter 13 Mössbauer Spectroscopy in Biological and Biomedical Research 272Alexander A Kamnev1,*, Krisztina Kovács2, Irina V Alenkina3, and Michael I. Oshtrakh13.1 Introduction 27213.2 Microorganisms-related studies 27313.3 Plants 27613.4 Enzymes 28013.5 Hemogoblin 28113.6 Ferritin and Hemosiderin 28313.7 Tissues 28413.8 Pharmaceutical Products 28613.9 Conclusions 286Acknowledgments 287References 287Chapter 14 Controlled Spontaneous Decay of Mossbauer Nuclei (Theory and Experiments) 292Vladimir I Vysotskii and Alla A Kornilova14.1 Introduction to the Problem of Controlled Spontaneous Gamma-decay 29214.2 General Consideration 29314.3 Controlled Spontaneous Gamma-decay of Excited Nucleus in the System of Mutually Uncorrelated Modes of Electromagnetic Vacuum 29514.4 Spontaneous Gamma-decay in the System of Synchronized Modes of Electromagnetic Vacuum 30214.5 Experimental Study of the Phenomenon of Controlled Gamma-decay of Mossbauer Nuclei 30314.6 Experimental Study of the Phenomenon of Controlled Gamma-decay by Investigation of Space Anisotropy and Self-focusing of Mossbauer Radiation 30914.7 Direct Experimental Observation and Study of the Process of Controlled Radioactive and Excited Nuclei Radiative Gamma-decay by the Delayed Gamma-gamma Coincidence Method 31114.8 Conclusion 314References 314Chapter 15 Natural's Strategy to Oxidize Tryptophan: EPR and Mossbauer Characterization of High-Valent Fe Intermediates 315Kednerlin Dornevil and Aimin Liu15.1 Two Oxidizing Equivalents Stored at a Ferric Heme 31515.2 Oxidation of L-Tryptophan by Heme-Based Enzymes 31615.3 The Chemical Reaction Catalyzed by MauG 31815.4 A High-Valent bis-Fe(IV) Intermediate in MauG 31915.5 High-Valent Fe Intermediate of Tryptophan 2,3-Dioxygenase 31915.6 Concluding Remarks 321References 322Chapter 16 Iron in Neurodegeneration 324Jolanta Gałązka-Friedman, Erika R Bauminger, and Andrzej Friedman16.1 Introduction 32416.2 Neurodegeneration and Oxidative Stress 32416.3 Mössbauer Studies of Healthy Brain Tissue 32516.4 Properties of Ferritin and Hemosiderin Present in Healthy Brain Tissue 32716.5 Concentration of Iron Present in Healthy and Diseased Brain Issue 32816.6 Asymmetry of the Mössbauer Spectra of Healthy and Diseased Brain Tissue 33016.7 Conclusion – the Possible Role of Iron in Neurodegeneration 331References 331Chapter 17 Emission (57Alexander A Kamnev17.1 Introduction 33317.2 Methodology 33417.3 Microbiological Applications 33617.4 Enzymological Applications 34017.5 Conclusions and Outlook 345Acknowledgments 345References 346Part V Iron Oxides 349Chapter 18 Mossbauer Spectroscopy in Study of Nanocrystalline Iron Oxides from Thermal Processes 351Jiří Tuček, Libor Machala, Jiří Frydrych, Jiří Pechoušek, and Radek Zbořil18.1 Introduction 35118.2 Polymorphs of Iron (III) Oxide, Their Crystal Structures, Magnetic Properties, and Polymorphous Phase Transformations 35218.3 Use of 57Fe Mössbauer Spectroscopy in Monitoring Solid State Reaction Mechanisms towards Iron Oxides 37118.4 Various Mössbauer Spectroscopy Techniques in Study of Applications Related to Nanocrystalline Iron Oxides 37818.5 Conclusion 389Acknowledgment 389References 389Chapter 19 Transmission and Emission 57Fe Mössbauer Studies on Perovskites and Related Oxide Systems 393Zoltán Homonnay and Zoltán Németh19.1 Introduction 39319.2 Study of high-Tc superconductors 39419.3 Study of Strontium ferrate and its substituted analogues 40119.4 Pursuing Colossal Magnetoresistance in Doped Lanthanum Cobaltates 407References 413Chapter 20 Enhancing the Possibilities of 57Fe Mössbauer Spectrometry to Study the Inherent Properties of Rust Layers 415Karen E García, César A Barrero, Alvaro L Morales, and Jean-Marc Greneche20.1 Introduction 41520.2 Mössbauer Characterization of Some Iron Phases Presented in the Rust Layers 41620.3 Determining Inherent Properties of Rust Layers by Mössbauer Spectrometry 42120.4 Final Remarks 426Acknowledgments 426References 426Chapter 21 Application of Mössbauer Spectroscopy in Nanomagnetics 429Lakshmi Nambakkat21.1 Introduction 42921.2 Spinel Ferrites 43021.3 Nano Sized Fe-Al Alloys Synthesized by High Energy Ball Milling 44121.4 Magnetic Thin Films/Multilayer Systems: 57Fe/Al MLS 446Conclusion 452Acknowledgment 453References 453Chapter 22 Mössbauer Spectroscopy and Surface Analysis 455José F Marco, J Ramón Gancedo, Matteo Monti and Juan de la Figuera22.1 Introduction 45522.2 The Physical Basis: How and Why Electrons Appear in Mössbauer Spectroscopy 45622.3 Increasing Surface Sensitivity in Electron Mössbauer Spectroscopy 45822.4 The Practical Way: Experimental Low Energy Electron Mössbauer Spectroscopy 46022.5 Mössbauer Surface Imaging Techniques 46522.6 Recent Surface Mössbauer Studies in an "ancient" Material: Fe3O4 466Acknowledgments 468References 468Chapter 23 57Fe Mössbauer Spectroscopy in the Investigation of the Precipitation of Iron Oxides470Svetozar Musić, Mira Ristić, and Stjepko Krehula23.1 Introduction 47023.2 Complexation of Iron Ions by Hydrolysis 47023.3 Precipitation of Iron Oxides by Hydrolysis Reactions 47223.4 Precipitation of Iron Oxides from Dense -FeOOH Suspensions 48023.5 Precipitation and Properties of Some Other Iron Oxides 48323.6 Influence of Cations on the Precipitation of Iron Oxides 490Acknowledgment 496References 497Chapter 24 Ferrates (IV, V, and VI): Mössbauer Spectroscopy Characterization 505Virender K Sharma, Yurii Perfiliev, Radek Zboril, Libor Machala, and Clive Wynter24.1 Introduction 50524.2 Spectroscopic Characterization 50624.3 Mössbauer Spectroscopy Characterization 508Acknowledgments 517References 517Chapter 25 Characterization of Dilute Iron-Doped Yttrium Aluminum Garnets by Mössbauer Spectrometry 521Kiyoshi Nomura and Zoltán Németh25.1 Introduction 52125.2 Sample Preparations by sol-gel Method 52325.3 X-ray Diffraction and EXAFS Analysis 52325.4 Magnetic Properties 52525.5 Mössbauer Analysis of YAG Doped with Dilute Iron 52625.6 Micro-discharge Treatment of Iron Doped YAG 528Conclusion 531Acknowledgment 532References 532Part VI Industrial Applications 533Chapter 26 Some Mössbauer Studies of Fe-As Based High Temperature Superconductors 535Amar Nath and Airat Khasanov26.1 Introduction 53526.2 Experimental 53526.3 Where Do the Injected Electrons Go? 53726.4 New Electron-rich Species in Ni-doped Single Crystals: Is it Superconducting? 53826.5 Can O2 play an Important Role? 539Acknowledgment 541References 541Chapter 27 Mossbauer Study of New Electrically Conductive Glass 542Tetsuaki Nishida and Shiro Kubuki27.1 Introduction 54227.2 Structural Relaxation of Electrically Conductive Vanadate Glass 544Acknowledgments 551References 551Chapter 28 Applications of Mössbauer Spectroscopy in the Study of Lithium Battery Materials 552Ricardo Alcántara, Pedro Lavela, Carlos Pérez Vicente, José L Tirado28.1 Introduction 55228.2 Cathode Materials for Li-ion Batteries 55428.3 Anode Materials for Li-ion Batteries 556Conclusions 561Acknowledgment 561References 562Chapter 29 Mössbauer Spectroscopic Investigations of Novel Bimetal Catalysts for Preferential CO Oxidation in H2  564Wansheng Zhang, Junhu Wang, Kuo Liu, Jie Jin, and Tao Zhang29.1 Introduction 56429.2 Experimental Section 56429.3 Results and Discussion 565Conclusion 574Acknowledgments 574References 575Chapter 30 The use of Mossbauer Spectroscopy in Coal Research-Is it Relevant or Not? 576F B Waanders30.1 Introduction 57630.2 Experimental Procedures 57730.3 Results and Discussion 578Conclusions 590References 591Part VII Environmental Applications 593Chapter 31 Water Purification and Characterization of Recycled Iron-Silicate Glass 595Shiro Kubuki and Tetsuaki Nishida31.1 Introduction 59531.2 Property and Structure of Recycled Silicate Glasses 59631.3 Summary 605Reference 606Chapter 32 Mössbauer Spectroscopy in the Study of Laterite Mineral Processing 608Eamonn Devlin, Michail Samouhos, Charalabos Zografidis32.1 Introduction 60832.2 Conventional Processing 60932.3 Microwave Processing 612Reference 619Index 621