30
M€OSSBAUER SPECTROSCOPY
M€OSSBAUER SPECTROSCOPY
APPLICATIONS IN CHEMISTRY,BIOLOGY, AND NANOTECHNOLOGY
Edited by
Virender K. Sharma, Ph.D.Göstar Klingelhöfer
Tetsuaki Nishida
Copyright� 2013 by John Wiley & Sons, Inc. All rights reserved.
Published by John Wiley & Sons, Inc., Hoboken, New Jersey.
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Library of Congress Cataloging-in-Publication Data:
M€ossbauer spectroscopy : applications in chemistry, biology, industry, and nanotechnology / [edited by] Virender K. Sharma, Ph.D.,
G€ostar Klingelh€ofer, Tetsuaki Nishida.
pages cm
Includes bibliographical references and index.
ISBN 978-1-118-05724-7 (hardback)
1. M€ossbauer spectroscopy. I. Sharma, Virender K., editor of compilation. II. Klingelh€ofer, G€ostar, 1956- editor of compilation.
III. Nishida, Tetsuaki, 1950- editor of compilation.
QD96.M6M638 2014
5430 .6–dc23 2013011056
Printed in the United States of America
10 9 8 7 6 5 4 3 2 1
We dedicate this book to the late Professor Attila Vertez,E€otv€os Lor�and University, Budapest, Hungary
Contents
Preface xix
Contributors xxi
Part I Instrumentation 1
Chapter 1 | In Situ M€ossbauer Spectroscopy with Synchrotron Radiationon Thin Films 3Svetoslav Stankov, Tomasz �Slezak, Marcin Zajac, Michał �Slezak, Marcel Sladecek, Ralf R€ohlsberger,Bogdan Sepiol, Gero Vogl, Nika Spiridis, Jan Ła _zewski, Krzysztof Parli�nski, and J�ozef Korecki
1.1 Introduction 31.2 Instrumentation 4
1.2.1 Nuclear Resonance Beamline ID18 at the ESRF 51.2.2 The UHV System for In Situ Nuclear Resonant Scattering Experiments
at ID18 of the ESRF 61.3 Synchrotron Radiation-Based M€ossbauer Techniques 10
1.3.1 Coherent Elastic Nuclear Resonant Scattering 101.3.2 Coherent Quasielastic Nuclear Resonant Scattering 251.3.3 Incoherent Inelastic Nuclear Resonant Scattering 30
1.4 Conclusions 38Acknowledgments 39References 39
Chapter 2 | M€ossbauer Spectroscopy in Studying Electronic Spin and ValenceStates of Iron in the Earth’s Lower Mantle 43Jung-Fu Lin, Zhu Mao, and Ercan E. Alp
2.1 Introduction 432.2 Synchrotron M€ossbauer Spectroscopy at High Pressures and
Temperatures 442.3.1 Crystal Field Theory on the 3d Electronic States 462.3.2 Electronic Spin Transition of Fe2þ in Ferropericlase 472.3.3 Spin and Valence States of Iron in Silicate Perovskite 492.3.4 Spin and Valence States of Iron in Silicate Postperovskite 52
2.4 Conclusions 54Acknowledgments 55References 55
Chapter 3 | In-Beam M€ossbauer Spectroscopy Using a Radioisotope Beam anda Neutron Capture Reaction 58Yoshio Kobayashi
3.1 Introduction 583.2 57Mn (!57Fe) Implantation M€ossbauer Spectroscopy 61
3.2.1 In-Beam M€ossbauer Spectrometer 613.2.2 Detector for 14.4 keV M€ossbauer g-Rays 623.2.3 Application to Materials Science—Ultratrace of Fe Atoms in Si
and Dynamic Jumping 62
vii
3.2.4 Application to Inorganic Chemistry 633.2.5 Development of M€ossbauer g-Ray Detector 65
3.3 Neutron In-Beam M€ossbauer Spectroscopy 663.4 Summary 66References 67
Part II Radionuclides 71
Chapter 4 | Lanthanides (151Eu and 155Gd) M€ossbauer Spectroscopic Studyof Defect-Fluorite Oxides Coupled with New Defect CrystalChemistry Model 73Akio Nakamura, Naoki Igawa, Yoshihiro Okamoto, Yukio Hinatsu, Junhu Wang,Masashi Takahashi, and Masuo Takeda
4.1 Introduction 734.2 Defect Crystal Chemistry (DCC) Lattice Parameter Model 764.3 Lns-M€ossbauer and Lattice Parameter Data of DF Oxides 79
4.3.1 151Eu-M€ossbauer and Lattice Parameter Data of M-Eus (M4þ¼Zr, Hf, Ce, U,and Th) 79
4.3.2 155Gd-M€ossbauer and Lattice Parameter Data of Zr1�yGdyO2�y/2 804.4 DCC Model Lattice Parameter and Lns-M€ossbauer Data Analysis 84
4.4.1 DCC Model Lattice Parameter Data Analysis of Ce–Eu and Th–Eu 854.4.2 Quantitative BL(Eu3þ��O)-Composition (y) Curves in Zr–Eu and Hf–Eu 884.4.3 Model Extension Attempt from Macroscopic Lattice Parameter Side 89
4.5 Conclusions 92References 93
Chapter 5 | M€ossbauer and Magnetic Study of Neptunyl(þ1) Complexes 95Tadahiro Nakamoto, Akio Nakamura, and Masuo Takeda
5.1 Introduction 955.2 237Np M€ossbauer Spectroscopy 965.3 Magnetic Property of Neptunyl Monocation (NpO2
þ) 975.4 M€ossbauer and Magnetic Study of Neptunyl(þ1) Complexes 98
5.4.1 (NH4)[NpO2(O2CH)2] (1) 985.4.2 [NpO2(O2CCH2OH)(H2O)] (2) 1005.4.3 [NpO2(O2CH)(H2O)] (3) 1015.4.4 [(NpO2)2((O2C)2C6H4)(H2O)3]�H2O (4) 104
5.5 Discussion 1065.5.1 237Np M€ossbauer Relaxation Spectra 1065.5.2 Magnetic Susceptibility and Saturation Moment: Averaged Powder Magnetization
for the Ground Jz ¼ �4j i Doublet 1075.6 Conclusion 113Acknowledgment 113References 113
Chapter 6 | M€ossbauer Spectroscopy of 161Dy in Dysprosium Dicarboxylates 116Masashi Takahashi, Clive I. Wynter, Barbara R. Hillery, Virender K. Sharma, Duncan Quarless,Leopold May, Toshiyuki Misu, Sabrina G. Sobel, Masuo Takeda, and Edward Brown
6.1 Introduction 1166.2 Experimental Methods 1176.3 Results and Discussion 117Acknowledgment 122References 122
viii CONTENTS
Chapter 7 | Study of Exotic Uranium Compounds Using 238U M€ossbauerSpectroscopy 123Satoshi Tsutsui and Masami Nakada
7.1 Introduction 1237.2 Determination of Nuclear g-Factor in the Excited State of 238U Nuclei 125
7.2.1 Background of 238U M€ossbauer Spectroscopy and Its Applicationto Magnetism in Uranium Compounds 125
7.2.2 238U M€ossbauer and 235U NMR Measurements of UO2 in theAntiferromagnetic State 125
7.2.3 Determination of the Nuclear g-Factor in the First ExcitedState of 238U 127
7.3 Application of 238U M€ossbauer Spectroscopy to Heavy FermionSuperconductors 1277.3.1 Introduction of Uranium-Based Heavy Fermion Superconductors 1277.3.2 Magnetic Ordering and Paramagnetic Relaxation in Heavy Fermion
Superconductors 1297.3.3 Summary of 238U M€ossbauer Spectroscopy of Uranium-Based
Heavy Fermion Superconductors 1337.4 Application to Two-Dimensional (2D) Fermi Surface System of Uranium
Dipnictides 1347.4.1 Introduction of Uranium Dipnictides 1347.4.2 Hyperfine Interactions Correlated with the Magnetic Structures in Uranium
Dipnictides 1357.4.3 Summary of 238U M€ossbauer Spectroscopy of Uranium Dipnictides 137
7.5 Summary 137Acknowledgments 138References 138
Part III Spin Dynamics 141
Chapter 8 | Reversible Spin-State Switching Involving a Structural Change 143Satoru Nakashima
8.1 Introduction 1438.2 Three Assembled Structures of Fe(NCX)2(bpa)2 (X¼S, Se) and Their
Structural Change by Desorption of Propanol Molecules [23] 1448.3 Occurrence of Spin-Crossover Phenomenon in Assembled
Complexes Fe(NCX)2(bpa)2 (X¼S, Se, BH3) by EnclathratingGuest Molecules [25–27] 145
8.4 Reversible Structural Change of Host Framework of Fe(NCS)2(bpp)2�2(Benzene) Triggered by Sorption of Benzene Molecules [29] 147
8.5 Reversible Spin-State Switching Involving a Structural Changeof Fe(NCX)2(bpp)2�2(Benzene) (X¼Se, BH3) Triggered by Sorptionof Benzene Molecules [30] 149
8.6 Conclusions 150References 151
Chapter 9 | Spin-Crossover and Related Phenomena Coupled with Spin,Photon, and Charge 152Norimichi Kojima and Akira Sugahara
9.1 Introduction 1529.2 Photoinduced Spin-Crossover Phenomena 153
9.2.1 LIESST for Fe(II) Complexes 153
CONTENTS ix
9.2.2 LIESST for Fe(III) Complexes 1579.2.3 Recent Topics of Photoinduced Spin-Crossover Phenomena 160
9.3 Charge Transfer Phase Transition 1619.3.1 Thermally Induced Charge Transfer Phase Transition 1619.3.2 Photoinduced Charge Transfer Phase Transition 164
9.4 Spin Equilibrium and Succeeding Phenomena 1689.4.1 Rapid Spin Equilibrium in Solid State 1689.4.2 Concerted Phenomenon Coupled with Spin Equilibrium and Valence
Fluctuation 173References 175
Chapter 10 | Spin Crossover in Iron(III) Porphyrins Involving theIntermediate-Spin State 177Mikio Nakamura and Masashi Takahashi
10.1 Introduction 17710.2 Methodology to Obtain Pure Intermediate-Spin Complexes 178
10.2.1 Saddled Deformation 17810.2.2 Ruffled Deformation 18210.2.3 Core Modification 184
10.3 Spin Crossover Involving the Intermediate-Spin State 18910.3.1 Spin Crossover Between S¼ 3/2 and S¼ 1/2 18910.3.2 Spin Crossover Between S¼ 3/2 and S¼ 5/2 192
10.4 Spin-Crossover Triangle in Iron(III) Porphyrin Complexes 19510.5 Conclusions 198Acknowledgments 198References 199
Chapter 11 | Tin(II) Lone Pair Stereoactivity: Influence on Structures andProperties and M€ossbauer Spectroscopic Properties 202Georges D�en�es, Abdualhafed Muntasar, M. Cecilia Madamba, and Hocine Merazig
11.1 Introduction 20211.2 Experimental Aspects 203
11.2.1 Sample Preparation 20311.3 Crystal Structures 204
11.3.1 The Fluorite-Type Structure: A Typically Ionic Structure 20411.3.2 Tin(II) Fluoride: Covalent Bonding and Polymeric Structure 20511.3.3 The a-PbSnF4 Structure: The Unexpected Combination of Ionic
Bonding and Covalent Bonding 20711.3.4 The PbClF-Type Structure: An Ionic Structure and a Tetragonal Distortion
of the Fluorite Type 20711.4 Tin Electronic Structure and M€ossbauer Spectroscopy 208
11.4.1 Tin Electronic Structure, Bonding Type, and Coordination 20811.4.2 Using M€ossbauer Spectroscopy to Probe the Tin Electronic Structure
and Bonding Mode 21111.5 Application to the Structural Determination of a-SnF2 213
11.5.1 History 21311.5.2 Using 119Sn M€ossbauer Spectroscopy to Determine that the Tin Positions
Used by Bergerhoff Were Incorrect 21411.6 Application to the Structural Determination of the Highly Layered
Structures of a-PbSnF4 and BaSnF4 21611.6.1 History 21611.6.2 Unit Cell of MSnF4 and Relationships with the Fluorite-Type MF2 217
x CONTENTS
11.6.3 M€ossbauer Spectroscopy, Bonding Type, Crystal Symmetry, and PreferredOrientation 220
11.6.4 Combining All the Results: The a-PbSnF4 Structural Type 22511.7 Application to the Structural Study of Disordered Phases 226
11.7.1 Disordered Fluoride Phases 22611.7.2 Disordered Chloride Fluoride Phases 232
11.8 Lone Pair Stereoactivity and Material Properties 24111.9 Conclusions 242Acknowledgments 243References 243
Part IV Biological Applications 247
Chapter 12 | Synchrotron Radiation-Based Nuclear Resonant Scattering:Applications to Bioinorganic Chemistry 249Yisong Guo, Yoshitaka Yoda, Xiaowei Zhang, Yuming Xiao, and Stephen P. Cramer
12.1 Introduction 24912.2 Technical Background 250
12.2.1 Theoretical Aspects of NFS 25012.2.2 Theoretical Aspects of SRPAC 25212.2.3 Experimental Aspects of NFS and SRPAC 255
12.3 Applications in Bioinorganic Chemistry 25812.3.1 Nuclear Forward Scattering 25812.3.2 SRPAC 264
12.4 Summary and Prospects 269Acknowledgments 269References 269
Chapter 13 | M€ossbauer Spectroscopy in Biological and Biomedical Research 272Alexander A. Kamnev, Krisztina Kov�acs, Irina V. Alenkina, and Michael I. Oshtrakh
13.1 Introduction 27213.2 Microorganisms-Related Studies 27313.3 Plants 27613.4 Enzymes 28013.5 Hemoglobin 28113.6 Ferritin and Hemosiderin 28313.7 Tissues 28413.8 Pharmaceutical Products 28613.9 Conclusions 286Acknowledgments 287References 287
Chapter 14 | Controlled Spontaneous Decay of M€ossbauer Nuclei(Theory and Experiments) 292Vladimir I. Vysotskii and Alla A. Kornilova
14.1 Introduction to the Problem of Controlled Spontaneous Gamma Decay 29214.2 The Theory of Controlled Radiative Gamma Decay 293
14.2.1 General Consideration 29314.3 Controlled Spontaneous Gamma Decay of Excited Nucleus in the System
of Mutually Uncorrelated Modes of Electromagnetic Vacuum 29514.3.1 Spontaneous Gamma Decay in the Case of Free Space 29614.3.2 Spontaneous Gamma Decay of Excited Nuclei in the Case of Screen
Presence 298
CONTENTS xi
14.4 Spontaneous Gamma Decay in the System of SynchronizedModes of Electromagnetic Vacuum 302
14.5 Experimental Study of the Phenomenon of Controlled Gamma Decayof M€ossbauer Nuclei 30314.5.1 Investigation of the Phenomenon of Controlled Gamma Decay by Analysis of
Deformation of M€ossbauer Gamma Spectrum 30314.6 Experimental Study of the Phenomenon of Controlled Gamma Decay
by Investigation of Space Anisotropy and Self-Focusing ofM€ossbauer Radiation 309
14.7 Direct Experimental Observation and Study of the Process of ControlledRadioactive and Excited Nuclei Radiative Gamma Decay by the DelayedGamma–Gamma Coincidence Method 311
14.8 Conclusions 314References 314
Chapter 15 | Nature’s Strategy for Oxidizing Tryptophan: EPR and M€ossbauerCharacterization of the Unusual High-Valent Heme Fe Intermediates 315Kednerlin Dornevil and Aimin Liu
15.1 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 A High-Valent Fe Intermediate of Tryptophan 2,3-Dioxygenase 32015.6 Concluding Remarks 321References 322
Chapter 16 | Iron in Neurodegeneration 324Jolanta Gałazka-Friedman, Erika R. Bauminger, and Andrzej Friedman
16.1 Introduction 32416.2 Neurodegeneration and Oxidative Stress 32416.3 M€ossbauer 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 Tissue:
Labile Iron 32816.6 Asymmetry of the M€ossbauer Spectra of Healthy and Diseased
Brain Tissue 33016.7 Conclusion: The Possible Role of Iron in Neurodegeneration 331References 331
Chapter 17 | Emission (57Co) M€ossbauer Spectroscopy: Biology-Related Applications,Potentials, and Prospects 333Alexander A. Kamnev
17.1 Introduction 33317.2 Methodology 33417.3 Microbiological Applications 33617.4 Enzymological Applications 340
17.4.1 Choosing a Test Object 34017.4.2 Prerequisites for Using the 57Co EMS Technique 34217.4.3 Experimental 57Co EMS Studies 34217.4.4 Two-Metal-Ion Catalysis: Competitive Metal Binding at the Active Centers 34417.4.5 Possibilities of 57Co Substitution for Other Cations in Metalloproteins 345
17.5 Conclusions and Outlook 345Acknowledgments 345References 346
xii CONTENTS
Part V Iron Oxides 349
Chapter 18 | M€ossbauer Spectroscopy in Study of Nanocrystalline Iron Oxidesfrom Thermal Processes 351Ji9r�ı Tu9cek, Libor Machala, Ji9r�ı Frydrych, Ji9r�ı Pechou9sek, and Radek Zbo9ril
18.1 Introduction 35118.2 Polymorphs of Iron(III) Oxide, Their Crystal Structures, Magnetic
Properties, and Polymorphous Phase Transformations 35218.2.1 a-Fe2O3 35318.2.2 b-Fe2O3 35818.2.3 g-Fe2O3 36018.2.4 e-Fe2O3 36418.2.5 Amorphous Fe2O3 369
18.3 Use of 57Fe M€ossbauer Spectroscopy in Monitoring Solid-StateReaction Mechanisms Toward Iron Oxides 37118.3.1 Thermal Decomposition of Ammonium Ferrocyanide—A Valence Change
Mechanism 37118.3.2 Thermal Decomposition of Prussian Blue in Air 37418.3.3 Thermal Conversion of Fe2(SO4)3 in Air—Polymorphous Exhibition of Fe2O3 37618.3.4 Nanocrystalline Fe2O3 Catalyst from FeC2O4�2H2O 376
18.4 Various M€ossbauer Spectroscopy Techniques in Study of ApplicationsRelated to Nanocrystalline Iron Oxides 37818.4.1 57Fe Transmission M€ossbauer Spectroscopy at Various Temperatures 37818.4.2 In-Field 57Fe Transmission M€ossbauer Spectroscopy 37918.4.3 In Situ High-Temperature 57Fe Transmission M€ossbauer Spectroscopy 38118.4.4 57Fe Conversion Electron and Conversion X-Ray M€ossbauer Spectroscopy 383
18.5 Conclusions 389Acknowledgments 389References 389
Chapter 19 | Transmission and Emission 57Fe M€ossbauer Studies on Perovskitesand Related Oxide Systems 393Zolt�an Homonnay and Zolt�an N�emeth
19.1 Introduction 39319.2 Study of High-TC Superconductors 394
19.2.1 Study of 57Co-Doped YBa2Cu3O7�d 39519.2.2 Study of 57Co-Doped Y1�xPrxBa2Cu3O7�d 397
19.3 Study of Strontium Ferrate and Its Substituted Analogues 40119.3.1 Study of Sr0.95Ca0.05Co0.5Fe0.5O3�d and Sr0.5Ca0.5Co0.5Fe0.5O3�d 401
19.4 Pursuing Colossal Magnetoresistance in Doped Lanthanum Cobaltates 40719.4.1 Emission M€ossbauer Study of La0.8Sr0.2CoO3�d Perovskites 40819.4.2 Emission and Transmission M€ossbauer Study of Iron-Doped
La0.8Sr0.2FeyCo1�yO3�d Perovskites 411References 413
Chapter 20 | Enhancing the Possibilities of 57Fe M€ossbauer Spectrometryto Study the Inherent Properties of Rust Layers 415Karen E. Garc�ıa, C�esar A. Barrero, Alvaro L. Morales, and Jean-Marc Greneche
20.1 Introduction 41520.2 M€ossbauer Characterization of Some Iron Phases Presented in the Rust
Layers 41620.2.1 Akaganeite 416
CONTENTS xiii
20.2.2 Goethite 41820.2.3 Magnetite/Maghemite 420
20.3 Determining Inherent Properties of Rust Layers by M€ossbauerSpectrometry 42120.3.1 Rust Layers in Steels Submitted to Total Immersion Tests 42120.3.2 Rust Layers in Steels Submitted to Dry–Wet Cycles 42420.3.3 Rust Layers in Steels Submitted to Outdoor Tests 426
20.4 Final Remarks 426Acknowledgments 426References 426
Chapter 21 | Application of M€ossbauer Spectroscopy to Nanomagnetics 429Lakshmi Nambakkat
21.1 Introduction 42921.2 Spinel Ferrites 430
21.2.1 Microstructure Determination 43021.2.2 Elucidation of Bulk Magnetic Properties in Nanoferrites Using In-Field M€ossbauer
Spectroscopy 43421.2.3 Core–Shell Effect on the Magnetic Properties in Superparamagnetic
Nanosystems 43621.3 Nanosized Fe–Al Alloys Synthesized by High-Energy Ball Milling 441
21.3.1 Nanosized Al–1 at% Fe 44221.4 Magnetic Thin Films/Multilayer Systems: 57Fe/AI MLS 446
21.4.1 Structural Characterization 44721.4.2 DC Magnetization Studies 44821.4.3 M€ossbauer (CEMS) Study 451
21.5 Conclusions 452Acknowledgments 453References 453
Chapter 22 | M€ossbauer Spectroscopy and Surface Analysis 455Jos�e F. Marco, Jos�e Ram�on Gancedo, Matteo Monti, and Juan de La Figuera
22.1 Introduction 45522.2 The Physical Basis: How and Why Electrons Appear in M€ossbauer
Spectroscopy 45622.3 Increasing Surface Sensitivity in Electron M€ossbauer Spectroscopy 45822.4 The Practical Way: Experimental Low-Energy Electron M€ossbauer
Spectroscopy 46022.5 M€ossbauer Surface Imaging Techniques 46522.6 Recent Surface M€ossbauer Studies in an “Ancient” Material:
Fe3O4 466Acknowledgment 468References 468
Chapter 23 | 57Fe M€ossbauer Spectroscopy in the Investigation of thePrecipitation of Iron Oxides 470Svetozar Musi�c, Mira Risti�c, and Stjepko Krehula
23.1 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 b-FeOOH
Suspensions 480
xiv CONTENTS
23.5 Precipitation and Properties of Some Other Iron Oxides 48323.5.1 Ferrihydrite 48323.5.2 Lepidocrocite (g-FeOOH) 48523.5.3 Magnetite (Fe3O4) and Maghemite (g-Fe2O3) 487
23.6 Influence of Cations on the Precipitation of Iron Oxides 49023.6.1 Goethite 49023.6.2 Hematite 49523.6.3 Magnetite and Maghemite 496
Acknowledgment 496References 497
Chapter 24 | Ferrates(IV, V, and VI): M€ossbauer Spectroscopy Characterization 505Virender K. Sharma, Yurii D. Perfiliev, Radek Zbo9ril, Libor Machala, and Clive I. Wynter
24.1 Introduction 50524.2 Spectroscopic Characterization 50624.3 M€ossbauer Spectroscopy Characterization 508
24.3.1 Ferryl(IV) Ion 50824.3.2 Ferrates(IV, V, and VI) 51024.3.3 Case Studies 513
Acknowledgments 517References 517
Chapter 25 | Characterization of Dilute Iron-Doped Yttrium AluminumGarnets by M€ossbauer Spectrometry 521Kiyoshi Nomura and Zolt�an N�emeth
25.1 Introduction 52125.2 Sample Preparations by the Sol–Gel Method 52325.3 X-Ray Diffraction and EXAFS Analysis 52325.4 Magnetic Properties 52525.5 M€ossbauer Analysis of YAG Doped with Dilute Iron 52625.6 Microdischarge Treatment of Iron-Doped YAG 52825.7 Conclusions 531Acknowledgments 532References 532
Part VI Industrial Applications 533
Chapter 26 | Some M€ossbauer Studies of Fe–As-BasedHigh-Temperature Superconductors 535Amar Nath and Airat Khasanov
26.1 Introduction 53526.2 Experimental Procedure 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 541
Chapter 27 | M€ossbauer Study of New Electrically Conductive Oxide Glass 542Tetsuaki Nishida and Shiro Kubuki
27.1 Introduction 54227.1.1 Electrically Conductive Oxide Glass 54227.1.2 Cathode Active Material for Lithium-Ion Battery (LIB) 543
CONTENTS xv
27.2 Structural Relaxation of Electrically Conductive Vanadate Glass 54427.2.1 Increase in the Electrically Conductivity of Vanadate Glass 54427.2.2 Cathode Active Material for Li-Ion Battery (LIB) 547
27.3 Summary 551Acknowledgments 551References 551
Chapter 28 | Applications of M€ossbauer Spectroscopy in the Study of LithiumBattery Materials 552Ricardo Alc�antara, Pedro Lavela, Carlos P�erez Vicente, and Jos�e L. Tirado
28.1 Introduction 55228.2 Cathode Materials for Li-Ion Batteries 554
28.2.1 Layered Intercalation Electrodes 55428.2.2 Phosphate Electrodes with Olivine Structure 55428.2.3 Insertion Silicate Electrodes 555
28.3 Anode Materials for Li-Ion Batteries 55628.3.1 Conversion Oxides 55628.3.2 Tin Alloys and Intermetallic Compounds 55828.3.3 Antimony Alloys and Intermetallic Compounds 560
28.4 Conclusions 561Acknowledgments 561References 562
Chapter 29 | M€ossbauer Spectroscopic Investigations of Novel Bimetal Catalystsfor Preferential CO Oxidation in H2 564Wansheng Zhang, Junhu Wang, Kuo Liu, Jie Jin, and Tao Zhang
29.1 Introduction 56429.2 Experimental Section 564
29.2.1 Catalyst Preparation 56429.2.2 Catalytic Activity Test 56529.2.3 M€ossbauer Spectra Characterization 565
29.3 Results and Discussion 56529.3.1 PtFe Alloy Nanoparticles Catalyst 56529.3.2 Ir–Fe/SiO2 Catalyst 567
29.4 Conclusions 574Acknowledgments 574References 575
Chapter 30 | The Use of M€ossbauer Spectroscopy in Coal Research: Is It Relevantor Not? 576Frans B. Waanders
30.1 Introduction 57630.2 Experimental Procedures 577
30.2.1 M€ossbauer Spectroscopy 57730.2.2 SEM Analyses 57730.2.3 XRD Analyses 57730.2.4 Samples and Sample Preparation 577
30.3 Results and Discussion 57830.3.1 M€ossbauer Analyses of the As-Mined Samples 57830.3.2 Weathering of Coal 57830.3.3 Corrosion of Mild Steel Due to the Presence of Compacted Fine Coal 58330.3.4 Coal Combustion 58430.3.5 Coal Gasification and Resultant Products 587
xvi CONTENTS
30.4 Conclusions 590Acknowledgments 591References 591
Part VII Environmental Applications 593
Chapter 31 | Water Purification and Characterization of RecycledIron-Silicate Glass 595Shiro Kubuki and Tetsuaki Nishida
31.1 Introduction 59531.1.1 Water-Purifying Ability of Recycled Iron Silicate Glass 59531.1.2 Iron Silicate Glass Prepared by Recycling Coal Ash 596
31.2 Properties and Structure of Recycled Silicate Glasses 59631.2.1 Water-Purifying Ability of Recycled Silicate Glasses 59631.2.2 Electromagnetic Property of Recycled Silicate Glasses 601
31.3 Summary 60531.3.1 Water-Purifying Ability of Recycled Silicate Glasses 60531.3.2 Electromagnetic Property of Recycled Silicate Glasses 606
References 606
Chapter 32 | M€ossbauer Spectroscopy in the Study of Laterite Mineral Processing 608Eamonn Devlin, Michail Samouhos, and Charalabos Zografidis
32.1 Introduction 60832.2 Conventional Processing 60932.3 Microwave Processing 612References 619
Index 621
CONTENTS xvii
Preface
Five decades ago, theM€ossbauer conceptwas invented. Since then the M€ossbauer spectroscopy has been applied in a widerange of fields including physics, chemistry, biology, and nanotechnology. The M€ossbauer spectroscopy is still beingapplied vigorously in understanding the hyperfine interactions of electromagnetic nature. This is evident from a similarnumber of publications on the M€ossbauer concept (�14,000/decade) in the last three decades. This book presents thecurrent knowledge on the applications of M€ossbauer spectroscopy. With this theme in the minds of editors, manyexperts were invited to contribute to the book on the use of the M€ossbauer effect in a number of subject areas. Theeditors also made sure that the contributors were from almost every region of the world (i.e., North America, SouthAmerica, Europe, Africa, and Asia) in order to cover different aspects of the M€ossbauer spectroscopy.
In Chapters 1 and 2, an introduction is made to the synchrotron M€ossbauer spectroscopy with examples. Examplesinclude the in situM€ossbauer spectroscopy with synchrotron radiation on thin films and the study of deep-earth minerals.Investigations of in-beam M€ossbauer spectroscopy using a 57Mn beam at the RIKEN RIBF is presented in Chapter 3. Thischapter demonstrates innovative experimental setup for online M€ossbauer spectroscopy using the thermal neutroncapture reaction, 56Fe (n, g) 57Fe. The M€ossbauer spectroscopy of radionuclides is described in Chapters 4–7. Chapter 4gives full description of the latest analysis results of lanthanides (151Eu and 155Gd) M€ossbauer structure and powder X-raydiffraction (XRD) lattice parameter (a0) data of defect fluorite (DF) oxides with the new defect crystal chemistry (DCC)a0 model. Chapter 5 reviews the 237Np M€ossbauer and magnetic study of neptunyl(þ1) complexes, while Chapter 6describes the M€ossbauer spectroscopy of organic complexes of europium and dysprosium. 238U M€ossbauer spectros-copy is presented in Chapter 7. There are three chapters on spin-state switching/spin-crossover phenomena (Chapter 8–10). Examples in these chapters are mainly on iron compounds, such as iron(III) porphyrins. The use of M€ossbauerspectroscopy of physical properties of Sn(II) is discussed in Chapter 11.
Chapters 12–17 are devoted to applications of the M€ossbauer spectroscopy to the biological chemistry. Chapter 12details the recent progress on the application of 57Fe NFS, 57Fe SRPAC, and 61Ni SRPAC to bioinorganic chemistry. Thefuture prospect of these techniques is also given. The role of M€ossbauer spectroscopy in biological and biomedicalresearch is described in Chapters 13 and 17. These chapters demonstrate how M€ossbauer spectroscopy can be appliedto study microorganisms, plants, tissues, enzymes, hemoglobin, ferritin, and hemosiderin. Chapter 15 deals with theM€ossbauer characterization of high-valent iron intermediates in the oxidation of L-tryptophan by heme-based enzymes.Chapter 16 is focused on the use of M€ossbauer spectroscopy to study iron in neurodegenerative diseases.
Recent advances on studying iron and iron oxides using M€ossbauer spectroscopy are described in Chapters 18–25.Chapter 18 discusses the nanocrystalline iron oxides, while Chapter 19 presents perovskite-related systems whereemission M€ossbauer spectroscopy contributes to exploring the structure and electronic or magnetic behavior of thesematerials. The use of 57Fe M€ossbauer spectrometry to study iron phases in rust layers is described in Chapter 20. Theprogress made on understanding bulk magnetic properties of nanosized powders of ferrites, mechanically alloyed/milledFe–Cr–Al intermetallics, and a Fe–Al multilayer system is presented in Chapter 21. The application of surface M€ossbauerspectroscopy to study very thin layers (a few atomic layers thick) of iron oxides is discussed in Chapter 22. Chapter 23describes in detail the precipitation of iron oxides from aqueous iron salt solutions using M€ossbauer spectroscopy.Chapter 24 is focused on the spectroscopic characterization of ferrates in high-valent oxidation states (þ4,þ5, andþ6).Chapter 25 deals with dilute iron-doped yttrium aluminum garnets.
M€ossbauer spectroscopy of materials of industrial interest is discussed in Chapters 26–30. Chapter 26 deals with Fe–As-based high-temperature superconductors. M€ossbauer study of cathode active material for lithium-ion battery (LIB)and electrically conductive vanadate glass is presented in Chapter 27. More details on the applications of M€ossbauerspectroscopy to LIB are given in Chapter 28. Chapter 29 is the example of applying M€ossbauer spectroscopy to developnovel bimetal heterogeneous catalysts for preferential CO oxidation in H2. Chapter 30 shows the successful use ofM€ossbauer spectroscopy to identify and quantify the iron mineral phases of South African coal fractions. The last twochapters are mainly on the applications of M€ossbauer spectroscopy to the environmental field, for example, describingthe recycling process of iron-containing “waste” of silicate glasses, which is related to purification of polluted water
xix
(Chapter 31). The variables control in the laterite mineral processing using M€ossbauer spectroscopy is another example(Chapter 32).
Finally, the editors of the book would like to acknowledge contributions by late Professor Attila Vertez, E€otv€osLor�and University. In addition to studying fundamentals of M€ossbauer spectroscopy, Attila applied the M€ossbauer effectto various fields. One of the coeditors, Virender K. Sharma, met Attila in fall 2002 when he was visiting Budapest underthe sustainability grant, received by Florida Tech, from the U.S. Department of States. During the visit, Attila was verykind to accept him in his group. Since then Virender had several interactions in Budapest and on one occasion inMelbourne, Florida. Because of the admiration for Attila, the M€ossbauer community organized a special symposium titled“Chemical Applications of M€ossbauer Spectroscopy,” honoring him at the American Chemical Society Spring Meeting atSan Francisco in March 2010. In the summer 2010, Virender traveled to Budapest to present the “Salute of Excellence”from the American Chemical Society. It was heartening to see that leading chemists from Hungary, including thepresident of the chemistry division of the Hungarian Academy of Science and president of E€otv€os Lor�and University, werepresent at that occasion. Attila will always be known as a great scientist with a gentleman touch and we will miss himdearly. This book is dedicated to late Professor Attila Vertez for his many accomplishments in M€ossbauer spectroscopy.
VIRENDER K. SHARMA
G€oSTAR KLINGELH€oFER
TETSUAKI NISHIDA
xx PREFACE
Contributors
Ricardo Alc�antara, Laboratorio de Qu�ımica Inorg�anica, Universidad de C�ordoba, C�ordoba, Spain
Irina V. Alenkina, Faculty of Physical Techniques and Devices for Quality Control, Institute of Physics and Technology,Ural Federal University, Ekaterinburg, Russian Federation
Ercan E. Alp, Advanced Photon Source, Argonne National Laboratory, Argonne, IL, USA
C�esar A. Barrero, Grupo de Estado S�olido, Facultad de Ciencias Exactas y Naturales, Universidad de Antioquia,Medell�ın, Colombia
Erika R. Bauminger, Racah Institute of Physics, Hebrew University of Jerusalem, Jerusalem, Israel
Edward Brown, Chemistry Department, Nassau Community College, Garden City, NY
Stephen P. Cramer, Department of Applied Science, University of California-Davis, Davis, CA, USA
Juan de la Figuera, Instituto de Qu�ımica F�ısica “Rocasolano”, CSIC, Madrid, Spain
Georges D�en�es, Department of Chemistry and Biochemistry, Concordia University, Montreal, Quebec, Canada
Eamonn Devlin, Institute of Materials Science, N.C.S.R. “Demokritos”, Attiki, Athens, Greece
Kednerlin Dornevil, Department of Chemistry, Georgia State University, Atlanta, GA, USA
Andrzej Friedman, Department of Neurology, Faculty of Health Science, Medical University of Warsaw, Warsaw,Poland
Ji9r�ı Frydrych, Regional Center of Advanced Technologies and Materials, Olomouc, Czech Republic
Jolanta Gałazka-Friedman, Faculty of Physics, Warsaw University of Technology, Warsaw, Poland
Jos�e Ram�on Gancedo, Instituto de Qu�ımica F�ısica “Rocasolano”, CSIC, Madrid, Spain
Karen E. Garc�ıa, Grupo de Estado S�olido, Facultad de Ciencias Exactas y Naturales, Universidad de Antioquia,Medell�ın, Colombia
Jean-Marc Greneche, LUNAM, Universit�e du Maine, Institut des Mol�ecules et Mat�eriaux du Mans, Le Mans Cedex,France
Yisong Guo, Department of Chemistry, Carnegie Mellon University, Pittsburgh, PA, USA
Barbara R. Hillery, Chemistry Department, Nassau Community College, Garden City, NY
Yukio Hinatsu, Department of Chemistry, Hokkaido University, Sapporo, Hokkaido, Japan
Zolt�an Homonnay, Faculty of Science, Eotvos Lorand University, Budapest, Hungary
Naoki Igawa, Quantum Bean Science Directorate, Japan Atomic Energy Agency, Tokai-mura, Naka-gun, Ibaraki, Japan
Jie Jin, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China
Alexander A. Kamnev, Laboratory of Biochemistry, Institute of Biochemistry and Physiology of Plants and Micro-organisms, Russian Academy of Sciences, Saratov, Russian Federation
Airat Khasanov, Department of Chemistry, University of North Carolina at Asheville, Asheville, NC, USA
Yoshio Kobayashi, Department of Engineering Science, The University of Electro-Communications, Tokyo, Japan
xxi
Norimichi Kojima, Graduate School of Arts and Sciences, The University of Tokyo, Meguro-ku, Tokyo, Japan
J�ozef Korecki, Institute for Synchrotron Radiation, Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen,Karlsruhe, Germany
Alla A. Kornilova, Moscow State University, Moscow, Russia
Krisztina Kov�acs, Laboratory of Nuclear Chemistry, Institute of Chemistry, E€otv€os Lor�and University, Budapest,Hungary
Stjepko Krehula, Division of Materials Chemistry, Rudjer Bo9skovi�c Institute, Zagreb, Croatia
Shiro Kubuki, Department of Chemistry, Graduate School of Science and Engineering, Tokyo Metropolitan University,Hachioji, Japan
Pedro Lavela, Laboratorio de Qu�ımica Inorg�anica, Universidad de C�ordoba, C�ordoba, Spain
Jan Ła _zewski, Institute for Synchrotron Radiation, Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen,Karlsruhe, Germany
Jung-Fu Lin, Department of Geological Sciences, Jackson School of Geosciences, The University of Texas at Austin,Austin, TX, USA
Aimin Liu, Department of Chemistry, Georgia State University, Atlanta, GA, USA
Kuo Liu, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China
Libor Machala, Regional Center of Advanced Technologies and Materials, Olomouc, Czech Republic
M. Cecilia Madamba, Department of Chemistry and Biochemistry, Concordia University, Montreal, Quebec, Canada
Zhu Mao, Department of Geological Sciences, Jackson School of Geosciences, The University of Texas at Austin,Austin, TX, USA
Jos�e F. Marco, Instituto de Qu�ımica F�ısica “Rocasolano”, CSIC, Madrid, Spain
Leopold May, Chemistry Department, Nassau Community College, Garden City, NY
Hocine Merazig, Laboratoire de Chimie Mol�eculaire, du Controle de l’Environnement et de Mesures Physico-Chimiques, D�epartement de Chimie, Facult�e des Sciences, Universit�e Mentouri, Constantine, Algeria
Toshiyuki Misu, Department of Chemistry, Faculty of Science, Toho University, Funabashi, Chiba, Japan
Matteo Monti, Instituto de Qu�ımica F�ısica “Rocasolano”, CSIC, Madrid, Spain
Alvaro L. Morales, Grupo de Estado S�olido, Facultad de Ciencias Exactas y Naturales, Universidad de Antioquia,Medell�ın, Colombia
Abdualhafed Muntasar, Department of Chemistry and Biochemistry, Concordia University, Montreal, Quebec,Canada
Svetozar Musi�c, Division of Materials Chemistry, Rugjer Bo9skovi�c Institute, Zagreb, Croatia
Masami Nakada, Advanced Science Research Center, Japan Atomic Energy Agency, Ibaraki, Japan
Tadahiro Nakamoto, Department of Materials Characterization, Toray Research Center, Inc., Otsu, Shiga, Japan
Akio Nakamura, Advanced Science Research Center, Japan Atomic Energy Agency, Tokai-mura, Naka-gun, Ibaraki,Japan
Mikio Nakamura, Department of Chemistry, Faculty of Science, Toho University, Funabashi, Chiba, Japan
Satoru Nakashima, Natural Science Center for Basic Research and Development, Hiroshima University,Higashi-Hiroshima, Japan
Lakshmi Nambakkat, Department of Physics, University College of Science, Mohanlal Sukhadia University, Udaipur,Rajasthan, India
xxii CONTRIBUTORS
Amar Nath, Department of Chemistry, University of North Carolina at Asheville, Asheville, NC, USA
Zolt�an N�emeth, Faculty of Science, Eotvos Lorand University, Budapest, Hungary
Tetsuaki Nishida, Department of Biological and Environmental Chemistry, Faculty of Humanity-Oriented Science andEngineering, Kinki University, Iizuka, Japan
Kiyoshi Nomura, School of Engineering, The University of Tokyo, Bunkyo-ku, Tokyo, Japan
Yoshihiro Okamoto, Quantum Beam Science Directorate, Japan Atomic Energy Agency, Tokai-mura, Naka-gun,Ibaraki, Japan
Michael I. Oshtrakh, Faculty of Physical Techniques and Devices for Quality Control, Institute of Physics andTechnology, Ural Federal University, Ekaterinburg, Russian Federation
Krzysztof Parli�nski, Institute for Synchrotron Radiation, Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen, Karlsruhe, Germany
Ji9r�ı Pechou9sek, Regional Center of Advanced Technologies and Materials, Olomouc, Czech Republic
Carlos P�erez Vicente, Laboratorio de Qu�ımica Inorg�anica, Universidad de C�ordoba, C�ordoba, Spain
Yurii D. Perfiliev, Chemistry Department, Florida Institute of Technology, Melbourne, FL, USA
Duncan Quarless, Chemistry Department, Nassau Community College, Garden City, NY
Mira Risti�c, Division of Materials Chemistry, Rugjer Bo9skovi�c Institute, Zagreb, Croatia
Ralf R€ohlsberger, Institute for Synchrotron Radiation, Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen, Karlsruhe, Germany
Michail Samouhos, School of Mining and Metallurgical Engineering, National Technical University of Athens,Athens, Greece
Bogdan Sepiol, Institute for Synchrotron Radiation, Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen,Karlsruhe, Germany
Virender K. Sharma, Chemistry Department, Florida Institute of Technology, Melbourne, Florida, USA
Marcel Sladecek, Institute for Synchrotron Radiation, Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen, Karlsruhe, Germany
Michał �Slezak, Institute for Synchrotron Radiation, Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen,Karlsruhe, Germany
Tomasz �Slezak, Institute for SynchrotronRadiation,Karlsruhe InstituteofTechnology (KIT), Eggenstein-Leopoldshafen,Karlsruhe, Germany
Sabrina G. Sobel, Chemistry Department, Nassau Community College, Garden City, NY
Nika Spiridis, Institute for Synchrotron Radiation, Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen,Karlsruhe, Germany
Svetoslav Stankov, Institute for Synchrotron Radiation, Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen, Karlsruhe, Germany
Akira Sugahara, Graduate School of Arts and Sciences, The University of Tokyo, Meguro-ku, Tokyo, Japan
Masashi Takahashi, Department of Chemistry, Faculty of Science, Toho University, Funabashi, Chiba, Japan
Masuo Takeda, Department of Chemistry, Faculty of Science, Toho University, Funabashi, Chiba, Japan
Jos�e L. Tirado, Laboratorio de Qu�ımica Inorg�anica, Universidad de C�ordoba, C�ordoba, Spain
Satoshi Tsutsui, Research and Utilization Division, SPring-8/JASRI, Sayo-cho, Sayo-gun, Hyogo, Japan; AdvancedScience Research Center, Japan Atomic Energy Agency, Ibaraki, Japan
CONTRIBUTORS xxiii
Ji9r�ı Tu9cek, Regional Center of Advanced Technologies and Materials, Olomouc, Czech Republic
Gero Vogl, Institute for Synchrotron Radiation, Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen,Karlsruhe, Germany
Vladimir I. Vysotskii, Mathematics and Theoretical Radiophysics Department, Kiev National Shevchenko University,Kiev, Ukraine
Frans B. Waanders, School of Chemical and Minerals Engineering, North West University, Potchefstroom, SouthAfrica
Junhu Wang, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China
Clive I. Wynter, Chemistry Department, Nassau Community College, Garden City, NY
Yuming Xiao, HPCAT, Advanced Photon Source, Argonne National Laboratory, Argonne, IL, USA
Yoshitaka Yoda, Research and Utilization Division, SPring-8/JASRI, Kouto, Sayo, Hyogo, Japan
Marcin Zajac, Institute for Synchrotron Radiation, Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen,Karlsruhe, Germany
Radek Zbo9ril, Regional Center of Advanced Technologies and Materials, Olomouc, Czech Republic; ChemistryDepartment, Florida Institute of Technology, Melbourne, FL, USA
Tao Zhang, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China
Wansheng Zhang, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, China
Xiaowei Zhang, Photon Factory, KEK, 1-1 Oho, Tsukuba, Ibaraki, Japan
Charalabos Zografidis, School of Mining and Metallurgical Engineering, National Technical University of Athens,Athens, Greece
xxiv CONTRIBUTORS
P A R T I
INSTRUMENTATION
C H A P T E R 1
IN SITUM €OSSBAUER
SPECTROSCOPY WITH
SYNCHROTRON RADIATION
ON THIN FILMS
SVETOSLAV STANKOV, TOMASZ �SLEZAK, MARCIN ZAJAC, MICHAŁ �SLEZAK, MARCEL SLADECEK,RALF R€oHLSBERGER, BOGDAN SEPIOL, GERO VOGL, NIKA SPIRIDIS, JAN ŁA _ZEWSKI,KRZYSZTOF PARLI�NSKI, AND J�oZEF KORECKI
Institute for Synchrotron Radiation, Karlsruhe Institute of Technology (KIT), Eggenstein-Leopoldshafen, Karlsruhe, Germany
1.1 INTRODUCTION
Soon after the first observation [1–3] by Rudolf M€ossbauer in 1958 of nuclear resonant recoilless absorption andemission of g-rays from nuclei of 191Ir, the M€ossbauer effect became a well-established spectroscopic method for probingthe electronic, magnetic, and dynamic properties of solids, liquids, and even gases [4]. The unprecedentedly high intrinsicenergy resolving power on the order of 10�13 offered by the M€ossbauer effect is determined by the natural linewidth ofthe nuclear resonant exited state. The relatively simple and easily accessible experimental setup, and the observation ofthe effect in isotopes of widely spread and technologically relevant elements such as iron and tin and their compoundsstimulated the explosion of applications of the M€ossbauer spectroscopy not only in solid state physics but also infundamental physics [5], chemistry [6], geology [7], biology [8], industry [9], and many other fields.
If a photon with an energy equal to the resonant energy impinges on the M€ossbauer nucleus in its ground state, thephoton may, with a probability given by the Lamb–M€ossbauer factor fLM, excite the nuclear resonant level without anenergy loss due to recoil. After the mean lifetime of this state, the nucleus returns back into its ground state either byemitting a photon or by ejecting an electron with probabilities 1/(1þa) and a/(1þa), respectively, where a is thecoefficient of total internal conversion. For most of the M€ossbauer isotopes, a is significantly greater that 1; therefore,the dominant mechanism for the de-excitation is internal conversion. The limited mean-free path of ejected electronsdefines an escape depth of only few nanometers. By detecting the conversion electrons (conversion electron M€ossbauerspectroscopy, CEMS), information about the electronic and magnetic properties of the materials’ surface can be derived.The high values of the cross section for nuclear resonant absorption and the small escape depths of the conversionelectrons established CEMS as a standard technique for investigating surface layers of materials [10]. Moreover, byanalyzing the energy of the ejected electrons depth-selective information can be retrieved [11,12]. This determined thevast range of applications of this technique to surface science and nanotechnology already soon after the first observationof the M€ossbauer effect.
The feasibility for in situ experiments on ultrathin 57Fe films consisting of only one atomic layer of iron by the CEMStechnique has been successfully demonstrated [13] in the mid-1980s. However, the relatively long data acquisition times
3
M€ossbauer Spectroscopy: Applications in Chemistry, Biology, and Nanotechnology, First Edition.
Edited by Virender K. Sharma, G€ostar Klingelh€ofer, and Tetsuaki Nishida.
� 2013 John Wiley & Sons, Inc. Published 2013 by John Wiley & Sons, Inc.
(�15 h) needed for accumulating spectra with reasonable statistics by using a conventional radioactive source havelimited further applications.
A new era in the M€ossbauer spectroscopy emerged in the year 1985 from the first observation of coherent elasticnuclear resonant scattering (NRS) of synchrotron radiation by the group of Erich Gerdau in Hamburg [14]. Thedemonstration that nuclear resonant experiments are indeed feasible by using synchrotron radiation instead ofradioactive source was a tremendous success. However, only the advent of the third-generation synchrotron radiationsources in the middle 1990s along with the rapid development of high-resolution X-ray optics [15–19] and fast avalanchephotodiode detectors (APDs) [20] established M€ossbauer spectroscopy with synchrotron radiation as a standardtechnique for probing electronic, magnetic, and dynamic properties of materials [21]. The enormous brilliance of the X-ray beams provided by insertion devices such as wigglers and undulators, which is by more than 10 orders of magnitudelarger in comparison with that of the conventional radioactive sources, allowed for the investigation of samples containingvery small quantities of the resonant isotope. This resulted in a significant expansion of applications to layered systems(thin- and ultrathin films, and multilayers), nanostructures (islands, clusters), and samples under extreme conditions, forexample, very high pressures and temperatures [22].
The possibility to finely tune the energy of the photons using high-resolution monochromators (HRMs) has resultedin a new technique for direct determination of the phonon density of states of the resonant element—the nuclearinelastic scattering (NIS) [23–25]. Thus, in the same experimental setup, one is able to probe simultaneously hyperfineinteractions and lattice dynamics of the sample.
Investigation of well-defined nanostructures often requires that the preparation, characterization, and maintenanceof the samples during experiments are performed under controlled, in most cases ultrahigh vacuum (UHV), conditions.Corresponding instrumentation [26,27] has been constructed and permanently installed at the nuclear resonancebeamline ID18 [28] of the European Synchrotron Radiation Facility (ESRF) in Grenoble, France. This opened up newperspectives for in situ investigations of electronic and magnetic properties, vibrational dynamics, and diffusionphenomena by several nuclear resonant scattering-based techniques such as coherent elastic nuclear resonant scattering,coherent quasielastic nuclear resonant scattering, and incoherent inelastic nuclear resonant scattering/absorption.
The aim of this chapter is to report on recent advances in the in situ M€ossbauer spectroscopy with synchrotronradiation on thin films that became possible due to the instrumentation developments at the nuclear resonance beamlineID18 of the ESRF. After a detailed description of the beamline and of the UHV system for in situ experiments, a briefintroduction into the basic NRS techniques is given. Finally, the application of these techniques to investigate magnetic,diffusion, and lattice dynamics phenomena in ultrathin epitaxial 57Fe films deposited on a W(110) substrate is presentedand discussed.
1.2 INSTRUMENTATION
The Classical M€ossbauer spectroscopy with a standard radioactive source has been performed in the energy domain,whereas the nuclear resonant scattering using synchrotron radiation measures the time-domain spectra. This impliesfundamental differences in the experimental approach and the associated instrumentation. The Synchrotron radiation atthird-generation sources is produced by insertion devices (wigglers or undulators) installed in the straight sections of thestorage ring, where relativistic electrons (positrons) circulate the ring [29]. One of the prerequisites for performing NRSexperiments is the timing mode of the storage ring operation. For nuclear resonant scattering applications, the storagering is filled with equidistant electron (positron) bunches that produce intensive X-ray pulses having a width of about100 ps. Especially suitable for NRS applications at the ESRF is the 16-bunch mode providing a time spacing of 176 nsbetween the bunches.
The second condition that has to be fulfilled is the utilization of fast detectors and associated timing electronics.Avalanche photodiodes have been successfully introduced [20] for NRS applications due to their quick time response,high dynamic range, and relatively high quantum efficiency. The time resolution ranges from 0.1 to 1.0 ns and the efficiencyfrom several percent to about 50% depending on the energy of the X-rays. The timing electronics is based on standardNIM modules, including constant fraction discriminators, gate generators, fast ADCs (analog digital converters), andMCAs (multichannel analyzers). A reference timing signal from the radio frequency system of the storage ring provides asynchronization of the electronics with the photon pulse arrival time.
To further improve the performance of the APD detectors for nuclear resonant scattering applications, the high-degree suppression of the nonresonant radiation is essential. This is achieved by using high-resolution monochromators
4 1 IN SITUM€OSSBAUER SPECTROSCOPY WITH SYNCHROTRON RADIATION ON THIN FILMS
