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NeutronSpinEcho Spectroscopy

Basics, Trends and Applications

13 Editors

Prof. Ferenc Mezei Dr. Thomas Gutberlet Dr. Catherine Pappas Paul Scherrer Institut Hahn-Meitner-Institut Berlin Laboratory for Neutron Scattering Glienicker Str. 100 5232 Villigen PSI 14109 Berlin, Germany Switzerland

Cover Picture:seeFig.2ofthecontributionbyA.Ioffeinthisvolume

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A catalog record for this book is available from the Library of Congress. Bibliographic information published by Die Deutsche Bibliothek Die Deutsche Bibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data is available in the Internet at http://dnb.ddb.de

ISSN 0075-8450 ISBN 3-540-44293-6 Springer-Verlag Berlin Heidelberg New York

This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustra- tions, recitation, broadcasting, reproduction on microfilm or in any other way, and storage in data banks. Duplication of this publication or parts thereof is permitted only under the provisions of the German Copyright Law of September 9, 1965, in its current version, and permission for use must always be obtained from Springer-Verlag. Violations are liable for prosecution under the German Copyright Law. Springer-Verlag Berlin Heidelberg New York a member of BertelsmannSpringer Science+Business Media GmbH http://www.springer.de
c Springer-Verlag Berlin Heidelberg 2003 Printed in Germany The use of general descriptive names, registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. Typesetting: Camera-ready by the authors/editor Camera-data conversion by Steingraeber Satztechnik GmbH Heidelberg Cover design: design & production,Heidelberg Printed on acid-free paper SPIN: 10893057 54/3141/du-543210 Preface

By involuntary timing this volume will appear almost exactly thirty years after neutron spin echo (NSE) was discovered and the echo effect was experimen- tally first demonstrated in April 1972 at the Budapest Research Reactor on the forested hills around the city. The idea to organize the present volume arose during a recent workshop1 which followed by twenty years the first workshop devoted to the technique of NSE and research using NSE held at ILL2,3. The context and content of the two workshops were, of course, very different. In 1979 there was just one operational NSE spectrometer, the IN11 at ILL and the discussion focussed on establishing the fundamental technique and review- ing the first set of successful applications of the method in condensed matter research. Today 13 NSE instruments serve a broad and well-established user community and more machines are being planned. Current examples of research results obtained by NSE spectroscopy well illustrate the broad relevance of the method for the study of a variety of phenomena, including phase transitions, magnetism, superconductivity and in particular soft matter in general, such as polymers, liquids, glassy and biological systems. A wealth of innovations proposed in the past two decades by quite a num- ber of people have been realized. The zero field (ZF) or resonance NSE (NRSE) variant was introduced some 15 years ago. At about the same time it was also realized and demonstrated that the NSE principle can also be efficiently used by neutron velocity dependent modulation of a parameter of the neutron beam other than polarization, for example intensity. More recent years have seen a particular surge of new ideas for extending both the techniques and the field of applications to new domains such as to use the NSE principle in small an- gle scattering, reflectometry, and to develop combinations of NSE and neutron optical phenomena such as nuclear refractive index and interference effects. On the other hand, instrument performance in those “classical” applications in quasi-elastic scattering has also tremendously progressed. Resolutions avail- able today exceed 200 ns (about 3 neV HWHM equivalent) compared to 10 ns 20 years ago. The technique of using high detector solid angles has also been established with the actual capability of taking NSE data simultaneously in an 1 International Workshop on Neutron Spin Echo Spectroscopy. Hahn-Meitner-Institut, Berlin, Germany, October 16.-17. 2000 2 Neutron Spin Echo, Institute Laue-Langevin, Grenoble, France, October 15.-16. 1979 3 Neutron Spin Echo ed. by F. Mezei, Spinger Verlag, Heidelberg, 1980 VI Preface angular range of about 30◦ to 80◦ with more than 200◦ in principle accessible if one can afford to acquire a vast collection of either supermirror analysers or polarized 3He filter cells. Since its advent in the early seventies a broad range of applications have been developed covering the study of a variety of phenomena in condensed mat- ter research. The present volume, after a general introduction to the principles of NSE, gives detailed technical descriptions of various approaches and new devel- opments in NSE instrumentation (Part I) and selected examples of NSE studies (Part II). The carefully selected contributions collected in this volume present to the interested reader and researchers recent developments, current status and future perspectives of NSE research. We believe they will not only introduce newcomers to the field by describing principal techniques and approaches but also highlight by examples the power and usefulness of NSE spectroscopy in various fields of exploration of condensed matter. The editors are most grateful to the authors of this volume for their cooper- ation and fascinating contributions and to Springer Verlag for invaluable advice and taking great care of this endeavor.

Berlin, Summer 2002 Ferenc Mezei Catherine Pappas Thomas Gutberlet List of Contributors

Wim G. Bouwman Bela Farago Interfacultair Reactor Instituut Institut Laue Langevin Delft University of Technology 6 rue Jules Horowitz Mekelweg 15 38042 Grenoble Cedex 9 2629 JB Delft France The Netherlands [email protected] [email protected] Edward M. Forgan Samrath L. Chaplot School of Physics and Astronomy Solid State Physics Division University of Birmingham Bhabha Atomic Research Centre Birmingham, B15 2TT Trombay, Mumbai 400085 United Kingdom India [email protected] [email protected]

Juan Colmenero Alexander I. Frank Unidad de F´ısica de Materiales Frank Laboratory of Neutron (CSIC–UPV/EHU) Physics Apartado 1072 Joint Institute for Nuclear Research 20080 San Sebasti´an 141980, Dubna Spain Russia [email protected] [email protected] Roland G¨ahler Georg Ehlers Institut Laue Langevin Institut Laue Langevin 6 rue Jules Horowitz 6 rue Jules Horowitz 38042 Grenoble 38042 Grenoble Cedex 9 France France name@e-mail.* [email protected]

Bernd Ewen Klaus Habicht MPI f¨ur Polymerforschung Hahn-Meitner-Institut Berlin Postfach 3148 Glienicker Str. 100 55021 Mainz 14109 Berlin Germany Germany [email protected] [email protected] VIII List of Contributors

Thomas Hellweg Ferenc Mezei TU Berlin Hahn-Meitner-Institut Berlin Iwan-N.-Stranski Institut f¨ur Glienicker Str. 100 Physikalische und Theoretische 14109 Berlin Chemie Straße des 17. Juni 112 Germany 10623 Berlin [email protected] Germany [email protected] Michael Monkenbusch Forschungszentrum J¨ulich Alexander Ioffe Institut f¨ur Festk¨orperforschung Forschungszentrum J¨ulich 52425 J¨ulich Institut f¨ur Festk¨orperforschung Germany 52425 J¨ulich [email protected] Germany [email protected] Catherine Pappas Hahn-Meitner-Institut Berlin Thomas Keller Glienicker Str. 100 MPI for Solid State Research 14109 Berlin Heisenbergstr. 1 Germany 70569 Stuttgart [email protected] Germany Thomas−[email protected] Helmut Rauch Atominstitut der Osterreichischen¨ Valentin T. Lebedev Universit¨aten Petersburg Nuclear Physics Stadionallee 2 Institute 1020 Wien 188300 Gatchina, St.-Petersburg dist. Austria Russia [email protected] [email protected] M. Theo Rekveldt Fran¸coise Leclercq Interfacultair Reactor Instituut LASIR-CNRS Delft University of Technology 13, rue de Toul Mekelweg 15 59046 Lille 2629 JB Delft France The Netherlands [email protected] [email protected]

St´ephane Longeville Hideki Seto Laboratoire L´eon Brillouin Faculty of Integrated Arts and (CEA-CNRS) Sciences CEA Saclay Hiroshima University 91191 Gif-sur-Yvette Higashi-Hiroshima 739-8521 France Japan [email protected] [email protected] List of Contributors IX

Gyula T¨or¨ok Bing-Shiou Yang Research Institute for Solid State Department of Chemical Engineering Physics and Optics Princeton University P.O.Box 49 Princeton, NJ 08544 1525 Budapest U.S.A. Hungary [email protected] [email protected] Contents

Introduction F. Mezei ...... 1

Part I Basic Science and Technology

Fundamentals of Neutron Spin Echo Spectroscopy F. Mezei ...... 5 1 Principles of Neutron Spin Echo Spectroscopy ...... 8 2 Approximations, Resolution Effects and Data Reduction ...... 11 3 Magnetic Scattering Effects ...... 13 Time-of-Flight Neutron Spin Echo: Present Status B. Farago ...... 15 1 Time-of-Flight Neutron Spin Echo ...... 20 2 A Practical Example ...... 30 3 Perspectives and Limitations ...... 31 Wide Angle Neutron Spin Echo and Time-of-Flight Spectrometer C. Pappas, A. Triolo, F. Mezei, R. Kischnik, G. Kali...... 35 1 General Description of the Spectrometer – Time-of-Flight Configuration ...... 36 2 Neutron Spin Echo Configuration...... 37 3 Neutron Optics ...... 43 4 Combination of NSE and TOF: Deuterated Atactic Polypropylene .... 44 Neutron Spin Echo Spectrometer at B.A.R.C. Trombay S.L. Chaplot, R. Mittal, K.N. Prabhatasree ...... 48 1 Instrument Design ...... 48 2 Neutron Polarization Changes...... 51 3 Neutron Spin Echo ...... 52 Compact Neutron Spin Echo Device with Foil Spin Flippers V.T. Lebedev, Gy. T¨or¨ok, G.P. Gordeev ...... 56 1 Compact Neutron Spin Echo Unit ...... 57 2 Neutron Spin Echo Focusing ...... 60 3 Quasielastic Scattering from Water ...... 63 XII Contents

Modified Neutron Spin Echo with Spectrum Modulation: Specific Feature and Applications V.T. Lebedev, G.P. Gordeev, Gy. T¨or¨ok ...... 65 1 Modified Neutron Spin Echo ...... 65 2 Main Spectrometer Specifications ...... 69 3 Dynamics of Magnetic Flux Inhomogeneities in Y-Ba-Cu-O Ceramics ...... 70 Neutron Resonance Spin Echo – Triple Axis Spectrometry (NRSE-TAS) T. Keller, B. Keimer, K. Habicht, R. Golub, F. Mezei ...... 74 1 Basic Principles of Spin Echo Phonon Focusing ...... 76 2 The NRSE-TAS at BENSC Berlin ...... 81 Elastic Neutron Scattering Measurements Using Larmor Precession of Polarized Neutrons M.Th. Rekveldt, W.G. Bouwman, W.H. Kraan, O. Uca, S.V. Grigoriev, K. Habicht, T. Keller ...... 87 1 Angle and/or Wavelength Encoding with Larmor Precession ...... 88 2 SESANS ...... 95 3 High Resolution Larmor Diffraction ...... 97 Technical Aspects of Larmor Precession with Inclined Front and End Faces M.Th. Rekveldt, W.G. Bouwman, W.H. Kraan, O. Uca, S.V. Grigoriev, R. Kreuger ...... 100 1 Options to Realize Inclined Faces ...... 100 2 Technical Details for Homogeneous Field Line Integrals ...... 108 Space-Time View of Neutron Spin Echo, Correlation Functions and Phonon Focusing K. Habicht, R. Golub, R. G¨ahler, T. Keller ...... 116 1 Treatment of Inelastic Scattering Spin Echo by Larmor Precession ...... 117 2 Quantum Mechanical Treatment of NSE and Inelastic Scattering .....120 3 Semi-classical (Ray Tracing) Discussion of Inelastic Scattering NSE . . . 123 4 Phonon Focusing ...... 125 5 Phonon Focusing in the Space-Time View ...... 128 Neutron Spin Echo as a Quantum Interference System H. Rauch, M. Suda ...... 133 1 Basic Formulation ...... 134 2 Spin Echo ‘Quasi–Distribution’ Functions ...... 136 Neutron Speed Echo Spectroscopy A. Ioffe ...... 142 1 NSE as an Interference Phenomenon ...... 143 Contents XIII

2 Modulation of the Spectra by Two Moving Diffraction Gratings ...... 147 3 Neutron Speed Echo Spectrometer ...... 150 4 The Limit of Geometric Optics ...... 152 5 Space-Time Description of a Neutron Speed Echo Spectrometer ...... 154 6 Comparison of NSE and NSPE Spectrometers ...... 156 7 Triple Axis Spectrometers with the NSPE Option ...... 160 Neutron Spin Precession Optics: Recent Results and Some Perspectives A.I. Frank, I.V. Bondarenko, A.V. Kozlov, G. Ehlers, P. Høghøj ...... 165 1 Interaction Time of Neutrons with an Object and the Larmor Clock . . 166 2 Experiment for the Measurement of the Delay Time in Refraction ....168 3 Direct Measurement of the Neutron Interaction Time with Quantum Objects ...... 170 4 Neutron Spin Precession and Phase Contrast Imaging with Very Slow Neutrons ...... 172 Future Developments in Resonance Spin Echo M. Bleuel, F. Demmel, R. G¨ahler, R. Golub, K. Habicht, T. Keller, S. Klimko, I. K¨oper, S. Longeville, S. Prokudaylo ...... 176 1 ZETA: NRSE + Three Axis at ILL ...... 177 2 RESEDA: NRSE at FRM-II ...... 181 3 Proposal of a High Resolution NRSE Spectrometer ...... 183 4 MIEZE and Its Applications ...... 186 5 Multi-angle Analysis for MUSES at LLB ...... 193 6 Neutron Computer Holography ...... 196 Neutron Spin Echo Spectrometers of the Next Generation – Where Are the Limits? M. Monkenbusch ...... 201 1 Future Needs ...... 201 2 Requirements and Generic Design ...... 204 3 Limitations and Open Questions ...... 211

Part II Applications in Physics, Chemistry and Life Sciences

Use of the Neutron Spin Echo Technique to Observe Flux Line Motion E.M. Forgan, P.G. Kealey, A. Pautrat, Ch. Simon, S.L. Lee, R. Cubitt, B. Farago, P. Schleger ...... 215 1 Flux Lines and Their Motion in Superconductors ...... 215 2 The Experimental Arrangement ...... 216 3 Theory and Experimental Results ...... 218 XIV Contents

Dynamics of Frustrated Magnetic Moments in Antiferromagnetically Ordered TbNiAl Probed by Spin Echo and Time-of-Flight Spectroscopy G. Ehlers, H. Casalta, R.E. Lechner, H. Maletta ...... 222 1 NSE and TOF Experiments ...... 224 Critical Slowing Down in a Simple Fluid System as Measured by Neutron Spin Echo Technique. Crossover Between Hydrodynamics and Critical Dynamics F. Leclercq, S. Pouget, P. Damay ...... 232 1 Theory and Background ...... 233 2 Experiments and Data Analysis ...... 237 3 Hydrodynamics and Critical Dynamics ...... 241 Soft Matter and Biology M. Monkenbusch ...... 246 1 Soft Matter Systems ...... 246 2 The NSE Signal ...... 247 3 Linear Polymers ...... 249 4 Block Copolymers ...... 259 5 More Complicated Polymer Architectures ...... 261 6 Microemulsions ...... 262 7 Glasses...... 264 8 Biology ...... 265 Dynamics of Glass Forming Polymers by Neutron Spin Echo J. Colmenero, A. Arbe, D. Richter, B. Farago, M. Monkenbusch ...... 268 1 Glass Forming Polymers ...... 268 2 The α-Relaxation ...... 270 Elastic and Quasielastic Neutron Scattering on Liquid Isotopic and Binary Blends of Low Molecular Mass Poly(siloxanes) B. Ewen, H. G¨otz, U. Maschke ...... 280 1 Theory of Collective Polymer Dynamics ...... 280 2 SANS and NSE Experiments ...... 282 Neutron Spin Echo Study of the Dynamics in BIS Cross-linked Poly(N-Isopropyl Acrylamide) Microgels: Dependence on the Cross-Linker Concentration T. Hellweg, W. Eimer, S. Pouget, K. Kratz ...... 291 1 Microgels ...... 291 2 Materials, Preparation and Methods ...... 292 3 Theory ...... 294 4 NSE Experiments: Results and Discussion ...... 295 Contents XV

Dynamical Fluctuation of Cylindrical Micelles and Membranes in Binary and Ternary Amphiphilic Microemulsion Systems S. Komura, T. Takeda, H. Seto, M. Nagao ...... 302 1 Amphiphilic Microemulsions ...... 302 2 The Zilman-Granek Theory ...... 304 3 NSE Experimental Results ...... 305 4 Analysis and Determination of Bending Modulus and Viscosity ...... 309 Dynamics of Hydrophobically Modified Polymer Doped Surfactant Bilayers: A Neutron Spin Echo Study B.-S. Yang, J. Lal, M. Mihailescu, M. Monkenbusch, D. Richter, J.S. Huang, W.B. Russel, R.K. Prud’homme ...... 312 1 Polymer Doped Surfactant Bilayers ...... 312 2 SANS and NSE Experiments ...... 314 3 Static Elastic and Dynamic Properties ...... 317 Neutron Resonance Spin Echo: Oxygen Transport in Crowded Protein Solutions S. Longeville, W. Doster, M. Diehl, R. G¨ahler, W. Petry ...... 325 1 Neutron Resonance Spin Echo Spectrometry ...... 325 2 Study of Myoglobin Diffusion with NRSE ...... 329

Index ...... 337