The Time Domain in Surface and Structural Dynamics

NATO ASI Series Advanced Science Institutes Series

A Series presenting the results of activities sponsored by the NA TO Science Committee, which aims at the dissemination of advanced scientific and technological knowledge, with a view to strengthening links between scientific communities.

The Series is published by an international board of publishers in conjunction with the NATO Scientific Affairs Division

A Life Sciences B Physics

C Mathematical and Physical Sciences

D Behavioural and Social Sciences E Applied Sciences

F Computer and Systems Sciences G Ecological Sciences H Cell Biology

Plenum Publishing Corporation London and New York

Kluwer Academic Publishers Dordrecht. Boston and London

Springer-Verlag Berlin. Heidelberg, New York, London. Paris and Tokyo

Series C: Mathematical and Physical Sciences - Vol. 228

The Time Domain in Surface and Structural Dynamics

edited by

Gary J. Long Department of Chemistry, University of Missouri-Rolla, Rolla, U.S.A.

and

Fernande Grandjean Department of Chemistry, University of Liege, Liege, Belgium

Kluwer Academic Publishers

Dordrecht / Boston / London

Published in cooperation with NATO Scientific Affairs Division

Proceedings of the NATO Advanced Study Institute on The Time Domain in Surface and Structural Dynamics II Ciocco, Italy June 15-26, 1987

Library of Congress Cataloging in Publication Data

NATO Advancea Stuay InstItute on the TIme DomaIn In Surface ana Structural DynamIcs (1967 11 CIOCCa, Italy)

The time domain In surface and structur~l Oynd~lc~ I eOlted by Gary ~. Long and Fernanae GrandJean.

p. cm. -- (NATO ASI "erles. SerIes C. Matnematlcal and phySIcal sCIences: vol. 228)

"Proceedings of the NAjO Advanced $tuO~ Institute on the Time Domain In Surface and Structural DynamIcs, 11 CIOCCD. Italy. ~une 15-26. 1987"--T.p. verso.

·Publlshed In cooperatIon .,th NATO SCIentIfIC AffaIrs D,VISIon." Includes Inoexes. ISBN-13: 978-94-010-7819-1 1. Sollds--Surfaces--Congresses. 2. Structural aynarulcs­

-Congresses. 3. Tlme-oomalo Qnalysls--Con9re~se~. 4. Nuclear magnetIc resonance spectrascopy--Congresses. 1. Long. Gary J .• 1941- II. GranoJean. Fernanoe. 1947- Ill. North AtlantIC Treaty Organization. SCientifiC Affairs DIVISion. IV. Title. V. SerIes NATO ASI serIes. SerIes C. Mdthem"tlcal .na phYSIcal SCIences: no. 22B. aCI76.8.S8N39 1987 530.4·1--ocI9

ISBN-13: 978-94-010-7819-1 e-ISBN-13: 978-94-009-2929-6 001: 10.1007/978-94-009-2929-6

Published by Kluwer Academic Publishers, P.O. Box 17, 3300 AA Dordrecht, The Netherlands.

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Table of Contents

Preface ........................................................... ~x

List of Contributors and Participants ........................... xi

Chapter 1. Timescales of Physical Measurements: Some Elementary Considerations ........................ 1 P. Day

Chapter 2. Time: Its History and Measurement. Billions of Years Within a Nanosecond ........ , ......... 7 F. Grandjean

Chapter 3. Galileo, His Life in Pisa and His Scientific Instruments .......................................... 19 U. Russo

Chapter 4. Time Domajn NMR and Magic Angle Spinning ............. 31 E. R. Andrew

Chapter 5. Chemical, Molecular and Spin Dynamics ................ 49 N. J. Clayden

Chapter 6. Effects of Molecular Motions on NMR Parameters of Solid State Spectra ............................... 65 S. Aime

Chapter 7. Deuterium NMR Studies of Dynamics in Solids .......... 81 R. G. Griffin, K. Beshah, R. Ebelhauser, T. H. Huang, E. T. Olejniczak, D. J. Siminovitch, D. M. Rice, and R. J. Wittebort

Chapter 8. Protein Dynamics and the Time Domain ................ 107 R. D. Young

Chapter 9. Domain Motions in Proteins .......................... 139 W. S. Bennett

Chapter 10. Quasi-elastic and Inelastic Neutron Scattering ...... 179 J. Dianoux

Chapter 11. Probing Structural Dynamics by Very High Resolution Neutron Three Axis Spin Echo Spectroscopy ........... 213 C. M. E. Zeyen

Chapter 12. Dynamic Processes as Followed by Electron Paramagnetic Resonance .............................. 233 J. P. Launay

Chapter 13. The Time Domain in Intramolecular Electron Transfer Reactions ........................................... 251 J. P. Launay

Chapter 14. Dynamics of Interionic Electron Transfer ............ 261 P. Day

Chapter 15. Mossbauer Spectroscopy and its Application to Studies of Time-dependent Phenomena ................. 271 S. Morup

Chapter 16. Mossbauer Spectral Lineshapes in the Presence of Electronic State Relaxation ......................... 287 F. Grandjean

Chapter 17. Mossbauer Spectroscopy Studies of Relaxation Phenomena in Ultrafine Particles .................... 309 S. Morup

Chapter 18. Mossbauer Spectroscopy Studies of Paramagnetic Relaxation .......................................... 321 S. Morup

Chapter 19. Competition between Delocalization and Crystallization for Electrons in the Low-temperature Modification of the Mixed-valence Iron Oxyphosphate, beta-Fe2P05 .... 335 B. Malaman, B. Ech-Chahed, and C. Gleitzer

Chapter 20. Electron Transfer in CaFe305 ........................ 339 R. Gerardin, E. Millon, J. F. Brice, o. Evrard, and G. Le Caer

Chapter 21. Time Differential Perturbed Angular Correlation Studies of Dynamic Systems ......................... 345 T. Butz

Chapter 22. Muon Spin Relaxation: A Novel Magnetic Resonance Technique to Study Dynamic and Static Magnetism ..... 369 C. Boekema

Chapter 23. Magnetic Dynamics in Oxides, As Observed by Muon Spin Relaxation ................................ 377 C. Boekema

Chapter 24. Magnetic Susceptibility Studies of Time-dependent Phenomena: Application to the Magnetic Relaxation Processes in Fine Particles and in Spin-glasses . 391 D. Fiorani

vli

Chapter 25. Muon Spin Research on Spin-glasses .................. 429 C. Boekema

Chapter 26. Adsorption Studies Using Low Energy Electron Diffraction ......................................... 439 R. D. Diehl

Chapter 27. Neutron Scattering Studies of the Structure, Phase Transitions, and Dynamics of Commensurate Herringbone Monolayers Physisorbed on Graphite ...... 467 H. Taub

Chapter 28. Non-bonded Intermolecular Interactions and their Modification in the Presence of a Surface ........ '" 499 F. Y. Hansen

Chapter 29. Timescale Considerations in the Characterization of Melting and Freezing in Microclusters ............... 535 H. L. Davis, T. L. Beck, P. A. Braier, and R. S. Berry

Author index .................................................... 551

Subject index ................................................... 569

Preface

About two years ago, while studying the dynamic properties of Fe3(CO)IJ ,we realized that there was virtually no single source of infonnation on the structural dynamics of materials. The time domain of different dynamic structural processes covers many orders of magnitude and may be in­vestigated by numerous, vastly different, experimental techniques. Indeed, the subject seemed ap­propriate for a NATO Advanced Study Institute at which we could bring together chemists, physicists, metallurgists, and bioscientists using the various techniques for the study of sundry time sensitive materials. The actual Advanced Study Institute, which met in II Ciocco, Italy, from 14 to 26 June 1987, was, in fact, a dynamic experience for those of us involved. Now we have come to the final phase, the communication of the results of this Advanced Study Institute to the general scientific community. In so doing, we hope to provide in one place a convenient source of infor­mation on dynamics at the surface and within a solid state material.

The beautiful mountainous setting of Tuscany and especially the idyllic surroundings of II Ciocco provided an ideal venue for the Advanced Study Institute. Our field trip to Pisa linked our topic to the history of time measurement through a visit to the Pisa cathedral where, presumably, Galileo first conceived the isochronism of the simple pendulum and its use in time measurement. History tells us that Pisa was also the birthplace, in 1170, of Leonardo Fibonacci, much less well known then Galileo, but perhaps just as important to modern science. Pibonacci, through his book, 'Liber Abaci' introduced and popularized the use of Arabic numerals throughout Europe.

The Advanced Study Institute was made possible through the generous support of the Scientific Affairs Division of NATO. This support is acknowledged with thanks by the editors and the par­ticipants. The additional financial support of the United States National Science Foundation, the Centro Nazionale di Ricerca, Italy, Carlo Erba Instrumentation, and the Tourism Office of the Province of Lucca was also beneficial to the overall success of the ASI. During the organization of the ASI, the editors greatly appreciated the extensive support and helpful ideas of Peter Day of Oxford University and Umberto Russo of Padova University, both of whom served on the inter­national organizing committee. The further organizational help of Christopher Dobson of Oxford University, Raymond Andrew of the University of Florida, and Renee Diehl of Liverpool Univer­sity insured the success of the ASI. Purther, we express our thanks to Bruno Giannasi and the gracious staff of II Ciocco, who made our stay so pleasant. In the preparation of this manuscript for publication, we wish to thank Ms. S. Maquet and P. Schmitz and Mr. J. C10es for their tech­nical assistance.

November 1987

Gary J. Long

Fernande Grandjean

List of Contriblltors and Participants

Silvio Aime (L,C)

Istituto di Chimica Generale e Inorganica, Universita degli Studi di Torino, Corso Massimo d'Azeglio 48, 1-10125 Torino, Italy

E. Raymond Andrew (L,C)

Department of Physics, University of Florida, 215 Williamson Hall, Gainesville, FL 32611, U.S.A.

Akkus Baki (P)

Istanbul Universitesi, Fen Fakultesi Fizik Bolumu, TK-34459 Istanbul, Turkey

T. L. Beck, P. A. Braier, R. S. Berry (C)

Department of Chemistry, University of Chicago, 5735 South Ellis Avenue, Chicago, IL 60637, U.S.A.

William S. Bennett (L,C)

Abt. Wittmann, Max-Planck Institut fur Molekulare Genetik, Ihnestrasse, 73, D-1000 Berlin 33, Federal Republic of Germany

K. Beshah, R. Ebelhauser, T. S. Huang, E. T. Olejniczak

D. M. Rice, D. J. Siminovitch, R. J. Wittebort (C)

Francis Bitter National Magnet Laboratory Massachusetts Institute of Technology Cambridge, MA 02139, U.S.A.

Carel Boekema (L,C)

Department of Physics, San Jose State University, San Jose, CA 95192, U.S.A.

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xii

Claude Bostoen (P)

U.I.A., Universiteitsp1ein 1, B-2610 Wi1rijk, Belgium

Tilman Butz (L,C)

Physik Department E15, Technische Universitat Munchen, James Franck Strasse, D-8046 Garching, Federal Republic of Germany

Enrico Campari (P)

Dipartimento di Fisica, Universita di Bologna, Via Irnerio 46, 1-40126 Bologna, Italy

Edward W. Castner (P)

Department of Chemistry, University of Chicago, 5735 South Ellis Avenue, Chicago, IL 60637, U.S.A.

Nigel J. C1ayden (L,C)

ICI, Chemistry and Polymers Group, P.O. Box 90, Wilton Midd1ebourgh, Cleveland TS6 8JE, England

Heidi L. Davis (P ,C)

Department of Chemistry, University of Chicago, 5735 South Ellis Avenue, Chicago, IL 60637, U.S.A.

Peter Day (O,L,C)

Inorganic Chemistry Laboratory, Oxford University, South Parks Road, Oxford OX1 3QR, England

Jose Dianoux (L,C)

Institut Laue Langevin, Avenue des Martyrs, B.P. 156 X, F-38042, Grenoble Cedex, France

Renee D. Diehl (L,C)

Department of Physics, University of Liverpool, Liverpool L69 3BX, England

Judith M. Fiddy (P)

Department of Physics, University of Liverpool, Liverpool L69 3BX, England

Dino Fiorani (L,C)

1stituto di Struttura Elettronica, CNR, Area della Ricerca di Roma, Via Salaria Km 29.5, Casella Postale 10, 1-00016 Monterotondo Sta7.ione (Roma) Italy

Paul Stephen Fowles (P)

Department of Physics, University of Liverpool, P.O. Box 147, Liverpool L69 3BX, England

R. Gerardin, E. Millon, J. F. Brice, O. Evrard (C)

CNRS, Laboratoire de Metallurgie, F-54042 Nancy Cedex, France

Then Gerhard (P)

Karlsruhe Universitat, 1nstitut fur Kern Physik Postfach 3640, D-7500 Karlsruhe, Federal Republic of Germany

Wolfgang Girnus (P)

1nstitut Physikalische Chemie, Strehlowweg 36, D-2900 Hambrug 52, Federal Republic of Germany

Andre Gourdon (P)

Laboratoire de Chimie des Metaux, Universite Pierre et Marie Curie, Place Jussieu 4, F-75252 Paris Cedex, France

Fernande Grandjean (O,L,C)

1nstitut de Physique, Universite de Liege, B5, B-4000 Sart-Tilman, Belgium

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XIV

Robert G. Griffin (L,C)

National Magnet Laboratory, NW 14-5113, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA 02139, U.S.A.

Jacques Guillin (P)

Institut fur Physik, Medizinische Universitat I,ubeck, Ratzeburger Allee 160, D-2400 Lubeck, Federal Republic of Germany

Fleming Y. Hansen (L,C)

Fysisk-Kemisk Institut, Technical University of Denmark, DK-2800 Lyngby, Denmark

Samar S. Hasnain (L)

Science and Engineering Research Council Daresbury Laboratory, Warrington, Cheshire WA4 4AD England

Mohamedally Kurmod (P)

Inorganic Chemistry Laboratory, Oxford University South Parks Road, Oxford OXI 3QR, England

Jean-Pierre Launay (L,C)

Laboratoire de Chimie des Metaux de Transition, Universite Pierre et Marie Curie, Place Jussieu 4, F-75230 Parix Cedex 05, France

Gerard Le Caer (P ,C)

CNRS, Laboratoire de Metallurgie, F-54042 Nancy-Cedex, France

Gary J. Long (0)

Department of Chemistry, University of Missouri-Rolla Rolla, MO 65401, U.S.A.

B. Malaman, B. Ech-Chahed, C. Gleitzer (C)

Laboratoire de Chimie du Solide Mineral, UA 158, Universite de Nancy I, B.P. 239 F-54506 Vandoeuvre-les-Nancy Cedex, France

Paolo Matteazzi (P)

1st. Chimica Industriale, Via Marzolo 9, 1-35100 Padova, Italy

Pierre Mihailovic (P)

Laboratoire de Chimie et Electrochimie des Materiaux Moleculaires, ESPCI, F-75005 Paris, France

Steen Morup (L,C)

Laboratory of Applied Physics II, Technical University of Denmark, Building 307, DK-2800 Lyngby, Denmark

Basaran Reha (P)

Istanbul Universitesi, Fen Fakultesi Fizik Bolumu, TK-34459 Istanbul, Turkey

Umberto Russo (O,L,C)

Dipartimento di Chimica Inorganica, Universita degli Studi di Padova, Via Loredan, 4, 1-35131 Padova, Italy

Cindy Schauer (P)

Department of Chemistry, Northwestern University, Evanston, IL 60201, U.S.A.

John Stevens (P)

University of Liverpool, P.O. Box 147 Liverpool L69 3BX, England

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Haskell Taub (L,C)

Department of Physics, University of Missouri-Columbia, Columbia, MO 65211, U.S.A.

Wolfgang Troeger (P)

Physik-Department E15, Technische Universitat Munchen, James Franck Strasse, D-8046 Garching, Federal Republic of Germany

Tamara A. Ulibarri (P)

Department of Chemistry, University of California, Irvine, CA 92717, U.S.A.

Simon D. Waddington (P)

Department of Physcis, University of Liverpool, P.O. Box 147, Liverpool L69 3BX, England

Hans W. Weber (P)

Karlsruhe Universitat, Institut fur Kern Physik Postfach 3640, D-7500 Karlsruhe, Federal Republic of Germany

Wolter Wegener (P)

SCK-CEN, Boeretang 200, B-2400 Mol, Belgium

Robert D. Young (L,C)

Department of Physics, Loomis Laboratory of Physics, University of Illinois at Urbana-Champaign, 1110 West Green Street, Urbana, IL 61801, U.S.A.

Claude M. E. Zeyen (P ,C)

Institut Laue Langevin, Avenue des Martyrs, B.P. 156 X, F-38042 Grenoble Cedex, France

(0) Organizer, (L) Lecturer, (P) Participant, (C) Contributor