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Chemical Crystallography with Pulsed Neutrons and Synchrotron X-Rays
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 Plenum Publishing Corporation B PhysiCS London and New York
C Mathematical D. Reidel Publishing Company and Physical Sciences Dordrecht, Boston, Lancaster and Tokyo
D Behavioural and Social Sciences Martinus Nijhoff Publishers E Applied Sciences Dordrecht, Boston and Lancaster
F Computer and Systems Sciences Springer-Verlag G Ecological Sciences Berlin, Heidelberg, New York, London, H Cell Biology Paris, and Tokyo
Series C: Mathematical and Physical Sciences Vol. 221
Chemical Crystallography with Pulsed Neutrons and Synchrotron X-Rays
edited by
Maria Armenia Carrondo Centro de Ouimica Estrutural, Instituto Superior Tecnico, Lisboa, Portugal
and
George A. Jeffrey Department of Crystallography, University of Pittsburgh, Pennsylvania, U.S.A.
D. Reidel Publishing Company
Dordrecht / Boston / Lancaster / Tokyo
Published in cooperation with NATO Scien1ific Affairs Division
Proceedings of the NATO Advanced Study Institute on Chemical Crystallography with Pulsed Neutrons and Synchrotron X-Rays Alvor, Algarve, Portugal March 17-27, 1987
Library of Congress Cataloging in Publication Data
NATO Advanced Study Institute on Chemical Crystallography with Pulsed Neutrons and Synchrotron X-Rays (1987: Alvor, Portugal)
Chemical crystallography with pulsed neutrons and synchrotron X-rays I edited by Maria Armenia Carrondo and George A. Jeffrey.
p. cm. - (NATO ASI series. Series C, Mathematical and physical sciences; vol. 221.) "Proceedings of the NATO Advanced SLdy Institute on Chemical Crystallography with
Pulsed Neutrons and Synchroton X-Rays, Alvor, Algarve, Portugal, March 17-27, 1987"-t.p. verso.
"Published in cooperation with NATO Scientific Affairs Division." Includes index. ISBN-13: 978-94-010-8287-7 e-ISBN-13: 978-94-009-4027-7 001: 10.1007/978-94-009-4027-7
1. Crystallography-4Angresses. 2. Pulsed neutron techniques-Congresses. 3. X-Ray crystallography-Congresses. I. Carrondo, Maria Armenia, 1948-II. Jeffrey, George A., 1915- . III. Title. IV. Series: NATO ASI series. Series C, Mathematical and physical sciences; no. 221. QD951.N38 1987 548'.3--c!c 19
Published by D. Reidel Publishing Company P.O. Box 17, 3300 AA Dordrecht, Holland
Sold and distributed in the U.S.A. and Canada by Kluwer Academic Publishers, 101 Philip Drive, Assinippi Park, Norwell, MA 02061, U.S.A.
In all other countries, sold and distributed by Kluwer Academic Publishers Group, p.o. Box 322, 3300 AH Dordrecht, Holland
87-26853 CIP
D. Reidel Publishing Company is a member of the Kluwer Academic Publishers Group
All Rights Reserved © 1988 by D. Reidel Publishing Company, Dordrecht, Holland. Softcover reprint of the hardcover 1 st edition 1988
No part of the material protected by this copyright notice may be reproduced or utilized in any form or by any means, electronic or mechanical, including photocopying, recording or by any information storage and retrieval system, without written permission from the copyright owner.
Preface
G.A. JEFFREY
G.H. LANDER
W.LF. DAVID
B. T.M. WILLIS
H. FUESS
J. B. FORSYTH
A. K. CHEETHAM
J. D. JORGENSEN
A. KVICK
W. SAENGER and C. BETZEL
P. J. BECKER
J. GOULON, M. Laos, P. FRIANT, and M. RUlz- LOPEZ
A. ALBINATI
J. PANNETIER
H. B. STUHRMANN
J. KARLE
Contents IX
- « Chemical Crystallography: Past, Present and Future» Discussion 7
- « Scientific Opportunities With Neutron Scattering" 9 Discussion 25
- « The Scope and Possibilities of Crystallography With Pulsed Neutrons» 27
Discussion 58 - « Some Aspects of Diffraction Physics With Pulsed Neutrons» 61
Discussion 75 - « Applications of Neutron Scattering in Chemistry: Pulsed and Continuous Sources in Comparison » 77
Discussion 115 - « Single Crystal Pulsed Neutron Diffraction» 117
Discussion 134 - • Pulsed Neutron Powder Diffraction» 137
Discussion 157 - « Pulsed Neutron Diffraction in Special Sample Environments» 159
Discussion 185 - « Applications of Synchrotron X-rays to Chemical CrystallograpllY " 187
Discussion 203 - « Synchrotron X-Ray and Neutron Radiation in Protein CrystallograpllY - Present and Future» 205
Discussion 216 - « Synchrotron Radiation For Electron Density Studies» 217
Discussion 244 - « Structural Applications of X-ray Absorption Spectroscopy (EXAFS and XANES) in Coordination Chemistry" 247
Discussion 292 • « Use of tile Rietveld Profile Analysis for Crystal Structure Determination and Refinement» 295
Discussion 311 - « Real-Time Neutron Powder Diffraction" 313
Discussion 355
- « Chemical Crystallography With Pulsed Neutrons and SYllcluotron Radiation» %7
Discussion :n5 - « Recent Theoretical Advances in Macromolecular Structure Determina.tion »
Discussion 379 385
vi
I.L. KARLE - « Solving Difficult Structures" 419 Discussion 441
C. RIEKEL - « Real Time Synchrotron Radiation Diffraction Experiments on Polymers" 443
H. D. BARTUNIK
P. LINDLEY
M. M. HARDING
Discussion - « Time-Resolved Applications of Synchrotron Radiation in Protein Crystallography"
Discussion - « Crystallographic Studies of Biological Macromolecules Using Synchrotron Radiation"
Discussion - « The Use of Synchrotron Radiation for Laue Diffraction and for the Study of Very Small Crystals"
Discussion FINAL PANEL DISCUSSION
Posters
C. BETZEL et al
C. BETZEL et al
P. LIGHTFOOT et al
E. HOVERSTREYDT et al
R.W. DATE etal
L. VAN MEERVELT et al
J .A. ALONSO et al
1.A. ALONSO et al W. DEPMEIER
M. PERRIN et al
P. ESTEBAN et al M. COSTA et al W. T. A. HARRISON et al
J. RODRIGUEZ et al
J. RODRIGUEZ et al
A. GlBAUD
- « Structure of Proteinase K Using Synchrotron Radiation, and Binding of two Dipeptide Chloromethyl Ketone Inhibithors to the Active Site" - « Protein CrystallograpllY Using Synchrotron Radiation at the EMBL Oustation Hamburg" - « The Structure of MnP04 .H"!.O by SynclLrotron X-ray Powder Diffraction" - « ENDIX - a Computer Program to Simulate Energy Dispersive X-ray and Syncllrotron Powder Diffraction Diagram" - « An Investigation of the Structure and Molecular Ordering of Liquid Crystal Phases" - « Relation Betwen The Crystalline Structure and the S E Phase of Vinyl - P - (PI - N - H exyloxyphenyl)benzoate " - « On TILe Influence of tiLe Non-bonded Pair of Pb(I/) in the Novel Ordered Perovskite Pb[ScodTio.2[,Tefl.2[,)I 0 3 '
- « Synthesis and Crystal Structure of Ta? Te20~ , - « Remarks on the Structures and Pilase Transitions in Aluminate Sodalites " - « Relationship Between CILemical Reactivity and Crystal Structure in the Organic Solid State" - « Study by EXAFS of Pt - Ru/ Al203 Catalysts" - « Electron Distribution in the Laves Phase, TiFe? " - « The Structure of Squaric Acid by Powder ~eutron Diffraction" - « Data Analysis in Time Resolved Powder Diffractometry , - « Phase Transition; in Sr2C020,.,: A Neutron Diffraction Study" - « A Rietveld Profile Analysis Treatment of Line-Bro<l:dening in K AlF4 layered compound"
485
487 S06
509 S36
.537
.560 S6:~
567
568
569
571
573
575
57i 579
582
583 585 586
587
589
590
592
Organizing Committee
P. Becker Laboratoire de Cristallographie, C.N.R.S., Grenoble, France
M.A. Carrondo t Centro de Qufmica Estrutural Complexo I, Instituto Superior Tecnico Lisboa, Portugal
M.B. Hursthouse Department of Chemistry, Queen Mary College, University of London, U.K
G.A. Jeffrey t
G.H. Lander
W. Saenger
t Co-Directors
Department of Crystallography University of Pittsburgh, Pittsburgh, U.S.A.
European Institut for Transuranian Elements, Karlsruhe
Institur fur Kristallographie, Freie Universitat Berlin, F .R.G.
* We deeply regret the absence of Prof. Simonetta from the Universita. di Milano, Italy, who had agreed to be a member of the Organizing Committee just before his death, in January 1986.
Preface
X-ray and neutron crystallography have played an increasingly important role in the chemical and biochemical sciences over the past fifty years. The principal obstacles in this methodology, the phase problem and computing, have been overcome. The former by the methods developed in the 1960's and just recognised by the 1985 Chemistry Nobel Prize award to Karle and Hauptman, the latter by the dramatic advances that have taken place in computer technology in the past twenty years.
Within the last decade, two new radiation sources have been added to the crystallographer's tools. One is synchrotron X-rays and the other is spallation neutrons. Both have much more powerful fluxes than the previous sources and they are pulsed rather than continuos. New techniques are necessary to fully exploit the intense continuos radiation spectrum and its pulsed property. Both radiations are only available from particular National Laboratories on a guest-user basis for scientists outside these National Laboratories.
Hitherto, the major emphasis on the use of these facilities has been in solid-state physics, and the material, engineering and biological sciences. We believe that there is equivalent potential to applications which are primarily chemical or biochemical.
We have combined synchrotron X-rays and pulsed spallation neutrons in this ASI for two reasons. One is because they have important common properties such that concepts developped by the instrumental scientists using one radiation could be useful to those using the other. The other reason is that both sources have new major facilities which have very recently become operational as for example, the Daresbury and Brookhaven dedicated X-ray synchrotrons and the Rutherford, Argonne and Los Alamos spallation neutron sources. For the near future more sources of both types are planned or in construction in Europe (ESRF), USA (6 GeV synchrotron source), Japan (ALS) and U.K. (ISIS II at RAL).
We have therefore brought to this meeting scientists who know the fundamental properties, advantages and limitations of both the pulsed neutrons and the synchrotron X-rays to interact with chemists, specially chemical crystallographers. The majority of these scientists have had no actual experience in using these national facilities. The portuguese and spanish
ix
x
scientific communities, in particular, shoul benefit not only from the lectures and tutorials but also from the opportunities to make direc~ contact with some of these instrumental scientists.
Since the participants are mainly chemists, the first part of the course had a strong educational component with emphasis on the basic physics involved in the production and use of these radiations.
The second part was aimed at discussing these techniques, at the frontiers of their applications, such as the exciting potential for real-time structural studies.
The book is organised with the lectures in the same sequence as presented. Each lecture was followed by a discussion, the main points of which are summarized after the lecture.
Prof. Jeffrey has always showed a great enthusiasm for spreading the knowledge of Chemical Crystallography among young researchers providing they are willing to learn the relevant Physics and Mathematics required to be masters of their science. He deplores the crescent trend towards "blackbox" science.
This course was designed to overcome this type of deficiency. Prof Jeffrey's long-standing love for Portugal and the Portuguese people, was the "seed" of our association on the organization of this course. The very special climate and scenary of the Algarve, particularly in the early spring, proved to be ideal for the site of the course.
Historically the sea was always an inspiration for creative ideias in the human minds. And so it was in the XV century with Infante D. Henrique, son of the Portuguese King D. Joao I, who devoted his life to the great enterprise of the Portuguese discoveries departing from the Algarve. The scientific backgrOund for these explorations was developped in Sagres, in what is now considered as one of the first Naval Research Laboratories, created by D. Henrique. Appropriately, this was chosen as the site of our excursion.
We wish to thank the sponsors, NATO Scientific Affairs Division in Brussels, and to Instituto Nacional de Investiga<;ao Cientifica, Junta Nacional de Investiga<;ao Cientifica e Tecnol6gica and Funda<;ao Calouste Gulbenkian in Lisbon, for their generous contributions.
We also thank the Organizing Committee for their help and guidance on the choice of lecturers. We are grateful to Prof. Skyes from Queen Mary
College, University of London, for the organization of the reporters and the preparation of the discussions after the lectures.
Maria Armenia Carrondo Centro de Qufmica Estrutural, Complexo I Instituto Superior Tecnico, Lisboa, Portugal
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