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Chemical Physics of Intercalation II 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 New York and London C Mathematical and Physical Sciences Kluwer Academic Publishers D Behavioral and Social Sciences Dordrecht, Boston, and London E Applied Sciences F Computer and Systems Sciences Springer-Verlag G Ecological Sciences Berlin, Heidelberg, New York, London, H Cell Biology Paris, Tokyo, Hong Kong, and Barcelona I Global Environmental Change Recent Volumes In this Series Volume 302-Microwave Discharges: Fundamentals and Applications edited by Carlos M. Ferreira and Michel Moisan Volume 303-Particle Production in Highly Excited Matter edited by Hans H. Gutbrod and Johann Rafelski Volume 304 -Growth Patterns in Physical Sciences and Biology edited by Juan-Manuel Garcia-Ruiz, Enrique Louis, Paul Meakin, and Leonard M. Sander Volume 305 -Chemical Physics of Intercalation II edited by Patrick Bernier, John E. Fischer, Siegmar Roth, and Stuart A. Solin Volume 306-lonization of Solids by Heavy Particles edited by Raul A. Baragiola Volume 307 -Negative Differential Resistance and Instabilities in 2-D Semiconductors edited by N. Balkan, B. K. Ridley, and A. J. Vickers Volume 308 - Photonic Band Gaps and Localization edited by C. M. Soukoulis Series 8: Physics Chemical Physics of Intercalation II Editedby Patrick Bernier Universite de Montpellier Montpellier, France John E. Fischer University of Pennsylvania Philadelphia, Pennsylvania Siegmar Roth Max-Planck-Institute fOr FestkOrperforschung Stuttgart, Germany and Stuart A. Solin NEC Research Institute Princeton, New Jersey SPRINGER SCIENCE+BUSINESS MEDIA LLC 1 Proceedings of the Second NATO Advanced Study Institute on Chemical Physics of Intercalation, held June 2!hJuly 9, 1992, at the Chateau de Bonas, France NATO-PCO-DATA BASE The electronic index to the NATO ASI Series provides full bibliographical references (with keywords ancl/or abstracts) to more than 30,000 contributions from international scientists published in aII sections of the NATO ASI Series. Access to the NATO-PCO-DATA BASE is possible in two ways: -via online FILE 128 (NATO-PCO-DATA BASE) hosted by ESRIN, Via Galileo Galilei, 1-00044 Frascati, Italy -via CD-ROM "NATO-PCO-DATA BASE" with user-friendly retrieval software in English, French, and German (©WTV GmbH and DATAWARE Technologies, Inc. 1989) The CD-ROM can be ordered through any member of the Board of Publishers or through NATO-PCO, Overijse, Belgium. Library of Congress Cataloging-in-Publication Data Chemleal physies of lnterealatlon II I edited by Patrlek Bernler ... [et a1.]. p. em. -- (NATD ASI serles. Serles B. Physles ; v. 3051 Includes blbl 10graphlcal references and lndex. ISBN 978-14613-6234-0 ISBN 978-1-4615-2850-0 (eBook) DOI 10.1007/978-1-4615-2850-0 1. Clathrate compounds--Congresses. r. Bernler. Patrlck. II. Tltle, Chemleal physles of lnterealation two. III. Serles. Q0474.C475 1994 541.2·242--de20 93-17706 CIP Additional material to this book can be downloaded from http://extra.springer.com. ISBN 978-1-4613-6234-0 ©1993 Springer Science+Business Media New York Originally published by Plenum Press in 1993 Softcover reprint of the hardcover 1s t edition 1993 AII rights reserved No part of this book may be reproduced, stored in retrieval system, or transmitted in any format or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written permission from the Publisher PREFACE This volume provides a record of the second ASI on the subject "Chemical Physics of Intercalation", which was patterned after its highly successful July 1987 predecessor. A growing community of chemists, physicists and materials scientists has come to appreciate the utility of extending the intercalation concept to generic guest-host compounds and solid solutions. The unifying themes are the complex phase equilibria which result from the competition between repulsive and attractive interactions between and within the guest and host substructures, the tunability of properties by control of guest concentration and superlattice periodicity, and the broad spectrum of potential applications which these materials may provide. The success of this initiative may be judged by noting the enlarged scope of materials covered in this volume as compared to its predecessor. The present volume covers the spectrum from 3-dimensional oxides, 2-dimensional classical layer intercalates, 1- dimensional doped polymers and zero-dimensional doped fullerene lattices. Hybrid systems such as polymers in layer hosts and nonporous hosts are also treated. Several chapters provide global unifying viewpoints by focussing on sold state chemical aspects, transport and optical properties, the occurrence of superconductivity, etc. The success of the ASI was due in large part to the efforts of the Association Scientifique Culturelle et Educative de Bonas, directed by M. Stockmann, and to the tireless efforts of Dr. Michele Ribet in handling administrative details. Although mainly supported by NATO, important financial assistance was also provided by the Centre Nationale de la Recherche Scientifique, the Ministere des Affairs Etrangeres, the french company M.G.P. I.S.A.R, the Max Planck Gesellschaft, the National Science Foundation and NEC Research Inc. P. Bernier J.E. Fischer S. Roth S.A. Solin v CONTENTS PART A. THE LECTURES Host Structures Modifications Induced by IntercalationlDeintercalation into Lamellar Chalcogenides .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 1 G.Ouvrard Superconducting Intercalation Compounds of C and Graphite . . . . . . . . . . . . .. 31 60 K. Liiders Conjugated Polymers in Layered Hosts: Formation of Emeraldine Salt and Polyfuran in FeOCI ............................................. 63 M.G. Kanatzidis, C.-G. Wu, D.C. DeGroot, J.L. Schindler, M. Benz, E. LeGoff and C.R. Kannewurf Alkali Metal Compounds of C an Intercalation Perspective ............... 73 60: D. W. Murphy and M.l Rosseinsky Staging in Intercalated Graphites, Polymers and Fullerenes . . . . . . . . . . . . . . . .. 93 EJ. Mele Synthesis and Reaction Chemistry of Layered Oxides with Perovskite Related Structures ........................................... 117 AJ. Jacobson Size-Mismatch Effects in Alloys .................................. 141 M.F. Thorpe and S.D. Mahanti The Structure, Morphology and Layer Rigidity of Clay Intercalation Compounds 161 SA Solin PART B. SEMINARS AND COMMUNICATIONS Electrochemical Spectroscopy and In-Situ Diffraction Studies of Intercalation Compounds ........................................ " 181 Y. Chabre VII Size-Mismatch Melting in Two Dimensions 193 N. Mousseau and M.F. Thorpe Tight-Binding Molecular Dynamics for Intercalation Chemistry. . . . . . . . . . . .. 197 M. Menon, J. Tang and K.R. Subbaswamy Quantum Chemical Calculations of C Vibrational Frequencies and Electronic 60 States ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 201 F. Negri, G. Orlandi and F. Zerbetto Electron Correlations and Electron-Lattice Coupling in C 209 60 G. Stollhoff and H. Scherrer Local Oscillator Model for Superconducting Fullerenes 219 Z. Gedik and S. Ciraci Some Optical Properties of Fullerenes .............................. 223 B. Friedman Electron Pair Transfer in A C 227 3 60 •.••.••••••••••••• • • • • • • • • • • • • • • • •• S. Larsson C Interaction with GaAs and Bi ................................. 223 60 U. del Pennino, S. Gozzi and P. Rudolf Photoluminescence of Solid State Fullerenes . . . . . . . . . . . . . . . . . . . . . . . . .. 239 H.J. Byre, W.K. Maser, W.W. Ruhle, A Mittelbach, W. Honle, H.G.v. Schnering, B. Movaghar and S. Roth Electronic Properties of MC as Seen by N.M.R. and E.P.R. and Compared to x 60 Graphite Intercalation Compounds .......................... 243 J. Conard Magnetic Properties of Alkali Metal Intercalated Fullerides . . . . . . . . . . . . . . .. 251 P. Byszewski, E. Kowalska and S. Kolesnik Electrochemical and X-Ray Diffraction Studies of the LiC System ......... 255 60 D. Djurado, M. Barral, Y. Chabre and J.E. Fischer Characterization of K-Doped C Using Positrons 261 60 S. Ishibashi, N. Terada and M. Tokumoto Superconductivity and ESR in Cesium-Doped C 265 60 •••••••••••••••••••••• N. Kinoshita, Y. Tanaka, M. Tokumoto and S. Matsumiya Magnetic Properties of Halogen Doped C 269 60 • . • • • • • • . • • • • • • • • • • • • • • • • •• H. Sekine, H. Maeda, M. Kosuge, Y. Tanaka and M. Tokumoto The Electromagnetic Properties of Conducting Polymers and Intercalated C60 ••• 273 e.o. W.P. Lee, E.B. Park, Yoon, AA Ovchinnikov and Y.W. Park VIII Domain Structures in Heavily Alkali-Metal Doped Poly(p-phenylene vinylene) .. 283 MJ. Winokur, P. Davis and D. Chen Charge Transport and Percolation in Conducting Polymers . . . . . . . . . . . . . . .. 291 J. Voit Synthesis, P and N Doping of Highly Oriented Poly acetylene HOPA . . . . . . . .. 299 D. Begin, F. Saldi, M. Lelaurian and D. Billaud Overview on the Chemistry of Intercalation into Graphite of Binary Metallic Alloys. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 303 P. Lagrange Study of FeCl3 and CoC1 Graphite Intercalation Compounds Reduced by Heavy Alkali 2 Metal Vapor ......................................... 311 C. Herold, J.-F. Mareche and G. Furdin Non-Redox Intercalation into the MPS3 Lamellar Materials: Chemistry and Physical Properties ........................................... 315 R. Clement, I. Lagadic, A. Uaustic, J.P. Audiere and L. Lomas Mineralomimetic Inclusion Behavior of Cadmium Cyanide Systems 325 T. Iwamoto, T. Kitazawa, S.-I. Nishikiori and R. Kuroda Modification of the Near Surface Properties of Layered Semiconducting Compounds by Ion Implantation .................................... 333 O. Amir and E. Lifshitz Intercalation Pressure, Application to Lix TiS 339 2 I. Samaras, C. Julien and M. Balkanski Intercalation by K, Cs, Ba, Pt, Si and C Atoms of the Graphite Monolayer on the Surface of Metals and its Mechanism . . . . . . . . . . . . . . . . . . . . . . .. 343 A. Y. Tontegode Optical and Electrical Investigation of Rare Earth Substituted YIB~CU307.0 Ceramics and Single Crystals .................................... 339 E. Holzinger-Schweiger, F. Meghdadi, G. Leising and H. Kahlert Mercury Intercalation in Titanium and Tantalum Disulfides 351 P. Moreau and G. Ouvrard Li Diffusion in Stage 2 Li-Graphite Intercalation Compounds Studied with Quasielastic Neutron Scattering .......... . . . . . . . . . . . . . . . . . . . . . . . . . .. 355 H.J. Kim, A. Magerl, J.E. Fischer, D. Vaknin, P. Heitjans and A. Schirmer Electron Transport in Bi2Se3 Intercalated with Hydrazine and Phenyl-Hydrazine 361 E. Hatzikraniotis, K. Chrissafis and K.M. Paraskevopoulos IX Infrared Spectroscopic Evidence for Mixed Valency in CdzP2S6{cobaltocene}o8 . 365 D.G. Clerc and D.A Cleary Intercalation Complexes of Kaolinite and Ethylenediamine: Structure and Bonds with the Lattice of Two Ethylene-Diamine Conformers ............... 369 T. Slonka Catalytic Oxidation of Sulphide Ions on MoS2 by Intercalation Mechanism .... 375 A Andreev, K. Kirilov, V. Ivanova, L. Prahov and E. Manova Synthesis and Characterization of the First Organosulfur Electron Donor Intercalates of the Metal Dicha1cogenides and Dihalides ..................... 379 T.E. Sutto, B.A Averill and J.-M. Fabre Intercalation of Mercury into IT-TaS and 2H-TaS2: a combined TDPAC and X-Ray 2 Study .............................................. 383 P. Ganal, W. Olberding, T. Butz and G. Ouvrard Oxidation of Synthetic Annite Mica Characterized by 57Fe Mossbauer Spectroscopy: Hydrogen De-Intercalation and Host-Layer Valence State Populations . 387 LA.D. Christie, D.G. Rancourt, H. Kodama, E. Murad and J.-L. Robert Specific Heat of the High Tc Organic Superconductor K-(EThCu[N(CN)2]Br ... 393 V.N. Kopylov and AV. Palnichenko Electrical Properties of Oxyethylene Intercalated Compounds .............. 397 P. Aranda, B. Casal, J.e. Galvan and E. Ruiz-Hitzky Index. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 401 x HOST STRUCTURES MODIFICATIONS INDUCED BY INTERCALATION/DEINTERCALAT lON INTO LAMELLAR CHALCOGENIDES GuyOuvrard Institut des Materiaux de Nantes, UMR 110 CNRS Laboratoire de Chimie des Solides 2 rue de la Houssiniere 44072 Nantes Cedex 03, France INTRODUCTION Intercalation process in two dimensional dichalcogenides has been extensively studied for more than twenty years. Many reviews have been written concerning this peculiar chemical reaction focussing on the electronic and structural modifications induced by in tercalation 1-4. The first evidence of structural change is the pristine cell parameters modification. These modifications can be related to the size of the guest species, the width of the van der Waals gap and the nature of the site occupied by intercalated entity, generally octahedron or trigonal prism. In many cases the host slabs modify their close-packed stacking in order to present the suitable coordination around the guest species. This is done by a rigid gliding of the MX2 layers, involving low energy processes due to the van der Waals nature of the sulfur-sulfur bonds between the sheets. These structural modifications, taking into account the chalcogen stacking mode between adjacent slabs, have been well explained by ionicity-structure considerations5. It has been shown, at least for alkali metal intercalation, that the structure of the intercalated phase can be related to the alkali metal cationic size and the ionicity of the bonds. Other structural considerations have been done about the staging phenomenon, explained in terms of minimization of repulsive forces between intercalated cations, both within the occupied van der Waals gap and through the slabs6. Finally it has been shown 7 that, for some specific compositions of the intercalates AxMX2 (x= 1/4, 1/3, 1/2, 2/3 ... ), the cationic repulsion between intercalated species induces a special ordering resulting in superstructures. The AxMX2 (A=alkali metal, X=S,Se) intercalates structures are thus clearly related to guest cation A size, electronegativity and concentration, the host structure itself remaining quasi-unaltered as compared to the pristine layer. This is so because, in agreement with the band structures, reduction of the MX2 phase takes place on the M cation which goes from the high oxidation state of IV, very stable in its environment, to the oxidation state of III or more seldom II, still a fairly stable state in the same coordination site. It is only recently that drastic host structure modifications involving cationic displacement with or without coordination Chemical Physics of Intercalation II, Edited by P. Bernier et al., Plenum Press, New York, 1993
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