Table Of ContentChemical Physics
of Intercalation II
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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
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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
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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
