Partially Ordered Systems Editor in Chief: L. Lam San Jose State University San Jose, California, USA

Editorial Board: E. Guyon D. Langevin Ecole Normale Superieure Laboratoire de Physique ENS Paris, France Paris, France H.E. Stanley Boston University Boston, Massachusetts, USA

Advisory Board: J. Charvolin W. Helfrich Institut Laue-Langevin Freie Universitat Grenoble, France Berlin, Germany P.A. Lee J.D. Litster Massachusetts Institute of Massachusetts Institute of Technology Technology Cambridge, Massachusetts, USA Cambridge, Massachusetts, USA D.R. Nelson M. Schadt Harvard University ROLIC Research Ltd Cambridge, Massachusetts, USA Allschwil, Switzerland

Springer New York Berlin Heidelberg Barcelona Heinz-Siegfried Kitzerow Christian Bahr Editors

Chirality in Liquid Crystals

Foreword by Sivaramakrishna Chandrasekhar

With 326 Illustrations Heinz-Siegfried Kitzerow Christian Bahr Department of Chemistry Institute of Physical Chemistry University of Paderborn University of Marburg Warburger Strasse 100 Hans-Meerwein-Strasse D-33098 Paderborn D-35032 Marburg Germany Germany [email protected] [email protected]

Editorial Board: Lui Lam Dominique Langevin Department of Physics Laboratoire de Physique des Solides San Jose State College Batiment 510 One Washington Square Universite Paris Sud San Jose, CA 95192 F-91405 Orsay USA France

Etienne M. Guyon H. Eugene Stanley EÂ cole Normale SupeÂrieure Center For Polymer Studies 45 Rue D'Ulm Physics Department F-75005 Paris Boston University France Boston, MA 02215 USA

Library of Congress Cataloging-in-Publication Data Chirality in liquid crystals / editors, Heinz-Siegfried Kitzerow, Christian Bahr. p. cm. Ð (Partially ordered systems) Includes bibliographical references and index. ISBN0-387-98679-0 (hard cover : alk. paper) 1. Liquid crystals. 2. Chirality. I. Kitzerow, Heinz-Siegfried. II. Bahr, Christian. III. Series. QD923.C55 2001 5410.04229Ðdc21 99-052790

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Springer-Verlag New York Berlin Heidelberg A member of BertelsmannSpringer Science‡Business Media GmbH This book is dedicated to Prof. Gerd Heppke with respect and kind regards. Foreword

It is indeed a pleasure for me to write the foreword for this volume brought out in honor of Prof. Gerd Heppke to felicitate him on his reaching sixty years of age. It comprises a collection of papers by friends and admirers on the broad theme of chirality in liquid crystals, which is an area of current interest and one in which Prof. Heppke himself has made signi®cant contributions. A Berliner by birth, Prof. Heppke has been associated with the Technical University Berlin for over thirty-®ve years in various capacities. After his Ph.D. and Habilitation, he became, successively, Assistant Professor (1972), Professor of Physical Chemistry (1982), Chairman of the University Research Area ``Liquid Crystals and Their Electrooptic Applications'' (1981±86), and Vice-Chairman of the Special Research Area ``Anisotropic Fluids,'' sup- ported by the Deutsche Forschungsgemeinschaft (1987±98). During this period he played a vital role in laying the foundation for a strong interdis- ciplinary thrust area involving some twenty research projects from di¨erent laboratories. Prof. Heppke is an editor of the journal Molecular Crystals and Liquid Crystals and is a nonexecutive director of the International Liquid Crystal Society. His research interests cover diverse aspects of liquid crystal science, as can be judged from his many publications (nearly two hundred) on the subject. The range of his contributions include: the polymorphic forms of smectic phases and the topology of their phase diagrams, critical and multicritical points, reentrant nematics, guest-host e¨ect, dual frequency addressable mixtures, optical storage e¨ects, determination of the screw sense of choles- terics, electric ®eld e¨ects in blue phases, chiral dopants with extremely high helical twisting power, ferroelectrics with very high spontaneous polariza- tion, antiferroelectric phases, electroclinic e¨ect, electromechanical e¨ect, electrooptic e¨ect in nematic discotics, selective re¯exion and blue phases in chiral discotics, ferroelectric columnar phases, banana shaped molecules, etc. He has organized several international conferences on liquid crystals and edited their proceedings. As a teacher and research guide, he has been the supervisor of numerous diploma and Ph.D. research students, several of whom have been recipients of awards and prizes for their excellent work

vii viii Foreword

(for example, one of his students, Dr. Christian Bahr, received the Glenn H. Brown Award for the synthesis and study of ferroelectric compounds exhibiting very high spontaneous polarization). Apart from his own personal research interests, one of Prof. Heppke's major achievements has been the part he has played in initiating inter- national exchange between his team at the Technical University Berlin and other liquid crystal groups throughout the world. Over the years, the TU group has had active collaboration and scienti®c exchange with the Raman Research Institute, Bangalore, India; the Universite Paris-Sud at Orsay; the Universite Montpellier II; the Massachussetts Institute of Technology; the University of Jammu, India; the Naval Research Laboratory, Washington DC; the University of Hawaii, USA; the University of Goteborg, Sweden; the University of Hull, UK; and research centers at Moscow, Tbilisi, and other places. It would be no exaggeration to say that all those who partici- pated in this program were without exception very much impressed by the kindness and hospitality extended to them by Prof. Heppke and his co- workers, and they also found the visits to be extremely useful scienti®cally. Finally, it remains for me to express on behalf of all the contributors to this volume, colleagues and friends, our warmest greetings to Gerd Heppke on the occasion of his sixtieth birthday and to wish him many more fruitful and active years ahead.

Sivaramakrishna Chandrasekhar Centre for Liquid Crystal Research Bangalore, India Preface

The existence or nonexistence of mirror symmetry plays an important role in nature. The lack of mirror symmetry, called chirality, can be found in sys- tems of all length scales, from elementary particles to macroscopic systems. Due to the collective behavior of the molecules in liquid crystals, molecular chirality has a particularly remarkable in¯uence on the macroscopic physical properties of these systems. Probably, even the ®rst observations of thermo- tropic liquid crystals by Planer (1861) and Reinitzer (1888) were due to the conspicuous selective re¯ection of the helical structure that occurs in chiral liquid crystals. Many physical properties of liquid crystals depend on chir- ality, e.g., certain linear and nonlinear optical properties, the occurrence of ferro-, ferri-, antiferro- and piezo-electric behavior, the electroclinic e¨ect, and even the appearance of new phases. In addition, the majority of optical applications of liquid crystals is due to chiral structures, namely the ther- mochromic e¨ect of cholesteric liquid crystals, the rotation of the plane of polarization in twisted nematic liquid crystal displays, and the ferroelectric and antiferroelectric switching of smectic liquid crystals. The intention of this book is to give an overview of the main aspects of chirality in liquid crystals, and to point out some of the open questions of current research. A complete description of this important subject within one volume is hardly possible. Thus, we have asked some experts to give a review of their ®eld of interest rather than collecting all aspects in a lexical manner. We hope that the following chapters give a representative impression of the interesting questions that are being investigated in the ®eld of chiral liquid crystals, even if some pieces are missing. We thank all authors who contributed to this book for their pleasant cooperation, and are very grateful to Prof. Chandrasekhar for his kindness in writing the foreword. Thomas von Foerster, Jeannette Mallozzi, Michael Koy, Keisha Franklin, Jerome Basma, and Springer-Verlag deserve our thanks for their valuable collaboration in publishing this volume. Gratefully, we appreciate the support by our colleagues who have agreed to the repro- duction of previously published data, and would like to thank all those who did not hesitate to send us photographs and diagrams for the purpose

ix x Preface of reproduction. We express our thanks to Mrs. Marlies Kensbock and Mrs. Isabella Koralewicz, who helped considerably in the editing process by keeping track of the manuscripts, assisting in the correspondence, and writing the table of contents. In addition, we thank Mrs. Gisela JuÈnnemann, Mrs. Susanne Keuker-Baumann, and Mrs. Claudia Stehr for their assistance in searching articles from the literature and drawing some of the ®gures. Gratefully, we acknowledge Dr. Janusch Partyka's help, who assisted in the handling of computer ®les and gave some valuable hints on typographical errors in the ®nal manuscript. Prof. Gerd Heppke, our teacher and former adviser, has made numerous contributions to the ®eld of chiral liquid crystals. The great merits of his hitherto existing works are addressed in the foreword by Prof. Chandra- sekhar. Thanks to Prof. Heppke's enthusiasm we are working in this ®eld, and thanks to his teaching and advice we were able to accumulate our knowledge of this interesting subject. On the occasion of his sixtieth birth- day, we would like to dedicate this book to Prof. Heppke. On behalf of his current and former students and co-workers, we take this opportunity to express our gratitude and appreciation, our congratulations on his birthday, and best wishes for his forthcoming activities.

Christian Bahr and Heinz-Siegfried Kitzerow Contents

Foreword vii Sivaramakrishna Chandrasekhar Preface ix Christian Bahr and Heinz-Siegfried Kitzerow Contributors xiii

1 Introduction 1 Heinz-Siegfried Kitzerow and Christian Bahr 2 Classroom Experiments with Chiral Liquid Crystals 28 Pawel Pieranski 3 From a Chiral Molecule to a Chiral Anisotropic Phase 67 Hans-Georg Kuball and Tatiana HoÈfer 4 Chemical Structures and Polymorphism 101 Volkmar Vill 5 Cholesteric Liquid Crystals: Defects and Topology 115 Oleg D. Lavrentovich and Maurice Kleman 6 Cholesteric Liquid Crystals: Optics, Electro-optics, and Photo-optics 159 Guram Chilaya 7 Blue Phases 186 Peter P. Crooker 8 Smectic Liquid Crystals: Ferroelectric Properties and Electroclinic E¨ect 223 Christian Bahr 9 Smectic Liquid Crystals: Antiferroelectric and Ferrielectric Phases 251 Hideo Takezoe and Yoichi Takanishi

xi xii Contents

10 Twist Grain Boundary Phases 296 Heinz-Siegfried Kitzerow

11 Columnar Liquid Crystals 355 Harald Bock 12 Some Aspects of Polyemer Dispersed and Polymer Stabilized Chiral Liquid Crystals 375 Gregory P. Crawford, Daniel SvensÏek, and Slobodan ZÏ umer 13 Chirality in Liquid Crystal Elastomers 433 Peter Stein and Heino Finkelmann 14 Phase Chirality of Micellar Lyotropic Liquid Crystals 447 Karl Hiltrop 15 Traveling Phase Boundaries with the Broken Symmetries of Life 481 Patricia E. Cladis

Index 495 Contributors

Christian Bahr Institute of Physical Chemistry, University of Marburg, D-35032 Marburg, Germany

Harald Bock Centre de Recherche Paul Pascal, F-33600 Pessac, France

Sivaramakrishna Chandrasekhar (Foreword) Centre for Liquid Crystal Research, Bangalore, India

Guram Chilaya Institute of Cybernetics, Academy of Sciences of Georgia, 380086 Tbilisi, Georgia

Patricia E. Cladis Advanced Liquid Crystal Technologies, Inc., Summit, NJ 07902-1314, USA

Gregory P. Crawford Division of Engineering, Brown University, Providence, Rhode Island 02912, USA

Peter P. Crooker Dept. of Physics and Astronomy, University of Hawaii, Honolulu, HI 96822, USA

Heino Finkelmann Institute of Macromolecular Chemistry, University of Freiburg, D-79104 Freiburg, Germany

Karl Hiltrop Physikalische Chemie, UniversitaÈt-GH Paderborn, D-33098 Paderborn, Germany

Tatiana HoÈfer Physikalische Chemie, UniversitaÈt Kaiserslautern, D-67663 Kaiserslautern, Germany

Heinz-S. Kitzerow Department of Chemistry, University of Paderborn, D-33098 Paderborn, Germany

xiii xiv Contributors

Maurice Kleman Laboratoire de Physique des Solides, Universite Paris-Sud, F-91405 Orsay, France

Hans-Georg Kuball Lehrstuhl fuÈl Physikalische Chemie, UniversitaÈt Kaiserslautern, D-67663 Kaisers- lautern, Germany

Oleg D. Lavrentovich Chemical Physics Interdisciplinary Program, Liquid Crystal Institute, Kent State University, Kent, Ohio 44242-0001, USA

Pawel Pieranski Laboratoire de Physique des Solides, Universite Paris-Sud, F-91405 Orsay, France

Peter Stein Institute of Macromolecular Chemistry, University of Freiburg, D-79104 Freiburg, Germany

Daniel SvensÏek Department of Physics, University of Ljubljana, 1000 Ljubljana, Slovenia

Yoichi Takanishi Department of Organic and Polymeric Materials, Tokyo Institute of Technology, Tokyo 152-8552, Japan

Hideo Takezoe Department of Organic and Polymeric Materials, Tokyo Institute of Technology, Tokyo 152-8552, Japan

Volkmar Vill Institut fuÈr Organische Chemie, UniversitaÈt Hamburg, D-20146 Hamburg, Germany

Slobodan ZÏ umer Physics Department, University of Ljubljana, 1000 Ljubljana, Slovenia