Ionic Soft Matter: Modern Trends in Theory and Applications
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1 Ionic Soft Matter: Modern Trends in Theory and Applications
2 NATO Science Series A Series presenting the results of scientific meetings supported under the NATO Science Programme. The Series is published by IOS Press, Amsterdam, and Springer (formerly Kluwer Academic Publishers) in conjunction with the NATO Public Diplomacy Division. Sub-Series I. Life and Behavioural Sciences IOS Press II. Mathematics, Physics and Chemistry III. Computer and Systems Science Springer (formerly Kluwer Academic Publishers) IOS Press IV. Earth and Environmental Sciences Springer (formerly Kluwer Academic Publishers) The NATO Science Series continues the series of books published formerly as the NATO ASI Series. The NATO Science Programme offers support for collaboration in civil science between scientists of countries of the Euro-Atlantic Partnership Council. The types of scientific meeting generally supported are Advanced Study Institutes and Advanced Research Workshops, and the NATO Science Series collects together the results of these meetings. The meetings are co-organized by scientists from, NATO countries and scientists from NATO s Partner countries countries of the CIS and Central and Eastern Europe. Advanced Study Institutes are high-level tutorial courses offering in-depth study of latest advances in a field. Advanced Research Workshops are expert meetings aimed at critical assessment of a field, and identification of directions for future action. As a consequence of the restructuring of the NATO Science Programme in 1999, the NATO Science Series was re-organized to the four sub-series noted above. Please consult the following web sites for information on previous volumes published in the Series Series II: Mathematics, Physics and Chemistry Vol. 206
3 Ionic Soft Matter: Modern Trends in Theory and Applications edited by Douglas Henderson Brigham Young University, Provo, U.S.A. Myroslav Holovko Institute for Condensed Matter Physics, National Academy of Sciences of Ukraine, Lviv, Ukraine and Andrij Trokhymchuk Institute for Condensed Matter Physics, National Academy of Sciences of Ukraine, Lviv, Ukraine and Brigham Young University, Provo, U.S.A. Published in cooperation with NATO Public Diplomacy Division
4 Proceedings of the NATO Advanced Research Workshop on Ionic Soft Matter: Modern Trends in Theory and Applications Lviv, Ukraine April 2004 A C.I.P. Catalogue record for this book is available from the Library of Congress. ISBN (PB) ISBN (PB) ISBN (HB) ISBN (HB) ISBN (e-book) ISBN (e-book) Published by Springer, P.O. Box 17, 3300 AA Dordrecht, The Netherlands. Printed on acid-free paper All Rights Reserved 2005 Springer No part of this work may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, microfilming, recording or otherwise, without written permission from the Publisher, with the exception of any material supplied specifically for the purpose of being entered and executed on a computer system, for exclusive use by the purchaser of the work. Printed in the Netherlands.
5 This book is dedicated to the people of the Ukraine whose devotion to freedom is undiminished in spite of a state organized famine, Nazi occupation and terror, Soviet totalitarianism, and an attempted fraudulent election.
6 Contents Dedication Preface v ix Field theoretical approach for ionic systems 1 D. di Caprio, J. Stafiej, J.P. Badiali Induced charge computation method 19 D. Boda, D. Gillespie, B. Eisenberg, W. Nonner, D. Henderson Concept of ion association in the theory of electrolyte solutions 45 M. Holovko Towards the role of the range of intermolecular interactions 83 I. Nezbeda, J. Kolafa Collective dynamics in ionic fluids 109 I. Mryglod, T. Bryk, V. Kuporov Criticality of ionic liquids in solution 143 W. Schröer Liquid-vapor criticality in Coulombic and related fluids 181 P.J.Camp,C.D.Daub,G.N.Patey Macroions in solution 199 V. Vlachy, B. Hribar Lee, J. Reščič, Yu.V. Kalyuzhnyi Anomalous small-angle X-ray scattering in rod-like polyelectrolytes 233 M. Ballauff Macroions under confinement 249 A.D. Trokhymchuk, D. Henderson, D.T. Wasan, A. Nikolov Grain interaction and ordering in a dusty plasmas 291 O. Bystrenko, T. Bystrenko, A. Zagorodny Dipolar fluid inclusions in charged matrices 315 M.J. Fernaud, E. Lomba vii
7 viii IONIC SOFT MATTER Solute ions at ice/water interface 333 A.D.J. Haymet, T. Bryk, E.J. Smith Proton transport in polymer electrolyte fuel cell membranes 361 E. Spohr DNA saline solutions near surfaces 381 B. M. Pettitt, A. Vainrub, K.-Y. Wong Charge transport in highly-radioactive substance 395 O. Zhydkov Participants 411 Index 417
8 Preface Recently there have been profound developments in the understanding and interpretation of liquids and soft matter centered on constituents with shortrange interactions. Ionic soft matter is a class of conventional condensed soft matter with prevailing contribution from electrostatics and, therefore, can be subject to possible long-range correlations among the components of the material and in many cases crucially affecting its physical properties. Among the most popular representatives of such a class of materials are natural and synthetic saline environments, like aqueous and non-aqueous electrolyte solutions and molten salts as well as variety of polyelectrolytes and colloidal suspensions. Equally well known are biological systems of proteins. All these systems are examples of soft matter strongly influenced, if not dominated, by long-range forces. For more than half of century the classical theories by Debye and Hückel as well as by Derjaguin, Landau, Verwey and Owerbeek (DLVO) have been at the basis of theoretical physical chemistry and chemical engineering. The substantial progress in material science during last few decades as well as the advent of new instrumentation and computational techniques made it apparent that in many cases the classical theories break down. New types of interactions (e.g. hydrodynamic, entropic) have been discovered and a number of questions have arisen from theoretical and experimental studies. Many of these questions still do not have definite answers. The Advanced Research Workshop (ARW) on ionic soft matter that has been held in Lviv (Ukraine) during April 14-17, 2004 under the NATO Physical and Engineering Science & Technology Programme, was dedicated to discuss some actual theoretical problems of ionic soft matter physics as well as some selected model applications of ionic media in the technological, environmental and biological processes that are governed by electrostatic forces. Our approach to gain these goals was to combine the recent advances in the understanding of ionic systems by covering various aspects from applied research to basic science. To succeed in this, the ARW brought together an international group of experts from different research sectors that includes mathematicians, physicists, chemists, biologists and engineers. ix
9 x IONIC SOFT MATTER The choice of Lviv as a host site of the Workshop was not by an accident. The traditions of physical and mathematical science in this historic Western Ukrainian city are linked to the names of Marian Smoluchowski and Stefan Banach who lived and worked in Lviv in the early and middle part of the last century. The Lviv physical school in its present form was founded by Ihor Yukhnovskii and is known as the Institute for Condensed Matter Physics. The lectures given during the ARW have provided an overview of the current state of the art on the interlaced research frontiers of ionic soft matter. Special attention has been focused on the fundamentals of ionic substances that include such important phenomena as association, adsorption, solvation, double layer, criticality, screening, thin film stability, collective dynamics and transport through biological and polymer membranes. Selected applied aspects of ionic soft matter have been discussed in details as well. These include: the behavior of ions at the ice surface and ice/water and lipid/water interfaces that is a fundamental process encountered in a wide range of biological systems and has relevance to problems in atmospheric chemistry; the proton transport properties in single pores polymer electrolyte membrane materials in order to understand those chemical and physical parameters which lead to an optimum performance in a low temperature fuel cell; the conformational, structural and dynamical features of the highly-charged macroions, polyelectrolyte chains and ionic surfactant complexes that are important for a wide range of applications ranging from drug formulations to coating materials; the charge and size selectivity of biological membranes that control a wide range biological functions; the sensitivity, specificity and the dynamic range of DNA array devices. Finally, some aspects related with the Chornobyl disaster have been included into the Workshop agenda. We would like to thank all those who contributed to this book. We also thank all the participants who attended the ARW and contributed to the success of both the meeting and this volume. We thanks the local organizers for their hospitality and profound contribution in promoting an exciting and rewarding meeting. A special thanks to Olexandre Ivankiv for his initiative at the early beginning as well as Olesya Mryglod who helped us at the final stages to prepare this book. Finally, we gratefully acknowledge the financial support of NATO under the PST.ARW grant that made the Workshop and this volume possible. DOUGLAS HENDERSON MYROSLAV HOLOVKO ANDRIJ TROKHYMCHUK
10 xi
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