Ionic Soft Matter:Modern Trends in Theory and Applications 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 Springer (formerly Kluwer Academic Publishers) III.Computer and Systems Science 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 NATOs 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. http://www.nato.int/science http://www.springeronline.com http://www.iospress.nl Series II:Mathematics,Physics and Chemistry – Vol.206 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 Proceedings of the NATO Advanced Research Workshop on Ionic Soft Matter:Modern Trends in Theory and Applications Lviv, Ukraine 14-17 April 2004 A C.I.P.Catalogue record for this book is available from the Library of Congress. ISBN-10 1-4020-3663-9 (PB) ISBN-13 978-1-4020-3663-7 (PB) ISBN-10 1-4020-3662-0 (HB) ISBN-13 978-1-4020-3662-0 (HB) ISBN-10 1-4020-3659-0 (e-book) ISBN-13 978-1-4020-3659-0 (e-book) Published by Springer, P.O.Box 17, 3300 AADordrecht, The Netherlands. www.springeronline.com 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. Thisbookisdedicatedtothe peopleoftheUkrainewhose devotiontofreedomis undiminishedinspiteofa stateorganizedfamine,Nazi occupationandterror,Soviet totalitarianism,andan attemptedfraudulent election. Contents Dedication v Preface ix Fieldtheoreticalapproachforionicsystems 1 D.diCaprio,J.Stafiej,J.P.Badiali Inducedchargecomputationmethod 19 D.Boda,D.Gillespie,B.Eisenberg,W.Nonner,D.Henderson Conceptofionassociationinthetheoryofelectrolytesolutions 45 M.Holovko Towardstheroleoftherangeofintermolecularinteractions 83 I.Nezbeda,J.Kolafa Collectivedynamicsinionicfluids 109 I.Mryglod,T.Bryk,V.Kuporov Criticalityofionicliquidsinsolution 143 W.Schröer Liquid-vaporcriticalityinCoulombicandrelatedfluids 181 P.J.Camp,C.D.Daub,G.N.Patey Macroionsinsolution 199 V.Vlachy,B.HribarLee,J.Rešcˇicˇ,Yu.V.Kalyuzhnyi Anomaloussmall-angleX-rayscatteringinrod-likepolyelectrolytes 233 M.Ballauff Macroionsunderconfinement 249 A.D.Trokhymchuk,D.Henderson,D.T.Wasan,A.Nikolov Graininteractionandorderinginadustyplasmas 291 O.Bystrenko,T.Bystrenko,A.Zagorodny Dipolarfluidinclusionsinchargedmatrices 315 M.J.Fernaud,E.Lomba vii viii IONICSOFTMATTER Soluteionsatice/waterinterface 333 A.D.J.Haymet,T.Bryk,E.J.Smith Protontransportinpolymerelectrolytefuelcellmembranes 361 E.Spohr DNAsalinesolutionsnearsurfaces 381 B.M.Pettitt,A.Vainrub,K.-Y.Wong Chargetransportinhighly-radioactivesubstance 395 O.Zhydkov Participants 411 Index 417 Preface Recently there have been profound developments in the understanding and interpretation of liquids and soft matter centered on constituents with short- range 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 ma- terial 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 so- lutions and molten salts as well as variety of polyelectrolytes and colloidal suspensions. Equallywellknownarebiologicalsystemsofproteins. Allthese systems are examples of soft matter strongly influenced, if not dominated, by long-rangeforces. 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 adventofnewinstrumentationandcomputationaltechniquesmadeitapparent thatinmanycasestheclassicaltheoriesbreakdown. Newtypesofinteractions (e.g. hydrodynamic,entropic)havebeendiscoveredandanumberofquestions havearisenfromtheoreticalandexperimentalstudies. Manyofthesequestions stilldonothavedefiniteanswers. The Advanced Research Workshop (ARW) on ionic soft matter that has beenheldinLviv(Ukraine)duringApril14-17,2004undertheNATOPhysi- calandEngineeringScience&TechnologyProgramme,wasdedicatedtodis- cuss some actual theoretical problems of ionic soft matter physics as well as someselectedmodelapplicationsofionicmediainthetechnological,environ- mentalandbiologicalprocessesthataregovernedbyelectrostaticforces. Our approachtogainthesegoalswastocombinetherecentadvancesintheunder- standingofionicsystemsbycoveringvariousaspectsfromappliedresearchto basic science. To succeed in this, the ARW brought together an international groupofexpertsfromdifferentresearchsectorsthatincludesmathematicians, physicists,chemists,biologistsandengineers. ix x IONICSOFTMATTER 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 YukhnovskiiandisknownastheInstituteforCondensedMatterPhysics. The lectures given during the ARW have provided an overview of the cur- rent 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 transportthroughbiologicalandpolymermembranes. Selectedappliedaspects ofionicsoftmatterhavebeendiscussedindetailsaswell. Theseinclude: the behaviorofionsattheicesurfaceandice/waterandlipid/waterinterfacesthat 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 opti- mum performance in a low temperature fuel cell; the conformational, struc- turalanddynamicalfeaturesofthehighly-chargedmacroions,polyelectrolyte chains and ionic surfactant complexes that are important for a wide range of applications ranging from drug formulations to coating materials; the charge andsizeselectivityofbiologicalmembranesthatcontrolawiderangebiolog- icalfunctions;thesensitivity,specificityandthedynamicrangeofDNAarray devices. Finally, some aspects related with the Chornobyl disaster have been includedintotheWorkshopagenda. 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 suc- cess of both the meeting and this volume. We thanks the local organizers for their hospitality and profound contribution in promoting an exciting and re- wardingmeeting. AspecialthankstoOlexandreIvankivforhisinitiativeatthe early beginning as well as Olesya Mryglod who helped us at the final stages topreparethisbook. Finally,wegratefullyacknowledgethefinancialsupport of NATO under the PST.ARW.979653 grant that made the Workshop and this volumepossible. DOUGLASHENDERSON MYROSLAVHOLOVKO ANDRIJTROKHYMCHUK
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