Table Of ContentIonic Soft Matter:Modern Trends
in Theory and Applications
NATO Science Series
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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.
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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
Description:Recently there have been profound developments in the understanding and interpretation of liquids and soft matter centered on constituents with sho- range interactions. Ionic soft matter is a class of conventional condensed soft matter with prevailing contribution from electrostatics and, therefore,
