Nonlinear Dielectric Spectroscopy PDF
Preview Nonlinear Dielectric Spectroscopy
Advances in Dielectrics Series Editor: Friedrich Kremer Ranko Richert Editor Nonlinear Dielectric Spectroscopy Advances in Dielectrics Series editor Friedrich Kremer, Leipzig, Germany Aims and Scope Broadband Dielectric Spectroscopy (BDS) has developed tremendously in the last decade.Fordielectricmeasurementsitisnowstateofthearttocovertypically8–10 decades in frequency and to carry out the experiments in a wide temperature and pressure range. In this way a wealth of fundamental studies in molecular physics became possible, e.g. the scaling of relaxation processes, the interplay between rotational and translational diffusion, charge transport in disordered systems, and moleculardynamicsinthegeometricalconfinementofdifferentdimensionality—to name but a few. BDS has also proven to be an indispensable tool in modern material science; it plays e.g. an essential role in the characterization of Liquid Crystals or Ionic Liquids and the design of low-loss dielectric materials. It is the aim of ‘‘Advances in Dielectrics’’ to reflect this rapid progress with a series of monographs devoted to specialized topics. Target Group Solid state physicists, molecular physicists, material scientists, ferroelectric scientists, soft matter scientists, polymer scientists, electronic and electrical engineers. More information about this series at http://www.springer.com/series/8283 Ranko Richert Editor Nonlinear Dielectric Spectroscopy 123 Editor Ranko Richert Schoolof Molecular Sciences Arizona State University Tempe,AZ USA ISSN 2190-930X ISSN 2190-9318 (electronic) Advances in Dielectrics ISBN978-3-319-77573-9 ISBN978-3-319-77574-6 (eBook) https://doi.org/10.1007/978-3-319-77574-6 LibraryofCongressControlNumber:2018935856 ©SpringerInternationalPublishingAG,partofSpringerNature2018 Thechapter“ThirdandFifthHarmonicResponsesinViscousLiquids”islicensedunderthetermsofthe CreativeCommonsAttribution4.0 InternationalLicense(http://creativecommons.org/licenses/by/4.0/). Forfurtherdetailsseelicenseinformationinthechapter. Thisworkissubjecttocopyright.AllrightsarereservedbythePublisher,whetherthewholeorpart of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission orinformationstorageandretrieval,electronicadaptation,computersoftware,orbysimilarordissimilar methodologynowknownorhereafterdeveloped. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publicationdoesnotimply,evenintheabsenceofaspecificstatement,thatsuchnamesareexemptfrom therelevantprotectivelawsandregulationsandthereforefreeforgeneraluse. The publisher, the authors and the editors are safe to assume that the advice and information in this book are believed to be true and accurate at the date of publication. Neither the publisher nor the authorsortheeditorsgiveawarranty,expressorimplied,withrespecttothematerialcontainedhereinor for any errors or omissions that may have been made. The publisher remains neutral with regard to jurisdictionalclaimsinpublishedmapsandinstitutionalaffiliations. Printedonacid-freepaper ThisSpringerimprintispublishedbytheregisteredcompanySpringerInternationalPublishingAG partofSpringerNature Theregisteredcompanyaddressis:Gewerbestrasse11,6330Cham,Switzerland Preface Dielectricspectroscopyhasalonghistoryofcharacterizingthemagnitudeandtime or frequency dependence of the polarization that results from an external electric field.Technicaldevelopmentshavefacilitatedaccesstoabroadrangeoftimescales andfrequencies,coveringatleasttherangefrom1psto1yearintermsofobserved equilibrium relaxation times. This broadband property together with the high resolution and measurement automation have turned dielectric relaxation mea- surements into a standard tool for characterizing the dynamics of a wide range of materials by measuring the permittivity, e. In a typical experiment, polarization P = ve E is proportional to the magnitude of the applied field E, implying that the 0 susceptibilityv=e–1remainsindependentoftheamplitudeoftheelectricfield.In fact, many experimental reports do not specify the field amplitude, because it is consideredirrelevantfortheresults.Atsufficientlyhighelectricfields,however,the dielectric behavior will depend on the field magnitude in this nonlinear regime. The term “nonlinear dielectric effect” refers to any signature of deviations from the linear correlation between polarization P and external electric field E. The interestinstudyingsuchnonlinearfeaturesgoesbacktoP.Debyeandhisbookon Polar Molecules published in 1929. At the time, only dielectric saturation was a known nonlinear effect, observed as a reduction in the amplitude of permittivity. About 10 years later, the chemical effect was recognized by Piekara, which amounted to an increase in amplitudes. Subsequently, it has been discovered that also time constants can be affected by high fields, leading to accelerated or frus- trated dynamics, depending on the type offield used, alternating versus static. The slowing down of dielectric relaxation by static electric fields in simple liquids was not discovered until 2014. In recent years, tremendous advances have been made regardingboththehigh-resolutionmeasurementsofnonlineardielectriceffectsand their understanding in terms of theoretical and modeling approaches. The aim of this book is to introduce the ideas and concepts of Nonlinear Dielectric Spectroscopy, outline its history, and provide insight into the present state of the art of the experimental technology and understanding of nonlinear dielectric effects. Emphasis will be on what can be learned from nonlinear exper- iments that could not be derived from the linear counterparts. It will become clear v vi Preface that nonlinear dielectric spectroscopy can be used as a tool to measure structural recoveryorphysicalaging,aswellaspotentialconnectionsbetweendynamicsand thermodynamicvariablessuchasenthalpyandentropy.Supercooledliquidsintheir viscousregimeareidealcandidatesforinvestigatingnonlineareffects,becausethey are particularly sensitive to changes in temperature, and are thus expected to be sensitive to changes in the electric field. Other interesting materials to be covered are plastic crystals and complex liquids near criticality. It is also to be pointed out that, compared with other techniques such as mechanical shear experiments, the nonlinearregime of dielectric spectroscopyis special inthesense that theenergies involved always remain small compared with thermal energies. Theoreticalapproachestononlineareffectsareparticularlycomplicatedbecause the tools available for the linear regime no longer apply. As a result, there is no single generally accepted theory regarding nonlinear dielectric responses of real liquids.Variousapproachestononlineardielectricfeatureshavebeenreported,and thedifferentaspectswillbecommunicatedinthefirstthreechapters.Theremaining chapters focus more on the experimental aspects, involving different experimental techniques and a range of materials such as liquids, supercooled liquids, plastic crystals, electrolytes, ionicliquids, and polymeric materials.The reader will notice that the contributions will offer different or even conflicting views on how to interpret the results observed with nonlinear dielectric spectroscopy. This feature reflects the present state of research activities, indicating that this field still bears numerousunresolvedquestionsthatwarrantfurtherresearchonnonlineardielectric spectroscopy for years to come. The editor is grateful to all the contributors to this volume for a smooth and effective collaboration on this joint project. Support from the staff of Springer and from the Series Editor, F. Kremer, is also gratefully acknowledged. Tempe, USA Ranko Richert January 2018 Contents Nonlinear Dielectric Response of Polar Liquids . . . . . . . . . . . . . . . . . . . 1 Dmitry V. Matyushov Nonlinear Dielectric Relaxation in AC and DC Electric Fields. . . . . . . . 35 P. M. Déjardin, W. T. Coffey, F. Ladieu and Yu. P. Kalmykov Stochastic Models of Higher Order Dielectric Responses . . . . . . . . . . . . 75 Gregor Diezemann Effects of Strong Static Fields on the Dielectric Relaxation of Supercooled Liquids. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101 Ranko Richert Nonresonant Spectral Hole Burning in Liquids and Solids . . . . . . . . . . 127 Ralph V. Chamberlin, Roland Böhmer and Ranko Richert Nonlinear Dielectric Effect in Critical Liquids . . . . . . . . . . . . . . . . . . . . 187 Sylwester J. Rzoska, Aleksandra Drozd-Rzoska and Szymon Starzonek Third and Fifth Harmonic Responses in Viscous Liquids . . . . . . . . . . . 219 S. Albert, M. Michl, P. Lunkenheimer, A. Loidl, P. M. Déjardin and F. Ladieu Dynamic Correlation Under Isochronal Conditions . . . . . . . . . . . . . . . . 261 C. M. Roland and D. Fragiadakis Nonlinear Dielectric Response of Plastic Crystals. . . . . . . . . . . . . . . . . . 277 P. Lunkenheimer, M. Michl and A. Loidl Nonlinear Ionic Conductivity of Solid Electrolytes and Supercooled Ionic Liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 301 B. Roling, L. N. Patro and O. Burghaus vii viii Contents Nonlinear Oscillatory Shear Mechanical Responses . . . . . . . . . . . . . . . . 321 Kyu Hyun and Manfred Wilhelm Index .... .... .... .... .... ..... .... .... .... .... .... ..... .... 369 Nonlinear Dielectric Response of Polar Liquids DmitryV.Matyushov Abstract Thelineardielectricconstantofapolarmolecularmaterialismostlythe functionofthemoleculardipolemomentandofthebinarycorrelationsbetweenthe dipoles.Thedielectricresponsebecomesnonlinearforasufficientlystrongelectric fieldgainingadielectricdecrementproportional,inthelowestorder,tothesquared field magnitude. The alteration of the dielectric response with the electric field is governed by a combination of binary and three- and four-particle dipolar correla- tions and thus provides new structural information absent in the linear response. Similarhigherordercorrelationsbetweenthemoleculardipolesenterthetempera- turederivativeofthelineardielectricconstant.Mean-fieldmodels,oftenappliedto constructtheoriesoflineardielectricresponse,failtoaccountforthesemulti-particle correlations and do not provide an adequate description of the nonlinear dielectric effect.Perturbationtheoriesofpolarliquidsofferapotentialresolution.Theyhave shownpromiseindescribingtheelevationoftheglasstransitiontemperaturebyan externalelectricfield.Theapplicationofsuchmodelsrevealsafundamentaldistinc- tioninpolarizationoflow-temperatureglassformersclosetotheglasstransitionand high-temperature,low-viscousliquids.Thedielectricresponseoftheformerisclose totheprescriptionofMaxwell’selectrostaticswheresurfacechargeiscreatedatany dielectric interface. On the contrary, rotations of interfacial dipoles are allowed in high-temperatureliquids,andtheyeffectivelyaveragethesurfacechargeouttozero. Modelscapturingthisessentialphysicswillberequiredforthetheoreticaldescription ofthenonlineardielectriceffectinthesetwotypesofpolarmaterials. 1 Introduction Thischapterdiscussestheoreticalapproachestononlinearresponseofpolarmaterials totheexternallyappliedelectricfield.Thedomainoflineartheoriesislimitedbythe assumptionofalinearscalingofthemacroscopicdipolemomentMwiththeapplied B D.V.Matyushov( ) DepartmentofPhysicsandSchoolofMolecularSciences, ArizonaStateUniversity,POBox871504,Tempe,AZ85287,USA e-mail:[email protected] ©SpringerInternationalPublishingAG,partofSpringerNature2018 1 R.Richert(ed.),NonlinearDielectricSpectroscopy,AdvancesinDielectrics https://doi.org/10.1007/978-3-319-77574-6_1
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