Molecular Nano Dynamics Edited by Hiroshi Fukumura, Masahiro Irie, Yasuhiro Iwasawa, Hiroshi Masuhara, and Kohei Uosaki Related Titles Matta,C. F.(ed.) Quantum Biochemistry 2010 ISBN:978-3-527-32322-7 Meyer, H.-D., Gatti,F.,Worth, G.A.(eds.) Multidimensional Quantum Dynamics MCTDHTheoryandApplications 2009 ISBN:978-3-527-32018-9 Reiher,M.,Wolf,A. Relativistic Quantum Chemistry TheFundamentalTheoryofMolecularScience 2009 ISBN:978-3-527-31292-4 Höltje,H.-D., Sippl, W.,Rognan, D.,Folkers, G. Molecular Modeling BasicPrinciplesandApplications Third,RevisedandExpandedEdition 2008 ISBN:978-3-527-31568-0 Matta,C. F.,Boyd,R. J.(eds.) The Quantum Theory of Atoms in Molecules FromSolidStatetoDNAandDrugDesign 2007 ISBN:978-3-527-30748-7 Rode, B.M.,Hofer,T.,Kugler,M. The Basics of Theoretical and Computational Chemistry 2007 ISBN:978-3-527-31773-8 Molecular Nano Dynamics Volume I: Spectroscopic Methods and Nanostructures Edited by Hiroshi Fukumura, Masahiro Irie, Yasuhiro Iwasawa, Hiroshi Masuhara, and Kohei Uosaki TheEditors AllbookspublishedbyWiley-VCHarecarefully produced.Nevertheless,authors,editors,and Prof.Dr.HiroshiFukumura publisherdonotwarranttheinformationcontained TohokuUniversity inthesebooks,includingthisbook,tobefreeof GraduateSchoolofScience errors.Readersareadvisedtokeepinmindthat 6-3AobaAramaki,Aoba-ku statements,data,illustrations,proceduraldetailsor Sendai980-8578 otheritemsmayinadvertentlybeinaccurate. Japan LibraryofCongressCardNo.: appliedfor Prof.Dr.MasahiroIrie RikkyoUniversity BritishLibraryCataloguing-in-PublicationData DepartmentofChemistry Acataloguerecordforthisbookisavailablefromthe Nishi-Ikebukuro3-34-1 BritishLibrary. Toshima-ku Tokyo171-8501 Bibliographicinformationpublishedby Japan theDeutscheNationalbibliothek TheDeutscheNationalbibliothekliststhis Prof.Dr.YasuhiroIwasawa publicationintheDeutscheNationalbibliografie; UniversityofElectro-Communications detailed bibliographicdataareavailableonthe DepartmentofAppliedPhysicsandChemistry Internetat http://dnb.d-nb.de. 1-5-1Chofu Tokyo182-8585 #2009WILEY-VCHVerlagGmbH&Co.KGaA, Weinheim and EmeritusProfessor Allrightsreserved(includingthoseoftranslationinto UniversityofTokyo otherlanguages).Nopartofthisbookmaybe 7-3-1Hongo,Bunkyo-ku reproducedinanyform–byphotoprinting, Tokyo113-0033 microfilm,oranyothermeans–nortransmittedor Japan translatedintoamachinelanguagewithoutwritten permissionfromthepublishers.Registerednames, Dr.HiroshiMasuhara trademarks,etc.usedinthisbook,evenwhennot NaraInstituteofScienceandTechnology specificallymarkedassuch,arenottobeconsidered GraduateSchoolofMaterialScience unprotectedbylaw. 8916-5Takayama,Ikoma Nara,630-0192 CoverDesign Adam-Design,Weinheim Japan Typesetting ThomsonDigital,Noida,India PrintingandBinding betz-druckGmbH,Darmstadt and NationalChiaoTungUniversity PrintedintheFederalRepublicofGermany DepartmentofAppliedChemistryand Printedonacid-freepaper InstituteofMolecularScience 1001TaHsuehRoad ISBN:978-3-527-32017-2 Hsinchu30010 Taiwan Prof.Dr.KoheiUosaki HokkaidoUniversity GraduateSchoolofScience N10,W8,Kita-ku Sapporo060-0810 Japan V Contents to Volume 1 Contents to Volume 2 XIII Preface XVII About the Editors XIX List of Contributors for Both Volumes XXIII PartOne SpectroscopicMethodsforNanoInterfaces 1 1 RamanandFluorescenceSpectroscopyCoupledwithScanning TunnelingMicroscopy 3 NorikoNishizawaHorimotoandHiroshiFukumura 1.1 Introduction 3 1.2 OutlineofSTMCombinedwithOpticalSpectroscopy 4 1.2.1 RamanSpectroscopy 4 1.2.2 FluorescenceSpectroscopy 6 1.3 TheoreticalApproaches 6 1.4 ExperimentalApproaches 8 1.4.1 STMCombinedwithRamanSpectroscopy 8 1.4.2 STMCombinedWithFluorescenceSpectroscopy 12 1.5 FutureProspects 13 References 16 2 VibrationalNanospectroscopyforBiomoleculesandNanomaterials 19 YasushiInouye,AtsushiTaguchi,andTaroIchimura 2.1 Introduction 19 2.2 SurfacePlasmonPolaritons 20 2.3 Near-FieldOpticalMicroscopyUsingaMetallicNano-Tip 22 2.4 Tip-EnhancedNear-FieldRamanSpectroscopyandImaging 24 2.4.1 RamanSpectroscopy 25 2.4.2 Near-FieldNano-RamanMicroscopy 25 2.4.3 Tip-EnhancedNear-FieldRamanSpectroscopyandImaging 26 VI ContentstoVolume1 2.5 TipEffectonNear-FieldRamanScattering 30 2.6 Conclusion 36 References 36 3 Near-FieldOpticalImagingofLocalizedPlasmonResonances inMetalNanoparticles 39 HiromiOkamotoandKoheiImura 3.1 Introduction 39 3.2 Near-FieldSpectroscopicMethod 40 3.3 FundamentalSpectroscopicCharacteristicsofGold Nanoparticles 42 3.4 WavefunctionImagesofPlasmonModesofGoldNanorod–— Near-FieldTransmissionMethod 42 3.5 UltrafastTime-ResolvedNear-FieldImagingofGoldNanorods 45 3.6 Near-FieldTwo-PhotonExcitationImagesofGoldNanorods 47 3.7 EnhancedOpticalFieldsinSphericalNanoparticleAssembliesand SurfaceEnhancedRamanScattering 48 3.8 ConcludingRemarks 51 References 52 4 StructureandDynamicsofaConfinedPolymerChainStudiedbySpatially andTemporallyResolvedFluorescenceTechniques 55 HiroyukiAoki 4.1 Introduction 55 4.2 ConformationofaConfinedPolymerChain 56 4.2.1 PolymerUltra-ThinFilm 56 4.2.2 Near-FieldOpticalMicroscopy 56 4.2.3 StructureofaSinglePolymerChain 58 4.3 DynamicsofaConfinedPolymerChain 61 4.3.1 PolymerBrush 61 4.3.2 FluorescenceDepolarizationMethod 61 4.3.3 DynamicsofaPolymerBrush 63 4.4 Summary 67 References 68 5 RealTimeMonitoringofMolecularStructureatSolid/LiquidInterfaces byNon-LinearSpectroscopy 71 HidenoriNoguchi,KatsuyoshiIkeda,andKoheiUosaki 5.1 Introduction 71 5.2 SumFrequencyGenerationSpectroscopy 72 5.2.1 BriefDescriptionofSFG 72 5.2.2 OriginofSFGProcess 73 5.2.3 SFGSpectroscopy 74 5.2.4 ExperimentalArrangementforSFGMeasurements 77 ContentstoVolume1 VII 5.2.4.1 LaserandDetectionSystems 77 5.2.4.2 SpectroscopicCells 78 5.3 SFGStudyofthePotential-DependentStructureofWaterataPt Electrode/ElectrolyteSolutionInterface 80 5.3.1 Introduction 80 5.3.2 ResultsandDiscussion 80 5.3.3 Conclusions 83 5.4 PhotoinducedSurfaceDynamicsofCOAdsorbedonaPlatinum Electrode 84 5.4.1 Introduction 84 5.4.2 ResultsandDiscussion 85 5.4.3 Conclusions 88 5.5 InterfacialWaterStructureatPolyvinylAlcohol(PVA)Gel/Quartz InterfacesInvestigatedbySFGSpectroscopy 89 5.5.1 Introduction 89 5.5.2 ResultsandDiscussions 90 5.5.3 Conclusions 92 5.6 Hyper-RamanSpectroscopy 94 5.6.1 SelectionRulesforHyper-RamanScattering 94 5.6.2 EnhancementofHyper-RamanScatteringIntensity 94 5.6.3 Conclusion 96 5.7 GeneralConclusion 96 References 97 6 Fourth-OrderCoherentRamanScatteringatBuriedInterfaces 103 HiroshiOnishi 6.1 WhyBuriedInterfaces? 103 6.2 OpticalTransitions 104 6.3 ExperimentalScheme 106 6.4 ApplicationtoaLiquidSurface 107 6.5 ApplicationtoaLiquid/LiquidInterface 108 6.6 ApplicationstoSolidSurfaces 109 6.7 FrequencyDomainDetection 112 6.8 ConcludingRemarks 113 References 113 7 DynamicAnalysisUsingPhotonForceMeasurement 117 HidekiFujiwaraandKeijiSasaki 7.1 Introduction 117 7.1.1 WeakForceMeasurements 117 7.1.2 PotentialAnalysisMethodUsingPhotonForceMeasurement 118 7.2 Measurement of the Hydrodynamic Interaction Force Acting between TwoTrappedParticlesUsingthePotentialAnalysisMethod 121 7.2.1 Two-BeamPhotonForceMeasurementSystem 121 VIII ContentstoVolume1 7.2.2 PotentialAnalysisMethodforHydrodynamicForce Measurement 122 7.2.3 TrappingPotentialAnalysis 124 7.3 KineticPotentialAnalysis 125 7.4 Summary 129 References 130 8 ConstructionofMicro-SpectroscopicSystemsandtheirApplicationto theDetectionofMolecularDynamicsinaSmallDomain 133 SyojiIto,HirohisaMatsuda,TakashiSugiyama,NaokiToitani, YutakaNagasawa,andHiroshiMiyasaka 8.1 Introduction 133 8.2 DevelopmentofaNear-Infrared35fsLaserMicroscopeandits ApplicationtoHigherOrderMultiphotonExcitation 133 8.2.1 ConfocalMicroscopewithaChromium:ForsteriteUltrafastLaserasan ExcitationSource 134 8.2.2 DetectionofHigherOrderMultiphotonFluorescencefromOrganic Crystals 135 8.2.3 MultiphotonFluorescenceImagingwiththeNear-Infrared35fsLaser Microscope 137 8.3 ApplicationofFluorescenceCorrelationSpectroscopytotheMeasurement ofLocalTemperatureataSmallAreainSolution 139 8.3.1 ExperimentalSystemofFCS 139 8.3.2 ThePrincipleoftheMethodofMeasurementofLocalTemperature UsingFCS 140 8.3.3 MeasurementofLocalTemperatureforSeveralOrganic Solvents 141 8.3.4 Summary 146 8.4 RelaxationDynamicsofNon-EmissiveStateforWater-SolubleCdTe QuantumDotsMeasuredbyUsingFCS 147 8.4.1 SamplesandAnalysisofExperimentalDataObtainedwithFCS 147 8.4.2 Non-EmissiveRelaxationDynamicsinCdTeQuantumdots 148 8.5 Summary 150 References 152 9 NonlinearOpticalPropertiesandSingleParticleSpectroscopyof CdTeQuantumDots 155 LingyunPan,YoichiKobayashi,andNaotoTamai 9.1 Introduction 155 9.2 NonlinearOpticalPropertiesofCdTeQDs 156 9.3 OpticalTrappingofCdTeQDsProbedbyNonlinearOptical Properties 158 9.4 SingleParticleSpectroscopyofCdTeQDs 162 9.5 Summary 166 References 167