Table Of ContentLocal Structural
Characterisation
InorganicMaterialsSeries
SeriesEditors:
ProfessorDuncanW.Bruce
DepartmentofChemistry,UniversityofYork,UK
ProfessorDermotO’Hare
ChemistryResearchLaboratory,UniversityofOxford,UK
ProfessorRichardI.Walton
DepartmentofChemistry,UniversityofWarwick,UK
SeriesTitles
FunctionalOxides
MolecularMaterials
PorousMaterials
Low-DimensionalSolids
EnergyMaterials
LocalStructuralCharacterisation
ForthcomingTitles
MultiLength-ScaleCharacterisation
StructureFromDiffractionMethods
Local Structural
Characterisation
Edited by
Duncan W. Bruce
University of York, UK
Dermot O’Hare
University of Oxford, UK
Richard I. Walton
University of Warwick, UK
Thiseditionfirstpublished2014
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LibraryofCongressCataloging-in-PublicationData
Localstructuralcharacterisation/editedbyDuncanW.Bruce,DermotO’Hare,RichardI.Walton.
pagescm
Includesbibliographicalreferencesandindex.
ISBN978-1-119-95320-3(cloth)
1.Chemicalstructure.2.Materials.I.Bruce,DuncanW.,editorofcompilation.
II.O’Hare,Dermot,editorofcompilation.III.Walton,RichardI.,editorofcompilation.
QD471.L6852014
543(cid:2).5–dc23
2013015036
AcataloguerecordforthisbookisavailablefromtheBritishLibrary.
ISBN:9781119953203
Setin10.5/13ptSabonbyLaserwordsPrivateLimited,Chennai,India
12014
Contents
InorganicMaterialsSeriesPreface xi
Preface xiii
ListofContributors xv
1 Solid-StateNuclearMagneticResonanceSpectroscopy 1
SharonE.Ashbrook,DanielM.DawsonandJohnM.Griffin
1.1 Overview 1
1.2 TheoreticalBackground 3
1.2.1 FundamentalsofNMR 3
1.2.2 AcquisitionofBasicNMRSpectra 4
1.2.3 Relaxation 7
1.2.4 InteractionsinNMRSpectroscopy 7
1.3 BasicExperimentalMethods 15
1.3.1 SpinI =1/2Nuclei 15
1.3.2 SpinI >1/2Nuclei 24
1.3.3 WidelineNMRSpectroscopy 30
1.4 CalculationofNMRParameters 31
1.4.1 IntroductiontoDensityFunctionalTheory 31
1.4.2 BasisSetsandPeriodicity 32
1.4.3 ReducingtheComputationalCostofCalculations 33
1.4.4 ApplicationofFirst-PrinciplesCalculations 34
1.5 ApplicationsofSolid-StateNMRSpectroscopy 36
1.5.1 LocalandLong-RangeStructure 36
1.5.2 MeasuringInternuclearInteractions 43
1.5.3 DisorderedMaterials 46
1.5.4 StudyingDynamics 50
1.5.5 ChallengingNucleiandSystems 54
1.5.6 ParamagneticMaterialsandMetals 56
1.6 CommonlyStudiedNuclei 59
1.6.1 Hydrogen 59
1.6.2 Lithium 61
1.6.3 Boron 62
vi CONTENTS
1.6.4 Carbon 62
1.6.5 Oxygen 62
1.6.6 Fluorine 63
1.6.7 Sodium 63
1.6.8 Aluminium 64
1.6.9 Silicon 64
1.6.10Phosphorus 64
1.6.11Xenon 65
1.7 NMRofMaterials 65
1.7.1 SimpleIonicCompoundsandCeramics 65
1.7.2 MicroporousMaterials 67
1.7.3 MineralsandClays 74
1.7.4 EnergyMaterials 76
1.7.5 Glasses 78
1.7.6 Polymers 81
1.8 Conclusion 83
References 84
2 X-rayAbsorptionandEmissionSpectroscopy 89
PieterGlatzelandAme´lieJuhin
2.1 Introduction:WhatisPhotonSpectroscopy? 89
2.2 ElectronicStructureandSpectroscopy 93
2.2.1 TotalEnergyDiagram 93
2.2.2 InteractionofX-rayswithMatter 96
2.3 CalculationofInner-ShellSpectra 106
2.3.1 TheSingle-ParticleExtendedPictureofElectronic
States 107
2.3.2 TheMany-BodyAtomicPictureofElectronic
States 109
2.3.3 ComparisonofTheoreticalApproaches 112
2.3.4 The Many-Body Extended Picture of Electronic
States 113
2.3.5 Single-ParticleCalculationoftheAbsorption
Cross-Section 114
2.3.6 Many-BodyAtomicCalculationofthe
Cross-Section 118
2.3.7 WhichApproachWorksBestforInner-Shell
Spectroscopy? 118
2.3.8 BeyondStandardDFTMethods 119
CONTENTS vii
2.4 ExperimentalTechniques 120
2.4.1 X-rayAbsorptionSpectroscopy 121
2.4.2 X-rayRamanScatteringSpectroscopy 130
2.4.3 Non-ResonantX-rayEmission(X-ray
Fluorescence) 131
2.4.4 ResonantInelasticX-rayScattering 137
2.5 ExperimentalConsiderations 155
2.5.1 ModernSourcesofX-rays 155
2.5.2 UltrafastX-raySpectroscopy 157
2.5.3 MeasuringXAS/XES 158
2.6 Conclusion 163
Acknowledgements 164
References 164
3 NeutronsandNeutronSpectroscopy 173
A.J.Ramirez-CuestaandPhilipC.H.Mitchell
3.1 TheNeutronandHowitisScattered 174
3.1.1 TheScatteringLaw 175
3.2 WhyNeutrons? 179
3.2.1 TheS(Q,ω)Map 180
3.2.2 ModellingofINSSpectra 181
3.2.3 ExampleoftheEffectsofSamplingoftheBrillouin
Zone 183
3.2.4 INSSpectrometers 184
3.2.5 MeasurementTemperature 189
3.2.6 AmountofSampleRequired 189
3.3 MolecularHydrogen(Dihydrogen)inPorousMaterials 190
3.3.1 TheRotationalSpectrumofDihydrogen 190
3.3.2 ThePolarisingPowerofCationsandH Binding 191
2
3.3.3 HydrogeninMetalOrganicFrameworks 195
3.3.4 HydrogenTrappedinClathrates 198
3.4 INSandCatalysis 201
3.4.1 HydroxylGroupsonSurfaces 206
3.5 CO andSO Capture 207
2 2
3.6 WhatCouldbeNext? 211
3.6.1 HowCouldWeImproveINS? 211
3.6.2 AHypotheticalINSInstrumentforCatalysis 216
3.7 Conclusion 219
References 220
viii CONTENTS
4 ElectronParamagneticResonanceSpectroscopyofInorganic
Materials 225
PiotrPietrzyk,TomaszMazurandZbigniewSojka
4.1 Introduction 225
4.2 ElectronSpininaMagneticField 226
4.2.1 ElectronZeemanEffectandtheResonance
Phenomenon 228
4.2.2 SpinRelaxation 230
4.2.3 Electron–NucleusHyperfineInteraction 233
4.2.4 EPRSpectrometers 238
4.2.5 Samples,SampleHoldersandRegistrationofEPR
Spectra 242
4.3 SpinHamiltonianandSymmetry 244
4.3.1 Theg Tensor 244
4.3.2 TheHyperfineATensor 250
4.3.3 TheFineStructureDTensor 256
4.3.4 TheQuadrupoleQTensor 260
4.3.5 Electron–ElectronExchangeInteractionsJ 261
4.3.6 TheSpinHamiltonian 264
4.4 PrincipalTypesofEPRSpectrumandTheirCharacteristic
Features 267
4.4.1 Single-CrystalSpectra 267
4.4.2 StaticandDynamicDisorder 269
4.4.3 EPRSpectraofPowderandNanopowder
Materials 274
4.4.4 UnusualSpectralFeatures 278
4.4.5 ComputerSimulationofPowderSpectra 280
4.5 AdvancedEMRTechniques 282
4.5.1 High-FieldandMultifrequencyEPR 282
4.5.2 PulsedEPRMethods 285
References 296
5 AnalysisofFunctionalMaterialsbyX-rayPhotoelectron
Spectroscopy 301
KarenWilsonandAdamF.Lee
5.1 Introduction 301
5.1.1 TheBasicPrinciplesofXPS 302
5.1.2 QuantificationofX-rayPhotoelectronSpectra 305
5.1.3 TheOriginofSurfaceSensitivity 308
CONTENTS ix
5.1.4 AngularResolvedXPS 309
5.1.5 ChemicalShiftInformationfromXPS 311
5.2 ImagingXPS 315
5.3 Time-ResolvedHigh-ResolutionXPS 318
5.3.1 SelectiveCatalyticAlcoholOxidation 319
5.3.2 SelectiveOxidationofAllylicAlcohols 322
5.3.3 C–XActivation 324
5.4 High-orAmbient-PressureXPS 326
5.4.1 AP-XPSStudiesoftheSurfaceChemistry
ofOxidisedMetalSurfaces 329
5.4.2 SelectiveHydrogenation 333
5.4.3 HP-XPS Studies of Core–Shell Nanoparticulate
Materials 335
5.5 ApplicationstoInorganicMaterials 335
5.5.1 BimetallicNanoparticles 335
5.5.2 XPSStudiesofHeteropolytungstateClusters 338
5.5.3 XPSStudiesofAcid–BaseSitesinOxide
Catalysts 342
5.6 Conclusion 345
References 345
Index 351
Inorganic Materials
Series Preface
Back in 1992, two of us (DWB and DO’H) edited the first edition of
InorganicMaterialsinresponsetothegrowingemphasisonandinterest
in materials chemistry. The second edition, which contained updated
chapters, appeared in 1996 and was reprinted in paperback. The aim
hadalwaysbeentoprovidechaptersthatwhilenotnecessarilycompre-
hensive, nonetheless gave a first-rate and well-referenced introduction
to the subject for the first-time reader. As such, the target audience was
fromfirst-yearpostgraduatestudentsupwards.Inthesetwoeditions,we
believeourauthorsachievedthisadmirably.
In the intervening years, materials chemistry has grown hugely and it
nowfindsitselfcentraltomanyofthemajorchallengesthatfaceglobal
society. We felt, therefore, that there was a need for more extensive
coverage of the area, and so Richard Walton joined the team and, with
Wiley,wesetaboutworkingonanewandlargerproject.
TheInorganicMaterialsSeriesistheresult,andouraimistoprovide
chapters with a similar pedagogical flavour to the first and second
editions, but now with much wider subject coverage. As such, the
work will be contained in several volumes. Many of the early volumes
concentrateonmaterialsderivedfromcontinuousinorganicsolids.Later
volumes, however, will emphasise methods of characterisation as well
as molecular and soft-matter systems, as we aim for a much more
comprehensive coverage of the area than was possible with Inorganic
Materials.
Wearedelightedwiththecalibreofauthorswhohaveagreedtowrite
for us and we thank them all for their efforts and cooperation. We
believe they have done a splendid job and that their work will make
thesevolumesavaluablereferenceandteachingresource.
DWB,York
DO’H,Oxford
RIW,Warwick
June2013
