WoodheadPublishingSeriesin ElectronicandOpticalMaterials
1 Circuitanalysis
J.E.Whitehouse
2 Signalprocessinginelectroniccommunications:Forengineersandmathematicians
M.J.Chapman,D.P.GoodallandN.C.Steele
3 Patternrecognitionandimageprocessing
D.Luo
4 Digitalfiltersandsignalprocessinginelectronicengineering:Theory,applications,architecture, code
S.M.BozicandR.J.Chance
5 Cableengineeringforlocalareanetworks
B.J.Elliott
6 DesigningastructuredcablingsystemtoISO11801:Cross-referencedtoEuropeanCENELEC andAmericanStandards
Secondedition
B.J.Elliott
7 Microscopytechniquesformaterialsscience
A.ClarkeandC.Eberhardt
8 Materialsforenergyconversiondevices
EditedbyC.C.Sorrell,J.NowotnyandS.Sugihara
9 Digitalimageprocessing:Mathematicalandcomputationalmethods
Secondedition
J.M.Blackledge
10 Nanolithographyandpatterningtechniquesinmicroelectronics
EditedbyD.Bucknall
11 Digitalsignalprocessing:Mathematicalandcomputationalmethods,softwaredevelopment andapplications
Secondedition
J.M.Blackledge
12 Handbookofadvanceddielectric,piezoelectricandferroelectricmaterials:Synthesis,properties andapplications
EditedbyZ.-G.Ye
13 Materialsforfuelcells
EditedbyM.Gasik
14 Solid-statehydrogenstorage:Materialsandchemistry
EditedbyG.Walker
15 Lasercoolingofsolids
S.V.PetrushkinandV.V.Samartsev
16 Polymerelectrolytes:Fundamentalsandapplications
EditedbyC.A.C.SequeiraandD.A.F.Santos
17 Advancedpiezoelectricmaterials:Scienceandtechnology
EditedbyK.Uchino
Opticalswitches:Materialsanddesign
EditedbyS.J.ChuaandB.Li
19 Advancedadhesivesinelectronics:Materials,propertiesandapplications
EditedbyM.O.AlamandC.Bailey
20 Thinfilmgrowth:Physics,materialsscienceandapplications
EditedbyZ.Cao
21 Electromigrationinthinfilmsandelectronicdevices:Materialsandreliability
EditedbyC.-U.Kim
22 Insitu characterizationofthinfilmgrowth
EditedbyG.KosterandG.Rijnders
23 Silicon-germanium(SiGe)nanostructures:Production,propertiesandapplicationsinelectronics
EditedbyY.ShirakiandN.Usami
24 High-temperaturesuperconductors
EditedbyX.G.Qiu
25 Introductiontothephysicsofnanoelectronics
S.G.TanandM.B.A.Jalil
26 Printedfilms:Materialsscienceandapplicationsinsensors,electronicsandphotonics
EditedbyM.PrudenziatiandJ.Hormadaly
27 Lasergrowthandprocessingofphotonicdevices
EditedbyN.A.Vainos
28 Quantumopticswithsemiconductornanostructures
EditedbyF.Jahnke
29 Ultrasonictransducers:Materialsanddesignforsensors,actuatorsandmedicalapplications
EditedbyK.Nakamura
30 Wasteelectricalandelectronicequipment(WEEE)handbook
EditedbyV.GoodshipandA.Stevels
31 ApplicationsofATILAFEMsoftwaretosmartmaterials:Casestudiesindesigningdevices
EditedbyK.UchinoandJ.-C.Debus
32 MEMSforautomotiveandaerospaceapplications
EditedbyM.KraftandN.M.White
33 Semiconductorlasers:Fundamentalsandapplications
EditedbyA.BaranovandE.Tournie
34 Handbookofterahertztechnologyforimaging,sensingandcommunications
EditedbyD.Saeedkia
35 Handbookofsolid-statelasers:Materials,systemsandapplications
EditedbyB.DenkerandE.Shklovsky
36 Organiclight-emittingdiodes(OLEDs):Materials,devicesandapplications
EditedbyA.Buckley
37 Lasersformedicalapplications:Diagnostics,therapyandsurgery
EditedbyH.Jelı´nkova´
38 Semiconductorgassensors
EditedbyR.JaanisoandO.K.Tan
39 Handbookoforganicmaterialsforopticaland(opto)electronicdevices:Properties andapplications
EditedbyO.Ostroverkhova
40 Metallicfilmsforelectronic,opticalandmagneticapplications:Structure,processing andproperties
EditedbyK.BarmakandK.Coffey
41 Handbookoflaserweldingtechnologies
EditedbyS.Katayama
42 Nanolithography:Theartoffabricatingnanoelectronicandnanophotonicdevicesandsystems
EditedbyM.Feldman
43 Laserspectroscopyforsensing:Fundamentals,techniquesandapplications
EditedbyM.Baudelet
WoodheadPublishingSeriesinElectronicandOpticalMaterials
44
Chalcogenideglasses:Preparation,propertiesandapplications
EditedbyJ.-L.AdamandX.Zhang
45 HandbookofMEMSforwirelessandmobileapplications
EditedbyD.Uttamchandani
46 Subseaopticsandimaging
EditedbyJ.WatsonandO.Zielinski
47 Carbonnanotubesandgrapheneforphotonicapplications
EditedbyS.Yamashita,Y.SaitoandJ.H.Choi
48 Opticalbiomimetics:Materialsandapplications
EditedbyM.Large
49 Opticalthinfilmsandcoatings
EditedbyA.PiegariandF.Flory
50 Computerdesignofdiffractiveoptics
EditedbyV.A.Soifer
51 SmartsensorsandMEMS:Intelligentdevicesandmicrosystemsforindustrialapplications
EditedbyS.NihtianovandA.Luque
52 Fundamentalsoffemtosecondoptics
S.A.KozlovandV.V.Samartsev
53 Nanostructuredsemiconductoroxidesforthenextgenerationofelectronicsandfunctional devices:Propertiesandapplications
S.Zhuiykov
54 Nitridesemiconductorlight-emittingdiodes(LEDs):Materials,technologiesandapplications
EditedbyJ.J.Huang,H.C.KuoandS.C.Shen
55 Sensortechnologiesforcivilinfrastructures
Volume1:Sensinghardwareanddatacollectionmethodsforperformanceassessment
EditedbyM.Wang,J.LynchandH.Sohn
56 Sensortechnologiesforcivilinfrastructures
Volume2:Applicationsinstructuralhealthmonitoring
EditedbyM.Wang,J.LynchandH.Sohn
57 Graphene:Properties,preparation,characterisationanddevices
EditedbyV.Ska´kalova´ andA.B.Kaiser
58 Silicon-on-insulator(SOI)technology
EditedbyO.KononchukandB.-Y.Nguyen
59 Biologicalidentification:DNAamplificationandsequencing,opticalsensing,lab-on-chipandportablesystems
EditedbyR.P.Schaudies
60 Highperformancesiliconimaging:FundamentalsandapplicationsofCMOSandCCDsensors
EditedbyD.Durini
61 Nanosensorsforchemicalandbiologicalapplications:Sensingwithnanotubes, nanowiresandnanoparticles
EditedbyK.C.Honeychurch
62 Compositemagnetoelectrics:Materials,structures,andapplications
G.Srinivasan,S.PriyaandN.Sun
63 Quantuminformationprocessingwithdiamond:Principlesandapplications
EditedbyS.PrawerandI.Aharonovich
64 Advancesinnon-volatilememoryandstoragetechnology
EditedbyY.Nishi
65 Lasersurfaceengineering:Processesandapplications
EditedbyJ.Lawrence,C.Dowding,D.WaughandJ.Griffiths
66 Powerultrasonics:Applicationsofhigh-intensityultrasound
EditedbyJ.A.Gallego-Jua´rezandK.F.Graff
67 Advancesindelay-tolerantnetworks(DTNs):Architectures,routingandchallenges
EditedbyJ.J.P.C.Rodrigues
68 Handbookofflexibleorganicelectronics:Materials,manufacturingandapplications
EditedbyS.Logothetidis
69 Machine-to-machine(M2M)communications:Architecture,performanceandapplications
EditedbyC.Anton-HaroandM.Dohler
70 Ecologicaldesignofsmarthomenetworks:Technologies,socialimpactandsustainability
EditedbyN.SaitoandD.Menga
71 Industrialtomography:Systemsandapplications
EditedbyM.Wang
72 Vehicularcommunicationsandnetworks:Architectures,protocols,operationanddeployment
EditedbyW.Chen
73 Modeling,characterizationandproductionofnanomaterials:Electronics,photonicsandenergy applications
EditedbyV.K.TewaryandY.Zhang
74 Reliabilitycharacterisationofelectricalandelectronicsystems
EditedbyJ.Swingler
75 Handbookofindustrialwirelesssensornetworks:Monitoring,controlandautomation
EditedbyR.BudampatiS.Kolavennu
76 Epitaxialgrowthofcomplexmetaloxides:Techniques,propertiesandapplications
EditedbyG.Koster,G.RijndersandM.Huijben
77 Semiconductornanowires:Materials,synthesis,characterizationandapplications
EditedbyJ.ArbiolandQ.Xiong
78 SuperconductorsinthePowerGrid
EditedbyC.Rey
79 Optofluidics,sensorsandactuatorsinmicrostructuredopticalfibres
EditedbyS.Pissadakis
80 HandbookofMagneticNano-andMicrowires
EditedbyM.Va´zquez
81 Robustdesignofmicroelectronicassembliesagainstmechanicalshock,temperatureandmoisture E-H.WongandY-W.Mai
82 Biomimetictechnologies:Principlesandapplications
EditedbyT.D.Ngo
83 Directedself-assemblyofblockco-polymersfornano-manufacturing
EditedbyR.GronheidandP.Nealey
Note:Pagenumbersfollowedby f indicatefiguresand t indicatetables.
A
Abinit,356
Accurateviscositymodel,428
Adaptiveintermolecularreactiveempirical bondorder(AIREBO),184 AGNR. See Armchair-edgegraphene nanoribbon(AGNR)
AkaikeInformationCriterion(AIC),429–430
Alcoholfuelcells. See Directethanolfuel cells(DEFCs)Directmethanolfuel cells(DMFCs)
Alloynanoparticles behavior(see Atomicbehavior) elementsselection,235–236 interactionpotential,234–235 moleculardynamicsprocedure,234 properties,233 segregation(see Atomicsegregation)
AMBERforcefield,32
Ambipolartransport,489
Anharmoniclatticedynamics(ALD) method,452–453
Anisotropiccontinuumtheory,56
Annularbright-field(ABF)imaging technique,115–116
Armchair-edgegraphenenanoribbon (AGNR),209–210
Atomicbehavior
bondorderparameterW6,241, 242–243,243f clustermorphology,245–246,246f coalescedcoolingprocess,245,245f coolingclusters,247–248,248f coolingrate,244 cuboctahedralnanoparticles,241 Cu-Coalloynanoparticlestructures, 244,245
Cucontentandatomicdistribution,248 differentatomicdiffusion,241–242,242f frozenstructures,241–242,242f, 243–244,243f
modeofcontrolling,248 PDF,246,247f sphericalcutoffradii,244 structuraltransformation,244 surfaceenergy,244
Atomicforcemicroscopy(AFM),98–99, 99f,102
Atomiclayerdeposition(ALD), 481–482 cycleof,514–515 MoS2 nanosheet-basedtransistor, 481–482,483f self-limitingfilmgrowthmechanism,514 temperaturerange,515 2DAl2O3 layer,515 2Dsandwichnanostructures,513–514 Atomicsegregation
Ag-corenanoparticle,236 Ag-surfacenanoparticle,236 bondorderparameter,240–241,240f energyandatomicnumbers, 237–238,238f icosahedral-decahedralstructural,241 simulatedandfittedenergy,238,239f temperaturedependence,239–240,239f temperature-energycurves,236–237,237f variation,240–241
Atomisticmodeling BTE,446 classicalMDsimulations,445–446 Green’sfunction,445 interfacialthermalresistance (see Interfacialthermalresistance) latticedynamics,445,447t materialresearch,443–444 multiscalesimulation,446–447 thermalconductivity(see Thermal conductivity) thermoelectricmaterials,444 transistorpowerdensity,444 Au-core/Pt-shellmodel,268f
B
Band-gapcalculations
density-functionaltheoryandderivative discontinuity,408–409 grapheneandhexagonalboronnitride, 414–415
HSpotential,411–412
Kohn-Shampotential,408–411 vLBpotential,412–414
Band-to-bandtunneling(BTBT)current, 216,217,217f
Bayesianmodelselection,430
Begrenzung effect,360–362
BlackphosphorusFETs anisotropicstructure,504 bandstructure,504,505f configuration,504–505,506f,507 grapheneandMoS2,507 structuralanisotropy,504
Boltzmanninversion,19
Boltzmann/randomdistribution,8 Boltzmanntransportequation(BTE), 445,446
Bondorder-length-strength(BOLS) mechanism,185,192–193
Born-Oppenheimerapproximation,5
Born’smethod,71,78–79
BornvonKarman(BvK)model,64–65
Bose-Einsteinstatistics,102 Bravaislattice,65
Brightfield(BF)imaging,115–116
Brillouinzone,67 Brownianmotion,421
Bulknanostructuredmaterials, 449–450
C
Carbon-basednanostructures,12
Carbonnanotube(CNT),12,38–41,41f, 171–172,175–176,455–456 arcdischarge,180 armchairtubes,208,209f atomicforcemicroscopy,183 CVD,179 vs. graphenenanoribbon,224–225,225f hexagonalarrays,182 laserablation,180 mechanicalproperties,182
metallicandsemiconductingnanotubes, 209,210f MWCNT,182 structuralproperties,181–182 SWCNT,182–183 tensilestiffnessvalue,182 tunnelFET(see Carbonnanotubestunnel FETs(CNT-TFET))
Young’smoduli,182–183 zigzag,209
CarbonnanotubestunnelFETs(CNT-TFET) aggressivescaling,218 BTBT,216,217f carbon-basedmaterials,220–221 CMOS-compatiblemethod,221 diameter-dependentbandgap,221–222 vs. MOSFET,223,224f NANOTCADViDES,222 n-typeandp-type,218–220 ONandOFF-stateperformance,216,217f, 220–221,220f on-statecurrentandinversesubthreshold slope,218–220 parameters,218,218t purificationmethods,221 Schottkybarrier,220–221 simulatedtransfercharacteristics, 222,223f spectroscopicmeasurements, 221–222,222f strategies/devicearchitectures,218,219t tunnelingmechanism,216
Carbon-vapor-deposition(CVD), 94–95,179
Cartesianframeofreference,65
Catalysts,30–31
CatalyticCOoxidation dealloying,272 downstreamprocess,272 factors,275–276 probemolecule,272 Pt-basednanoalloyproperties, 274f,275 PtNiCo/CandPtIrCo/Ccatalysts, 274f,275 reactionrates,273,274f self-tunableoxophilicityandstructural integrity,275 insitu HE-XRD/PDF,275
type-Isites,272–273,273f type-IIsites,272–273,273f watergasshiftreaction,272
CdSe/ZnTecore-shellnanowires, 133–134,133f
CGMD. See Coarse-grainedmolecular dynamics(CGMD)
CHARMMforcefield,32
Chemicalvapordeposition(CVD), 491–493
Christoffelmatrix,72
Coarse-grainedmoleculardynamics (CGMD) forcefields,14–15 lipidcomponent,33 mesoscalemodeling,12–14 Newtoniandynamics,17–18 parameters,18 potentialenergy,16–17
Coaxialcore-shellnanowires
CdSe/ZnTenanowires,133–134,133f ZnO/ZnSeandZnO/ZnS,130–132, 131f,132f
CoComodel,265–266,265t
Cohesiveenergydensity(CED),11 COMPASSforcefield,26,27
Computationalmodeling asymmetriccappeddecahedron,271–272 complexphaseproperties,270 DFT-calculatedlatticeconstants, 270,271f latticeexpansionandshrinking,275–276 Mackayicosahedron,271–272 moleculardynamicssimulations,271–272 nanoscalephaseevolution,270 Pt-core/Au-shellstructure,271–272 spin-polarizedDFTmethod,270,271f Vienna Abinitio SimulationPackage,270
Configurationinteraction(CI)method,5–6
Consistentvalenceforcefield(CVFF),10f
ContinuumGF(CGF),71 Continuumtheory,56–57
Convergentbeamelectrondiffraction (CBED),117–118,119–120
Core-shellInGaN/GaNmulti-quantum-well heterostructures
ammoniaflux,325 Ga-polarorientation,324–325 “green-gap,”,330
homogeneousc-axisGaNwiresand heterostructures,324 lightextraction,330 multi-colordevices,330 nano-characterization APTreconstruction,328–329 EBIC,329 EDS,327–328 EELS,327–328 emissionproperties,328–329 IDB,328–329 quantumconfinement,330 quantumwellgeometryandstrains, 327–328 Ramanspectroscopy,327 X-raydiffractionmeasurement,327 opticalandstructuralproperties,324 quantum-confinedStarkeffect,324 sidewallemission,325–326 top-downandbottom-up-approaches,324 Core-shelltypenanostructure,256 Coupled-clustercalculationswithsingleand doubleexcitations(CCSD),6 Coupled-clustermethods,6 3C-SiCthinfilm laser-inducedconversion,340–344 Si(111),MBE,337–339
DDark-field(DF)imaging,115–116 Datta’sapproach,205–206 Debye-Huckelinteraction,14 Debye-Huckelscreeningapproximation,33 DEFC. See Directethanolfuelcells(DEFCs) Densityfunctionaltheory(DFT),6–7, 255–256,407 Abinit,356 DFTcomputation(see Computational modeling) electronenergylossfunctioncalculations, 355 exchange-correlationfunctional,354–355 GPAW,356 local densityapproximation,353–354 opticallimit,355 QuantumESPRESSO,356 SIESTA,355 VASP,356
Densityofstates(DOS),35 circularcoordinates,212 definition,210–211 deltafunction,211,212–213 Fermifunctions,210–211,213 Van-Hovesingularities,213 zigzagnanotube vs. 2Dgraphenesheet, 211,211f Differentialscanningcalorimetry(DSC), 169–170 chemicalcomposition,172 indomethacin,170–171 nanocomposites,173 oxidationtemperature,171–172 sizeandmorphology,170–171 Diracdeltafunction,61,67 Diracpoints,450–451
Directethanolfuelcells(DEFCs),254–255 applications,276 catalyticselectivitydata,278–279 C-Cbondcleavage,278 CO2 productrelease,279,279f designandcontrol,276 electrocatalyticactivity,279 highefficiency,276,278 highpowerdensity,276 lightweight,276 lowcost,276 lowpollution,276 PdCualloycatalysts,278–279
Directmethanolfuelcells(DMFCs),254–255 applications,276 electrocatalyticactivity,279 enhancefuelsustainability,276 EOR,276 fuelutilizationandcellperformance,276 HE-XRD/PDFtechniques,276 highconversionefficiency,276 highpowerdensity,276 lightweight,276 lowcost,276 lowpollution,276 massactivity,276,277f open-circuitconditions,276 relativePt-specificmassactivity,276–278 safetyimprovement,276 surfaceadsorptionandhydrogenation, 276,277f synergisticeffect,276–278,277f
Discretelatticetheory,57 Dissipativeparticledynamics(DPD)method atomisticforcefieldcalculations, 40,41f Brownianforces,18 Flory-Hugginstheory,14 “hardandsticky”particlemodel,13 inter-particleforce,16 Newtoniandynamics,17 nonionicsurfactants,32 parameterization,19 Divideandconquer(DC),7 DMFC. See Directmethanolfuelcells (DMFCs) Donnanapproximations,33
Doubletipnanoneedles,118,119f DPDmethod. See Dissipativeparticle dynamics(DPD)method
Dreidingforcefield,10–11
Duffin’slemma,71
Dynamicdensityfunctionaltheory(DDFT) dynamics,18 parameterization,18,19 PS-b-PBpolymer,34f useof,33
Dynamiclightscattering(DLS),420 Dynamicram(DRAM)cells,399–401 Dysonequation,70
EEAM. See Embeddedatommethod(EAM) Electricpolarizationeffects,56 Electronbeaminducedcurrent(EBIC) measurements,329
Electron-correlatedmethods,5–6
Electronenergylossspectroscopy(EELS), 115–116
Embeddedatommethod(EAM),31, 234–235
Energyconversionefficiency,444
EnergydispersiveX-rayspectroscopy (EDS),115–116
EOR. See Ethanoloxidation reaction(EOR)
Equilibriummoleculardynamics(EMD) simulation,445–446
Ethanoloxidationreaction(EOR),276
Exchange-correlationenergy,6
F
Fabricationmethods
ALD(see Atomiclayerdeposition(ALD))
2Dnanocrystals,508–513
FastFouriertransformations(FFT),126–127
Faujasite(FAU),28,29f
Field-effecttransistor(FET),481
Finiteelementmethods(FEM),21,424–426
Fischer-Tropschcatalysts,29
Flocculationmodel,421–423
Flory-Hugginstheory,14
Fluxmethod,426–427
Fockmatrix,5
Fockoperator,6
Force-constantmatrix,65–66,69–70
Forcefields
AMBERforcefield,32 classicalmechanics,10–11,10f consistentvalenceforcefield,10f dreidingforcefield,32
GROMOS/Berger,32
MARTINIforcefield,14,17 mesoscalemodeling,14–15
MonteCarlosimulation,9
PCFF,39f Shinodaforcefield,14–15
Force-matchingmethod,19
Fouriertransforms,61,62,67
Fragmentmolecularorbital(FMO) method,7
Frictionforce,99,100f
Friedel’slaw,117–118
Fullwidthathalfmaximum(FWHM), 394–395
G
Galdermamodelednonionicsurfactants,33 Gelation,423
GFmethod. See Green’sfunction(GF) method
Graphene,12,25,25f,180–181,180f.
Seealso Graphite
AFMtopography,343f dynamicripples,102–106,103f
EELF,361f,362f few-layer-graphene,341–343 graphenenanostructures,337 HOPG,341–343
LLGtechniques,337 Ramanspectrum,340–341 SEMsurfacemorphology,339f TEMmicrograph,343f Graphenenanoribbons(GNRs),94–95,95f, 96–98,97f,461–462
Graphite
Brillouinzone,207,208f Datta’sapproach,205–206 Diracpoints,207 energydispersioncurve,207 grapheneunitcell,204–205 hexagonalstructure,204,204f nanoribbons,209–210
Schrodingerequation,204–205 valenceandconductionbands,206 vectordistances,204f,205–206 wavefunction,204–205 Graphiticnanomaterials graphene,180–181,180f Ramanspectroscopy,184–186 simulationtechniques(see Molecular dynamics(MD)) thermalexpansion(see Carbonnanotube (CNT))
Green’sfunction(GF)method atomisticpotentialmodels,445 bridginglengthscales,55–56 characteristicsof,63 Diracdeltafunction,61 discretelatticemodel,63–68 Fouriertransforms,61,62 GFMD,73–75 LSGF,68–71 MSGFmethod,58,59,71–73 responsefunction,59 spring constant j,59–60,60f timescales,57–58 2Dgrapheneapplication,76–81,77f,80f
H
Hagen-Poiseuilleflow,422 Hamiltonianmatrixsparse,6–7 Harbola-Sahni(HS)potential,411–412 Hartree-Fock-Roothan(HFR)method,5 Hartree-Focktheory,5,6 Hexagonalboronnitride,360–362 Hierarchicalmethods,20–21
Highangleannulardark-field(HAADF) images,115–116
Highestoccupiedmolecularorbital (HOMO),408
High-resolutiontransmissionmicroscopy (HRTEM)imaging,115–116,120, 121f
Homotopyanalysismethods(HAMs),430 Hybridmethods,21–22,21f HybridQM/MMmethods,29
I
InGaN/GaNcore-shell,325–326
Inorganicnanostructures catalysts,30–31 MOFs,29–30,30f zeolites,28–29
Interfacialthermalresistance CNT,455–456 researchmotivation,454–455 solid-liquidinterfaces,456–457
Isothermaltitrationcalorimetry(ITC),170
K
Kanzakiforce,71,73
Kineticfriction,98–102
KineticMonteCarlo(KMC),30
Koch-Friedlanderpredictions,424
Kohn-Sham(KS)potential,408–411
Kullback-Leibler(KL)divergence,429–430
L LAMMPS,91
Landauerformalism,92–94
Langevindynamics,14
Langevinthermostat,98–99
Lattice-Boltzmann(LB),13
Latticedefects,56
Latticedynamics,445,447t
Latticemodels,14
LatticestaticsGreen’sfunction(LSGF), 68–71
Lipids,31–33
Liposomes,31
Lithium-ionbattery,36–38,37f
Low-densitylinearpolyethylene(LLDPE), 35–36
Lowe-Andersenthermostat,18
M
Magneto-hydrodynamic(MHD)nanofluid, 430
Many-bodyperturbationtheory(MBPT),6 MARTINIforcefield,14–15,15f,16f,17, 18–19,32
MathematicalPrinciplesofNatural Philosophy,7
MDsimulation. See Moleculardynamics (MD)
Meantimetofailure(MTTF),395,396 Mermin-Wagnertheorem,102 Mesoscalemodels,12–20,13f
Metal-ligandbinding,21–22
Metal-organicframeworks(MOFs), 29–30,30f
Metal-organicvaporphaseepitaxy (MOVPE) core-shellInGaN/GaNMQWs heterostructures(see Core-shell InGaN/GaNmulti-quantum-well heterostructures) electronmicroscopytechniques,327–328 GaNmicropillars,328–329 reactorgeometries,325 onsapphiresubstrates,329 sidewallemission,325–326 Methodofmoments(MOM),427 Modelselectioncriteria(MSC),429 Modifiedembeddedatommethod(MEAM), 90–91
Moleculardynamics(MD),8–9,12,88–91, 445–446,447t algorithm,187–188 atomic-levelstresstensor,195 atomisticmodeling,58 dynamicripplesingraphene, 102–106,103f equationsofmotion,189–190 forcecomputation,189 initialconditionsandparameters,188–189 interatomicpotential,190 kineticfriction,101 MEAM/Tersoff-Brennerpotentials,90–91 Newton’ssecondlawofmotion,88–89 nonbondedLennard-Jonescutoff, 196,196t potentialenergy,88–89 samplinggeometry,196,197f
samplingphase,195 simplevelocityrescaling,196 thermodynamicquantities,190 X-raydiffraction,195–196
Molecularmechanics,8
Molecularorbitals(MOs),5
Molecularstatics(MS)
GNRs,94–95,95f,96–98
MEAMorTersoff-Brennerpotentials, 90–91 potentialenergy,88–89
SWCNTs,92,93f,94f
Moller-Plesset(MP)perturbation,6
Molybdenumdisulfide(MoS2)nanocrystals crystalphaseandelectronicband structures,484,486f fabricationof,481–482,483f FET,481
fluorine-dopedtinoxide(FTO)substrates, 486–487
opticalandPLproperties,486,487f photoluminescence(PL)effect,481 structureandAFMimaging,481,482f thickness-modulatedphototransistor, 483f,484
transfercharacteristic,484,485f
UV-vis-NIRabsorptionspectra,484–486 XPSmeasurements,487–489,488f
MOMwithinterpretiveclosure(MoMIC), 427
MonteCarlo(MC)method,9,446
Multiparticlecollisiondynamics(MPC),13
Multiplequantumwells(MQWs),323.
Seealso Core-shellInGaN/GaNmultiquantum-wellheterostructures Multiplequantumwells(MQWs),323 MultiscaleGreen’sfunction(MSGF) method,58,59,71–73 N
Nanoalloy(NA)catalysts alcoholfuelcells,254–255 binaryandternarysystems,253–254,254f COandalcoholoxidationreactions,254 DFT,255–256 encapsulatednanoparticles,258–259 GriffithandPaulingconfigurations, 255–256
HE-XRD/PDFstudy,260–261 HRTEMandEDScompositionmapping, 259,260f metalnanocrystalcores,258–259 PDFanalysis,261–262,261f reactor-typecell,261–262 strongmetal-supportinteraction,254 synthesis,256–258 ternaryPtVFeparticles,255–256 thermaltreatment,258–259 thermochemicalprocess,258–259,258f XAFSspectra,262 XANESspectra,260–261 Nanoparticleself-assembly DLS,420 finiteelementmethod,424–426 flocculationphenomena,421–423 fluxmethod,426–427 maximumlikelihoodestimator(MLE), 428 methodofmoments(MOM),427 modelselectioncriteria(MSC),429 nanofluidmodel,428–430 nanofluids,430–431 PBEs,423,424 PSDs,423 sectionalmethods(SM),428 Nanopatterneddevices a-Taconcentration,376f Cuelectroplating,372 Curecrystallization,376 depositiontechnology,371–372 electromigrationreliability,372 iPVDtechnologyandCuinterconnects, 398–399 metrologytechniques,394–397 microwavePECVDtechnology,390–394 MW-PECVDSiO2,381f,391f MW-PECVDtechnology,399 oxidefilms,379 SiO2 deposition,379–380,399 stressmigration,372–375,373f Tadepositions,372 transmissionelectronmicrographs, 372–375 trenchorientation,374f upperinsulatinglayer,377–378 upperSiO2 layer,379 XRDtool,376
Nanophotonics applications,352–353
Blochhydrodynamicmodel,357–358 continuummodels,collectivemodes, 356–357
DFT,352,353–356 electromagneticcontinuummodels, 364–367
graphene/noblemetalmultilayer composites,359–360
Lambin’smodel,357–358 plasmonics,360–362 plasmonoscillations,352 plasmonresonances,351–352 siliceneandgermanenesystems,362–364
Navier-Stokesfluidmechanics,13 Newtoniandynamics,17–18 Newtonianmechanics,7 Newton’ssecondlawofmotion,88–89 Ni-Cinteraction,95–96 Nonbondinteractions,10–11
NonequilibriumGreen’sfunction(NEGF), 447t
Nonequilibriummoleculardynamics (NEMD)simulation interfacethermalconductance,456–457 nanowire-basedheterostructures,454 Sinanowires,453–454 solid-liquidinterfaces,455–456 thermalconductivityofsilicene,452–453
Nonionicsurfactants,33
Nose ´ -Hooverthermostatalgorithm, 89–90,101
One-dimensional(1D)nanoheterostructure axiallyheterostructurednanowires, 126–128,126f,127f,128f,129f coaxialcore-shellnanowires(see Coaxial core-shellnanowires)
Pddecoration,134–137,135f QDSSC,137–139,138f,139f
One-dimensional(1D)nanostructures 1Dnanoheterostructure,125–139 superlatticenanowires,122–125, 123f,124f
TEM,115–117
2Dconfinementendows,115
ZnOnanostructures(see ZnO nanostructures)
ONIOMapproach,23–24
Optimizedeffectivepotential(OEP)method, 409–410
Pairdistributionfunction(PDFs)analysis, 246,247f,261–262,261f
Parrinello-Rahmanfluctuationmethod,27
Particle-basedsimulation
MD(see Moleculardynamics(MD))
MS(see Molecularstatics(MS))
Particlesizedistributions(PSDs),423
Peptideself-assembly,34
Peptosomes,34
Phenylrings,15
Phononglass-electroncrystal,448,449f
Photooxidationeffect
BEEblueshifts,298–299 CdSeQDs-PMMAcomposites,299–300 fluorescentcolors,299
PMMA-QDs/toluenesolution,296–297 QYs vs. UVirradiationtimes,299 UVlightirradiation,296–297
Piezoelectriceffects,56
Plasmoniccouplingeffect
Agnanostructures,304–310 layerthickness,303–304 sizeeffects,301–302
Plasmons
Agnanostructures,304–310 CQDssizeeffect,301–302 microscalefluorescentcolorpatterns, 312–314
PMMA-graphenecompositemodel,26,27f
Polycrystalline SnO2-coatedZnO nanowires,134–135
Polyethylene,25f,26
Polyethylene/graphenenanocomposites, 25,25f
Polymernanocomposites(PNCs),24–27, 25f,26f,28f
Polymernanodielectrics,34–36
Polystyrene-block-polybutadiene,33
Populationbalanceequation(PBE),423,424
Potentialdefects,56 Potentialenergy,16–17,16f
Potentialofmeanforce(PMF),18–19
Pulsedlaserdeposition(PLD),130–131
Q
QM/MMmethods,21–24,22f,23f
QM-Potapproach,22
Quadraturemethodofmoments(QMOM), 427
Quantumcapacitance
Cq,213 gateterminal,214 inversesubthresholdslope,215 I-Vdevice,215 MOSFETdevice,213,214–215,214f
ONandOFFcurrent,215,215f one-dimensionalFETs,215f,216 Quantumdots(QDs),56,115
Quantum-dot-sensitizedsolarcells (QDSSC),137–139,138f,139f
QuantumESPRESSO,356
Quantummechanics(QM)methods,4–7
R
Ramanspectroscopy,327 AIREBO,184
BOLSmechanism,185,192–193 bulk vs. individualSWCNT,191–192 instrumentsetup,185,186f laserpowersetting,185 linearfrequencydownshift,185,186f, 187f,188f,194 SEM,185
SWCNTs,185 temperatureslopes,185,189t
Resolutionoftheidentity(RI)approach,6 Rootmean-squaredisplacement (RMSD),104
S
Scanningelectronmicroscopy(SEM) analysis,185
Scanningtransmissionelectronmicroscope (STEM)mode,115–116
Scatchard-Hildebrandtheory,19 Schodinger’swaveequation,4 Schrodingerequation,445 Seebeckcoefficient,444
Select-areaelectrondiffraction(SAED) patterns,115–116
Self-assembly. See Nanoparticleselfassembly
Semiconductorcolloidalquantumdots (CQDs)
band-to-bandandSSs,292 BEEandSSE,291–292 BEEintensity,294–295 chemicalandphysicalproperties,289–290 chemicalsynthesisandphysicaltreatment, 293 hot-injectionroute,290–291 lightemissionefficienciesandstability, 289–290 light-emittingdiodes,290–291 optoelectronictechnologies,290–291 photoluminescence(PL)spectra,291–292 photooxidationeffect,296–300 plasmoniccouplingeffect,300–311 PLspectrum,294,294f,295f Ramanscattering,290–291 surfacestatesemission,291 whiteLEDs,314–315 WLE,single-size,296 ZnSshell,290 Shinodaforcefield,15,15f,19
Shirleymethod,501 SIESTA,355 Silicene,451–453
Singleanddoubleelectronconfigurations (CISD),5–6
Single,double,andalimitedclassoftriple excitations(CCSD(T)),6
Single,double,triple,andquadruple excitations(CISDTQ),5–6
Single-wallcarbonnanotubes(SWCNT), 92–94,93f CNT(see Carbonnanotube(CNT)) Ramanspectroscopy(see Raman spectroscopy)
SODF. See Strainandstressori-entation distributionfunctions(SODF)
Solidelectrolyteinterphase(SEI),37,38f Sphericalharmonics Clebsch-Gordoncoefficients,148–149 cubic crystalsymmetry,148–149 Eulermatrixelements,154 groundstate,149
Sphericalharmonics (Continued)
Legendrefunction,150–152 orthorhombicsamplesymmetry,148–149 Rietveldprogram,154–155 selectionrule,152,152t,153t straintensor,153–154 stresstensor,154
WSODF,148–149
Stacking-fault-inducedgrowth,ZnO nanobelts,120–122
Staticcalculations,91–98
Steelepotential,26
STEM-HAADFmode,124,124f
Stillinger-Weber(SW)parameters,452–453
Strainandstressori-entationdistribution functions(SODF) averagedmacrostrain,147 averagedstrains/stresses,147–148 coefficientsofexpansion(see Spherical harmonics) diffractionstressfactors,148 directioncosines,147 Hookeequations,145–146 intergranulartensor,147 Laueequation,146–147 plasticinteractions,148 reducedpoledistribution,147 samplereferencesystem,146 strainpoledistribution,147,148
Structuraldefects,56
StudioStudiopackage,26
Superlatticenanowires,122–125,123f
Surfaceplasmonresonances(SPRs), 351–352
Surfactants,33
SWCNT. See Single-wallcarbonnanotubes (SWCNT)
SynchrotronX-ray-basedtechniques Au-AupartialPDF,267,268f
AumPt100-m particlesanneal,267,268f fcc-latticeparameters,266–267,266f fct-typemodel,262,263–265
HE-XRDdiffractionpatterns, 263–265,264f hypotheticalfccmodel,263–265
OR-RRtreatmentatmosphere,262,263f PtComodelandCoKedgedata, 265–266,265t PtNiConanoalloy,266–267,266f
insitu real-time,267,269f structuralcharacterizations,260–261,261f thermochemicalevolutionprocesses,267
TTaylorseries,65–66
Tersoff-Brennerpotential,90–91 Tersoffpotential,64,76–77
TGA. See Thermogravimetricanalysis (TGA)
Thermalanalysismethods calorimetry,174 CNT,171–172 curekinetics,174 DSC,169–170 experimentalenthalpy,174 ITC,170 nanomedical-basedproducts,175 thermogravimetricanalysis,168–169
Thermalconductivity bulknanostructuredmaterials,449–450 energyconversionefficiency,448 grapheneandgraphene-based heterostructures,450–451 nanowire-basedheterostructures,454 phononglass-electroncrystal,448,449f silicene,451–453 single-componentnanowires,453–454
Thermogravimetricanalysis(TGA), 168–169 adsorbedproteinmass,173 chemicalcomposition,172 masslossmeasurements,172 microscale,175–176 nanocomposites,173 oxidationtemperature,171–172 solution-basedprocess,170–171
Thermostaticcontrol,89–90
Thin-filmdeposition,479,480t
Thin-filmferroelectric(FE)material capacitanceanddielectricloss,158 coupledscans,159,160f Curie-Weisstemperature,163–164,163f dielectricmeasurement,158 dielectricpermittivityandloss,159,159f dislocationdensity,162–163,162f elasticstrains,157,161,161f energydensity,157–158
inhomogeneousstrain,157 latticeparameters,155 opticalproperties,158 polarization,156–157 potentialapplications,155–156 properties,156 relaxationprocess,161–162
Scintagfour-circlediffractometers,158 tetragonaldistortion,159–161 two-circledouble-axisdiffractometers, 158
Throughsiliconvias(TSVs),399–401
Transmembraneproteins,32
Transmissionelectronmicroscope(TEM), 327–328. Seealso One-dimensional (1D)nanostructures
Triethylenetetramine(TETA),27
Tungstenoxide(WO3)nanocrystals
AFMimages,494,495f bearinganalysis,494,496t blackphosphorusFETs,504–507 chargecarriermobility,500 Coulombcharges,500 experimentalcharacteristicson,495–498, 497f FETdevice,498–500,499f H+ intercalationprocess,495–498, 500–501 nonstoichiometricproperties,493 photocatalysisandsensing,493–494 WO3–x,503
XPSmeasurementsandanalysis,501, 502–503,502f
2Dhybrid-domainsuperlattices armchairandzigzagcases,465,466–468 bandgap,461–462 boundaryenergyandstress,464–465,466, 467f,467t C–BNsuperlatticemodels,465–466 deformationbehaviors,464,469f DFTcomputations,461–462 elasticproperties,464 electronicproperties,471–472,471f GNRsandBNNRs,468 graphene–BNribbons,464 Monkhorst-Packscheme,465–466 N-andB-terminatededges,468–469 oscillatingbehavior,470–471,470f plane-wavebasis,468
SIESTAprogram,465 synthesis,462–463,463f Tersoffpotential,469 Two-dimensional(2D)nanocrystals featuresof,513 graphene,508 molecular-levelthickness,511–513 nanosheet-based2Dcompositematerials, 509f,510–511 propertiesandapplications,510,510f Two-dimensionalsemiconductors fabricationmethods(see Fabrication methods)
MoS2 nanocrystals(see Molybdenum disulfide(MoS2)nanocrystals) semiconductornanocrystals,477–481, 478f WO3 nanocrystals,493–503 WSe2 nanocrystals,489–493
Ultraviolet(UV)laser,293
vanderWaalsinteractions,16,90 Vapor-liquid-solid(VLS),117 ViennaAb-initioSimulationPackage (VASP),356 VLS-grownternarynanowires,126–127
W
WSe2 p-n diode ambipolartransport,489 current-voltagecharacteristics,489–490 CVD,491–493 electroluminescenceefficiency,489–490 electroluminescencespectrum,491,492f fabricationmethods,493 lateraldiode,489,490f photovoltaicpowergeneration,491,492f Wurtzite(WZ)structure,117–118 X
XAFS. See X-rayabsorptionfinestructure (XAFS) X-rayabsorptionfinestructure(XAFS),256
X-raydiffraction
residualstrains/stresses(see Strainand stressori-entationdistribution functions(SODF))
strainbroadening,crystallinedefects (see Thin-filmferroelectric(FE) material)
three-dimensionalcrystalline,145 X-rayphotoelectronspectroscopy(XPS) measurements,487–489,488f
Y Young’smodulus,27 Z
Z-contrastimaging,119–120
Zeolites,22,28–29,29f
Zigzag-edgeribbonsgraphenenanoribbon (ZGNR),209–210
Zincblende(ZB)structure, 117–118
ZnOnanostructures polaritydetermination,117–120 stacking-fault-inducedgrowth, 120–122,121f
ZnO/ZnScore-shellnanowire,130–131, 131f,132f
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1.1Introduction
Molecularmodelinghaslongbeenusedtopredictthepropertiesofmoleculesand crystalsattheatomicscale,wherethesizeislessthan10nm.Anumberoftechniquesarerequiredinordertoprovideacompletepictureviamolecularmodeling. Asarule,moreaccuratetechniquesrequiresubstantiallymorecomputertime andarehencelimitedtosmallersizesystems.Asonetriestomodellargersystems, moreapproximationsarerequiredinorde rtomaintainreasonablecomputational resources.
Inthepast,asinglemethodappropriatetoone’sresearchtopiccouldbeselected. However,theemergenceof nanomaterialsinthelastf ewdecadeshasposedaparticularchallengebecausemodelingonm ultiplelengthandtimescalesinvolvesa hierarchyofmethodsasshownin Figure1.1 .Nanomaterialsmayconsistofseveral thousandatomsandarestillgovernedby quantummechanical (QM)effects,but eventhebestQMmodelingmethodsarelimitedtoaround103 atoms.Howthen, canwecreatemodelsthatincorporatet herequisiteaccuracybutarefastenough tobeapplicabletolargelengthscales?Thisisthequestionthatwewillexplore inthepresentchapter.
Section1.2 willprovideanoverviewofthemajormodelingmethodscurrentlyin use.QM,forcefield-based,andcoarse-grainedapproachesareintroduced;thenit willbeshownhowthesemethodscanbecombinedintomultiscalemodels.However, adiscussionofcontinuummodelsisnotincluded. Section1.3 containsexamplesof howthesemethodshavebeenappliedtodifferentclassesofmaterials,includinginorganicnanomaterials,nanocomposites,andbio-likematerials. Section1.4 provides somecasestudiesthatdelveintogreaterdetail:lithiumionbatteries,nanodielectrics, andresinsforaerospaceapplications.
Figure1.1 Lengthandtimescalesofdifferentmodelingmethods.Eachscaleislabeledbya methodandexampleapplication. 4
1.2.1Quantummechanics
1.2.1.1Introduction
Calculationsbasedon abinitio QMmethodsarethemostaccurateofallmolecular modelingapproaches.Thesecalculations,basedonthesolutionofSchrodinger’s waveequation,requirenoempiricalparametersorpreviousexperimentalknowledge.Theyareessentialformodelingchemicalreactionsandforstudyingelectronicallyexcitedstates.However,suchmethodsarelimitedtosystemscontainingon theorderof 103 atomsandtodynamicsimulationsofafewpicoseconds.The lengthandtimescalesofrelevancetolaboratoryresearchproblemsareconsiderably larger:systemscontainingAvogadro’snumberofatoms( 1023 )evolvingfor minutesorhours. Abinitio methodsareneverthelesse ssentialforobtainingchemicalaccuracy.Bythemselves,theycanbeappliedtomodelsystemsthatprovide insightintoreal-worldchemicalbehavior.Inaddition,whenusedinmultiscale modeling,theyprovideanaccuratefoundationthatcanbeextendedtomuchlarger, practicalsystems.
Allthemethodsdescribedinthissectionwillbebasedonthetime-independent SchrodingerequationandtheBorn-Oppenheimerapproximation(Bornand Oppenheimer,1927).Thisassumesthatthemotionofatomicnucleiisslowcompared toelectronicmotionandallowsustodefineapotentialenergysurface.Wecanspecify aparticularmoleculargeometryandassumethenucleiarestationarywhilewesolve forthewavefunction.Giventhewavefunction,wecanobtaintheenergyandforces ontheatomsandsearchforminimumenergystructures,orwecanobtainproperties suchasionizationpotentials,dipolemoments,andIRandRamanspectra.
1.2.1.2Hartree-Focktheory
TheHartree-Fockmethod(Fock,1930)asimplementedby Roothan(1951) formed thefirstpracticalapproachtoobtainingenergiesandwavefunctionsforpolyatomic molecules.Inthisapproach,thewavefunction C consistsofananti-symmetrized determinantofmolecularorbitals(MOs) ’i.Eachorbitalisfurtherbrokendowninto asetofatomicorbitals, wm
The cim areMOcoefficientsthatexpresstheMOsintermsofatomicorbitals.Adetailed expositionoftheRoothanequationsisbeyondthescopeofthepresentchapter.Insimplifiedform,however,theequationscanbereducedtothematrixexpression:
whichmustbesolvedfor C. Here F istheso-calledFockmatrix, C isthematrixofMO coefficients, S istheoverlapbetweentwoatomicorbitals,and e aretheeigenvaluesof F correspondingtotheenergiesofeachMO.Equation (1.2) appearsdeceptivelysimple.Infact,theFockmatrix F dependson C,thecoefficientswearetryingtosolvefor. Henceaniterativeapproachisneeded:Aninitialguessfor C0 isusedtoconstruct F, andthensolvetheRoothanequationstoyieldanewresult, C1.Theprocesscontinues until Ci doesnotchangefromoneiterationtothenext.
TheHartree-Fock-Roothan(HFR)methodhasbeenusedextensivelysinceitsinception. Asapracticalmethodforlarge-scalecalculations,however,HFRistooslow.Formally, thecomputationalcostincreasesas N4 increases,where N isthenumberofelectrons. Althoughbroadlysuccessful,itisnotaccurateenoughformanycases,suchasmetal-metal bonds,heatsofformation,andchemicalbondbreaking(SzaboandOstlund,1982).
1.2.1.3Electron-correlatedmethods
HFRisbasedonamean-fieldthatignoresinstantaneouscorrelationsamongtheelectrons.Anumberofapproacheshavebeendevelopedtocomputethismissingcontribution,referredtoasthe correlationenergy.Allofthesemethodsincreasethe accuracyoftheresults,buttheyalsoincreasethecomputationalcostsignificantly. Asaconsequence,thesemethodsarenotusedextensivelyinmultiscaleapproaches, andsowillbetouchedupononlybriefly.
Theconfigurationinteraction (CI)method(Shavitt,1977)usestheHFRwave functionasthestartingpoint.Itthenconstructsadditionalelectronconfigurations byexcitingelectronsfromtheoccupiedMOstotheunoccupied(virtual)MOs,each ofwhichisdescribedbyitsownSlaterdeterminant.TheCIwavefunctionistakenasa linearcombinationofthesedeterminants.A full-CI wouldincludeallpossibleexcitationsofelectrons.Thiswouldprovidethetotalcorrelationenergy,butthecalculationwouldbeprohibitivelyexpensivebecausethenumberofconfigurationsscales factorially(as N!).Thechoiceofdeterminantsistypicallylimitedtochemicallysignificantelectronconfigurations.Selectingtheconfigurationsfromallsingleand
doubleelectronconfigurations(CISD)canyield80-90%ofthecorrelationenergy (HarrisonandHandy,1983)forafractionofthecost.Includingsingle,double,triple, andquadrupleexcitations(CISDTQ)canachieveover99%ofthecorrelationenergy.
Analternativeapproachisthatbasedonmany-bodyperturbationtheory(MBPT), someformsofwhicharecommonlycalledMøller-Plesset(MP)perturbation theory(MøllerandPlesset,1934).TheFockoperatoristakenasthezeroth-order Hamiltonian,andtheperturbationisthedifferencebetweentheFockoperatorand theexactHamiltonian.MP2isthesimplestapproximationandcanrecover 80% ofthecorrelationenergy,butscalesonlyas N5 .
Coupled-clustermethodsapplymoresophisticatedperturbations.Coupled-cluster calculationswithsingleanddoubleexcitations(CCSD)(BartlettandPurvis,1980), forexample,obtainmorethan90%ofthecorrelationenergy,andscaleas N6.Currently,coupled-clustermethodsincludingsingle,double,andalimitedclassoftriple excitations(CCSD(T))(PurvisandBartlett,1982)representsomeofthemostaccurate calculationspossible.Becausethesescaleas N7,however,theyarenotwidelyusedin commercialapplications.
1.2.1.4Densityfunctionaltheory
Densityfunctionaltheory(DFT)representsanalternativeapproachbasedonHartreeFocktheory.DFTbeginswithatheoremby HohenbergandKohn(1964),latergeneralizedby Levy(1979),whichstatesthatallground-statepropertiesarefunctionals ofthechargedensityfield r.Thetotalenergy, Et,maybewrittenas:
where T[r]isthekineticenergy, U[r]istheclassicalelectrostaticenergydueto Coulombicinteractions,and Exc [r]includestheexchangeandcorrelationcontributions.Hartree-Fockincludesthecompleteexchangeenergybutnoneofthecorrelation. DFT,bycontrast,includesaportionofbothexchangeandcorrelation.Theexpression for Exc requiresanapproximationtobecomecomputationallypractical.Thesimplest approximationisthelocaldensityapproximation,whichisbasedontheknown exchange-correlationenergyoftheuniformelectrongas(HedinandLundqvist, 1971;CeperleyandAlder,1980;LundqvistandMarch,1983).Analyticalrepresentationshavebeenmadebyseveralresearchers(HedinandLundqvist,1971;Ceperleyand Alder,1980;vonBarthandHedin,1972;Voskoetal.,1980;PerdewandWang,1992). Improvedexpressionsfor Exc canbeobtainedbyexpandingitasafunctionof rr or r2 r (Ziegler,1991;PerdewandWang,1992;Leeetal.,1988). Perdew(2013) recently outlinedaschemeforsystematicallygeneratingevenmoreaccuratefunctionals.
Byusingtheso-calledresolutionoftheidentity(RI)approach(Feyereisenetal., 1993),DFTmethodscanbemadetoscaleas N3,whichisconsiderablylessexpensive thananyelectron-correlatedmethod.Despiteitssimplicity,DFTcanpredictbond lengthstopicometer(10 12 m)accuracyandenthalpiesofreactiontowithinapproximately5kcal/mol(LabanowskiandAndzelm,1991).
Thisperformanceisadequateforcalculationsonnanoclusterscontaining10002000atoms,butisstilltooslowforQMcalculationsonmodelsgreaterthan
10nm.OthermethodsarerequiredtopushDFTtothatscale.LinearscalingDFT (Skylarisetal.,2005)hassignificantlyextendedthecapabilityofDFT.Linearscaling isachievedbyperformingatransformationontheMOstolocalizethem.Thismakes theHamiltonianmatrixsparse,significantlyreducingcomputationaleffort.
LinearscalingDFThasbeenappliedtosystemswithmorethan1000atoms, includingproteins,semiconductors,andmicroelectronics(Skylarisetal.,2005).LinearscalingmethodsrequireconsiderablylessCPUtimethanconventionalDFT methods,butevenso,calculationsarestillexpensive.Thisisbecausecomputational overheadisrequiredtolocalizetheMOs.Thisoverheadisrecoveredwhendoing largercalculations,butnotinthecaseofsmallercalculations.Thebreak-evenpoint isaround300-400atoms.Belowthat,conventionalDFTmethodsappeartobemore efficient;abovethatlinearscalingmethodswinout.
1.2.1.5Othermethods
Anumberofothermethodshavebeendevelopedwiththegoalofdeliveringhigher accuracyforlowercomputationalcost.Themostrelevantforthischapterarethefragmentationmethodsrecentlyreviewedby Gordonetal.(2012).Asthenamesuggests, suchmethodsmakecalculationsmoretractablebybreakingmoleculesintofragments andcombiningresultsintoatotal.Theseapproachesincludethedivideandconquer (DC)(Yang,1991)andfragmentmolecularorbital(FMO)(Kitauraetal.,1999) methods,tonamejusttwo.InDC,an adhoc totaldensityisconstructedfromfragment calculations,followedbyasingleenergyevaluation.IntheFMOmethod,oneperformsfragmentcalculationsintheelectrostaticfieldofotherfragments,untilthe resultsareinternallyself-consistent.Suchmethodshavebeenappliedtopolypeptides (Lietal.,2002;Jensenetal.,2005)andevenprotein-ligandinteractions(Fukuzawa etal.,2005;Sawadaetal.,2006)thatcontainthousandsofatoms.
Despitethepromiseofsuchmethods,theyremainunderutilized.Reasonsforthis includethelackofcommerciallyavailable(i.e.,easy-to-use)packagesanduncertainly abouttheiraccuracy(Gordonetal.,2012).Theyremainpromising,however,andcan beexpectedtoplayasignificantroleasmodelersdemandcalculationsonlarger molecularandsolid-statesystemsinthenearfuture.
1.2.2Classicalmechanics
ThenextclassofmolecularmodelingtoolsisbasedonclassicalorNewtonian mechanics.Infact,mostfoundationsofclassicalmechanicscanbefoundinNewton’s MathematicalPrinciplesofNaturalPhilosophy firstpublishedin1687.Themaindifferenceswith abinitio methodsisthathere(i)electronsarenotexplicitlyincluded (atomsarethesmallestfragments)and(ii)intrinsic(empirical)parametersare employedtodescribethebehaviorandrelationsof atomtypes.Anatomtypeincludes theatomicnumberoftheatomaswellasinformationsuchasthehybridizationstate andthelocalenvironment(e.g.,neighboratomsitisbondedto).Aforcefieldoran atomisticpotentialisemployedtodescribetheinteractionsbetweenalltheatoms ofthemodel;therearemanytypesofsuchforcefieldsorpotentialfunctionsandthey toowillbereviewedinthepresentsection.
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child, a bit of the index held between the antagonised thumb and medius is shown. The same sign expresses both parents, with additional explanations. To say, for instance, my mother, you would first pantomime “I,” or, which is the same thing, my, then woman, and finally, the symbol of parentage. My grandmother would be conveyed in the same way, adding to the end, clasped hands, closed eyes, and like an old woman’s bent back. The sign for brother and sister is perhaps the prettiest; the two first finger-tips are put into the mouth, denoting that they fed from the same breast. For the wife—squaw is now becoming a word of reproach amongst the Indians—the dexter forefinger is passed between the extended thumb and index of the left.
Of course there is a sign for every weapon. The knife—scalp or other—is shown by cutting the sinister palm with the dexter ferient downward and towards oneself: if the cuts be made upward with the palm downwards, meat is understood. The tomahawk, hatchet, or axe, is denoted by chopping the left hand with the right; the sword by the motion of drawing it: the bow by the movement of bending it, and a spear or lance by an imitation of darting it. For the gun the dexter thumb or fingers are flashed or scattered, i.e. thrown outwards and upwards, to denote fire. The same movement made lower down expresses a pistol. The arrow is expressed by knocking it upon an imaginary bow, and by snapping with the index and medius. The shield is shown by pointing with the index over the left shoulder where it is slung ready to be brought over the breast when required.
The pantomime, as may be seen, is capable of expressing detailed narratives. For instance, supposing an Indian would tell the following tale:—“Early this morning I mounted my horse, rode off at a gallop, traversed a ravine, then over a mountain to a plain where there was no water, sighted bisons, followed them, killed three of them, skinned them, packed the flesh upon my pony, remounted, and returned home,”—he would symbolize it thus:
Touches nose—“I.”
Opens out the palms of his hand—“this morning.”
Points to east—“early.”
Places two dexter forefingers astraddle over sinister index —“mounted my horse.”
Moves both hands upwards and rocking-horse fashion towards the left—“galloped.”
Passes the dexter hand right through thumb and forefinger of the sinister, which are widely extended—“traversed a ravine.”
Closes the finger-tips high over the head and waves both palms outwards—“over a mountain to a plain.”
Scoops up with the hand imaginary water into the mouth, and waves the hand from the face to denote no—“where there was no water.”
Touches eye—“sighted.”
Raises the forefingers crooked inwards on both sides of the head —“bison.”
Smites the sinister palm downwards with the dexter first—“killed.” Shows three fingers—“three of them.”
Scrapes the left palm with the edge of the right hand—“skinned them.”
Places the dexter on the sinister palm and then the dexter palm on the sinister dorsum—“packed the flesh upon my pony.”
Straddles the two forefingers on the index of the left —“remounted.”
Finally, beckons towards self—“returned home.”
“While on the subject of savage modes of correspondence, it may not be out of place to quote an amusing incident furnished by the Western African traveller Hutchinson. There was, it seems, a newspaper established in the region in question for the benefit of the civilized inhabitants, and an old native lady having a grievance, “writes to the editor.” Let us give her epistle, and afterwards Mr. Hutchinson’s explanation of it:
“To Daddy Nah, Tampin Office
“H D , Do yah nah beg you tell dem people for me make dem Sally own pussin know Do yah. Berrah well. Ah lib nah Pademba Road one buoy lib dah ober side lakah dem two docta lib overside you Tampin office Berrah well Dah buoy head big too much he say nah Militie Ban he got one long long ting so so brass someting lib da dah go flip flap dem call am key Berry well Had dah buoy kin blow she ah na marnin, oh na sun time, oh na evenin, oh nah middle night oh all same no make pussin sleep Not ebry bit dat more lib dah One Boney buoy lib overside nah he like blow bugle When dem two woh woh buoy blow dem ting de nize too much to much. When white man blow dat ting and pussin sleep he kin tap wah make dem buoy carn do so. Dem buoy kin blow ebry day, eben Sunday dem kin blow. When ah yerry dem blow Sunday ah wish dah bugle kin blow dem head bone inside. Do nah beg you yah tell all dem people bout dah ting, wah dem to buoy dah blow. Tell am Amstrang Boboh hab feber bad. Tell am Titty carn sleep nah night. Dah nize go kill me two picken oh. Plabba done Good by, Daddy.
“C J .”
“For the information of those not accustomed to the Anglo-African style of writing or speaking, I deem a commentary necessary in order to make this epistle intelligible. The whole gist of Crashey Jane’s complaint is against two black boys who are torturing her morning, noon, and night—Sunday as well as every day in the week—by blowing into some ‘long, long brass ting,’ as well as a bugle. Though there might appear to some unbelievers a doubt as to the possibility of the boys furnishing wind for such a lengthened performance, still the complaint is not more extravagant than those made by many scribbling grievance-mongers amongst ourselves about the organ nuisance.
“The appellative Daddy is used by the Africans as expressive of their respect as well as confidence. ‘To Daddy in the stamping (alias printing) office,’ which is the literal rendering of the foregoing address, contains a much more respectful appeal than ‘To the Editor’ would convey, and the words ‘Berrah well’ at the end of the first sentence are ludicrously expressive of the writer’s having opened the subject of complaint to her own satisfaction and of being prepared to go on with what follows without any dread of failure.
“The epithet ‘woh-woh’ applied to the censured boys means to entitle them very bad; and I understand this term, which is general over the coast, is derived from the belief that those persons to whom it is applied have a capacity to bring double woe on all who have dealings with them. ‘Amstrang Boboh,’ who has the fever bad, is Robert Armstrong, the stipendiary magistrate of Sierra Leone, and the inversion of his name in this manner is as expressive of negro classicality as was the title of Jupiter Tonans to the dwellers on Mount Olympus.”
It is probable that to his passion for “picture making” Mr. Catlin is indebted for his great success among North-American children of the wilderness. A glance through the two big volumes published by that gentleman shows at once that he could have little time either for eating, drinking, or sleeping; his pencil was all in all to him. No one would suppose it by the specimens Mr. Catlin has presented to the public, but we have his word for it, that some of the likenesses he painted of the chiefs were marvels of perfection—so much so, indeed, that he was almost tomahawked as a witch in consequence. He says:
“I had trouble brewing from another source; one of the medicines commenced howling and haranguing around my domicile amongst the throng that was outside, proclaiming that all who were inside and being painted were fools and would soon die, and very naturally affecting thereby my popularity. I, however, sent for him, and called him in the next morning when I was alone, having only the interpreter with me, telling him that I had had my eye upon him for several days and had been so well pleased with his looks that I had taken great pains to find out his history, which had been explained by all as one of a most extraordinary kind, and his character and standing in his tribe as worthy of my particular notice; and that I had several days since resolved, that as soon as I had practised my hand long enough upon the others to get the stiffness out of it (after paddling my canoe so far as I had) and make it to work easily and succesfully, I would begin on his portrait, which I was then prepared to commence on that day, and that I felt as if I could do him justice. He shook me by the hand, giving me the Doctor’s grip, and beckoned me to sit down,
which I did, and we smoked a pipe together After this was over he told me that he had no inimical feelings towards me, although he had been telling the chiefs that they were all fools and all would die who had their portraits painted; that although he had set the old women and children all crying, and even made some of the young warriors tremble, yet he had no unfriendly feelings towards me, nor any fear or dread of my art. ‘I know you are a good man (said he), I know you will do no harm to any one; your medicine is great, and you are a great medicine-man. I would like to see myself very well, and so would all of the chiefs; but they have all been many days in this medicine-house, and they all know me well, and they have not asked me to come in and be made alive with paints. My friend, I am glad that my people have told you who I am; my heart is glad; I will go to my wigwam and eat, and in a little while I will come and you may go to work.’ Another pipe was lit and smoked, and he got up and went off. I prepared my canvass and palette, and whistled away the time until twelve o’clock, before he made his appearance, having employed the whole forepart of the day at his toilette, arranging his dress and ornamenting his body for his picture.
“At that hour then, bedaubed and streaked with paints of various colours, with bear’s-grease and charcoal, with medicine-pipes in his hands, and foxes’ tails attached to his heels, entered Mah-to-he-bah (the old bear) with a train of his profession, who seated themselves around him, and also a number of boys whom it was requested should remain with him, and whom I supposed it possible might have been his pupils whom he was instructing in the mysteries of his art. He took his position in the middle of the room, waving his evil calumets in each hand and singing the medicine song which he sings over his dying patient, looking me full in the face until I completed his picture at full length. His vanity has been completely gratified in the operation; he lies for hours together day after day in my room in front of his picture gazing intently upon it, lights my pipe for me while I am painting, shakes hands with me a dozen times each day, and talks of me and enlarges upon my medicine virtues and my talents wherever he goes, so that this new difficulty is now removed, and instead of preaching against me he is one of my strongest and most enthusiastic friends and aids in the country.
“Perhaps nothing ever more completely astonished these people than the operations of my brush. The art of portrait painting was a subject entirely new to them and of course unthought of, and my appearance here has commenced a new era in the arcana of medicine or mystery. Soon after arriving here I commenced and finished the portraits of the two principal chiefs. This was done without having awakened the curiosity of the villagers, as they had heard nothing of what was going on, and even the chiefs themselves seemed to be ignorant of my designs until the pictures were completed. No one else was admitted into my lodge during the operation, and when finished it was exceedingly amusing to see them mutually recognizing each other’s likeness and assuring each other of the striking resemblance which they bore to the originals. Both of these pressed their hand over their mouths awhile in dead silence (a custom amongst most tribes when anything surprises them very much); looking attentively upon the portraits and myself and upon the palette and colours with which these unaccountable effects had been produced.
“Then they walked up to me in the most gentle manner, taking me in turn by the hand with a firm grip, and, with head and eyes inclined downwards, in a tone of a little above a whisper, pronounced the words te-ho-pe-nee Wash-ee, and walked off.
“Readers, at that moment I was christened with a new and a great name, one by which I am now familiarly hailed and talked of in this village, and no doubt will be as long as traditions last in this strange community.
“That moment conferred an honour on me which you, as yet, do not understand. I took the degree (not of Doctor of Law, nor Bachelor of Arts) of Master of Arts—of mysteries, of magic, and of hocus pocus. I was recognized in that short sentence as a great medicine white man, and since that time have been regularly installed medicine, or mystery,—which is the most honourable degree that could be conferred upon me here, and I now hold a place amongst the most eminent and envied personages, the doctors and conjurati of this titled community.
“Te-ho-pe-nee Wash-ee—pronounced ‘tup’penny’—is the name I now go by, and it will prove to me no doubt of more value than gold, for I have been called upon and feasted by the doctors, who are all mystery-men, and it has been an easy and successful passport already to many strange and mysterious places, and has put me in possession of a vast deal of curious and interesting information which I am sure I never should have otherwise learned. I am daily growing in the estimation of the medicine-men and the chiefs, and by assuming all the gravity and circumspection due from so high a dignity (and even considerably more), and endeavouring to perform now and then some art or trick that is unfathomable, I am in hopes of supporting my standing until the great annual ceremony commences, on which occasion I may possibly be allowed a seat in the medicine lodge by the doctors, who are the sole conductors of this great source and fountain of all priestcraft and conjuration in this country. After I had finished the portraits of the two chiefs and they had returned to their wigwams and deliberately seated themselves by their respective firesides and silently smoked a pipe or two (according to an universal custom), they gradually began to tell what had taken place; and at length crowds of gaping listeners, with mouths wide open, thronged their lodges, and a throng of women and girls were about my house, and through every crack and crevice I could see their glistening eyes which were piercing my hut in a hundred places, from a natural and restless propensity—a curiosity to see what was going on within. An hour or more passed in this way and the soft and silken throng continually increased until some hundreds of them were clung and piled about my wigwam like a swarm of bees hanging on the front and sides of their hive. During this time not a man made his appearance about the premises; after awhile, however, they could be seen folded in their robes gradually sidling up towards the lodge with a silly look upon their faces, which confessed at once that curiosity was leading them reluctantly where their pride checked and forbade them to go. The rush soon after became general, and the chiefs and medicine-men took possession of my room, placing soldiers (braves, with spears in their hands) at the door, admitting no one but such as were allowed by the chiefs to come in. The likenesses were instantly recognized, and many of the
gaping multitude commenced yelping; some were stamping off in the jarring dance, others were singing, and others again were crying; hundreds covered their mouth with their hands and were mute; others, indignant, drove their spears frightfully into the ground, and some threw a reddened arrow at the sun and went home to their wigwams.
“The pictures seen, the next curiosity was to see the man who made them, and I was called forth. Readers, if you have any imagination, save me the trouble of painting this scene. I stepped forth and was instantly hemmed in in the throng. Women were gazing, and warriors and braves were offering me their hands, whilst little boys and girls by dozens were struggling through the crowd to touch me with the ends of their fingers, and while I was engaged from the waist upwards in fending off the throng and shaking hands my legs were assailed (not unlike the nibbling of little fish when I have been standing in deep water) by children who were creeping between the legs of the bystanders for the curiosity or honour of touching me with the end of their finger. The eager curiosity and expression of astonishment with which they gazed upon me plainly showed that they looked upon me as some strange and unaccountable being. They pronounced me the greatest medicineman in the world, for they said I had made a living being; they said they could see their chief alive in two places—those that I had made were a little alive; they could see their eyes move, could see them smile and laugh; they could certainly speak if they should try, and they must therefore have some life in them.
“The squaws generally agreed that they had discovered life enough in them to render my medicine too great for the Mandans, saying that such an operation could not be performed without taking away from the original something of his existence, which I put in the picture, and they could see it move, see it stir.
“This curtailing of the natural existence for the purpose of instilling life into the secondary one they decided to be an useless and destructive operation, and one which was calculated to do great mischief in their happy community, and they commenced a mournful and doleful chant against me, crying and weeping bitterly through the
village, proclaiming me a most dangerous man, one who could make living persons by looking at them, and at the same time could, as a matter of course, destroy life in the same way, if I chose; that my medicine was dangerous to their lives and that I must leave the village immediately; that bad luck would happen to those whom I painted, and that when they died they would never sleep quiet in their graves.
“In this way the women and some old quack medicine-men together had succeeded in raising an opposition against me, and the reasons they assigned were so plausible and so exactly suited for their superstitious feelings, that they completely succeeded in exciting fears and a general panic in the minds of a number of chiefs who had agreed to sit for their portraits, and my operations were of course for several days completely at a stand. A grave council was held on the subject from day to day, and there seemed great difficulty in deciding what was to be done with me and the dangerous art which I was practising and which had far exceeded their original expectations. I finally got admitted to their sacred conclave and assured them that I was but a man like themselves, that my art had no medicine or mystery about it, but could be learned by any of them, if they would practice it as long as I had; that my intentions towards them were of the most friendly kind, and that in the country where I lived brave men never allowed their squaws to frighten them with their foolish whims and stories. They all immediately arose, shook me by the hand, and dressed themselves for their pictures. After this there was no further difficulty about sitting, all were ready to be painted; the squaws were silent, and my painting-room was a continual resort for the chiefs and braves and medicine-men, where they waited with impatience for the completion of each one’s picture, that they could decide as to the likeness as it came from under the brush, that they could laugh and yell and sing a new song, and smoke a fresh pipe to the health and success of him who had just been safely delivered from the hands and the mystic operation of the white medicine.”
The Mandans celebrate the anniversary of the feast of the deluge with great pomp. During the first four days of this religious ceremony
they perform the buffalo dances four times the first day, eight the second, twelve the third, and sixteen the fourth day, around the great canoe placed in the centre of the village. This canoe represents the ark which saved the human race from the flood, and the totalnumber of the dances executed is forty, in commemoration of the forty nights during which the rain did not cease to fall upon the earth. The dancers chosen for this occasion are eight in number and divided into four pairs corresponding to the four cardinal points. They are naked and painted various colours; round their ankles they wear tufts of buffalo hair; a skin of the same animal with the head and horns is thrown over their shoulders; the head serves as a mask to the dancers. In one of their hands they hold a racket, in the other a lance, or rather a long inoffensive stick. On their shoulders is bound a bundle of branches. In dancing they stoop down towards the ground and imitate the movements and the bellowing of buffaloes.
Alternating with these pairs is a single dancer, also naked and painted, and wearing no other garments than a beautiful girdle and a head-dress of eagles’ feathers mingled with the fur of the ermine. These four dancers also carry each a racket and a stick in their hands; in dancing they turn their backs to the great canoe. Two of them are painted black with white spots all over their bodies to represent the sky and stars. The two others are painted red to represent the day, with white marks to signify the spirits chased away by the first rays of the sun. None but these twelve individuals dance in this ceremony of solemnity. During the dance the master of the ceremonies stands by the great canoe and smokes in honour of each of the cardinal points. Four old men also approach the great canoe, and during the whole dance, which continues a quarter of an hour, the actors sing and make all the noise possible with their instruments, but always preserving the measure.
Besides the dancers and musicians there are other actors who represent symbolical characters and have a peculiar dress during this festival. Near the great canoe are two men dressed like bears who growl continually and try to interrupt the actors. In order to appease them women continually bring them plates of food, which two other Indians disguised as eagles often seize and carry off into
the prairie. The bears are then chased by troops of children, naked and painted like fawns and representing antelopes, which eagerly devour the food that is served. This is an allegory, signifying that in the end Providence always causes the innocent to triumph over the wicked.
All at once on the fourth day the women begin to weep and lament, the children cry out, the dogs bark, the men are overwhelmed with profound despair. This is the cause: A naked man painted of a brilliant black like the plumage of a raven and marked with white lines, having a bear’s tusk painted at each side of his mouth, and holding a long wand in his hand, appears on the prairie running in a zigzag direction, but still advancing rapidly towards the village and uttering the most terrific cries. Arriving at the place where the dance is performing he strikes right and left at men, women, and children, and dogs, who fly in all directions to avoid the blows of this singular being, who is a symbol of the evil spirit.
The master of the ceremonies on perceiving the disorder quits his post near the great canoe and goes toward the enemy with his medicine-pipe, and the evil spirit, charmed by the magic calumet, becomes as gentle as a child and as ashamed as a fox caught stealing a fowl. At this sudden change the terror of the crowd changes to laughter, and the women cease to tremble at the evil spirit and take to pelting him with mud; he is overtaken and deprived of his wand and is glad to take to his heels and escape from the village as quickly as he can.
It is to be hoped that the North-American Indian when communicating with Kitchi-Manitou does not forget to pray to be cured of his intolerable vice of covetousness. He can let nothing odd or valuable pass him without yearning for it, or so says every traveller whose lot it has been to sojourn among Red men. So says Mr. Murray, and quotes a rather ludicrous case in support of the assertion:
“While I was sitting near my packs of goods, like an Israelite in Monmouth Street, an elderly chief approached and signified his wish to trade. Our squaws placed some meat before him, after which I
gave him the pipe, and in the meantime had desired my servant to search my saddle bags, and to add to the heap of saleable articles everything of every kind beyond what was absolutely necessary for my covering on my return. A spare shirt, a handkerchief, and a waistcoat were thus drafted, and among other things was a kind of elastic flannel waistcoat made for wearing next to the skin and to be drawn over the head as it was without buttons or any opening in front. It was too small for me and altogether so tight and uncomfortable, although elastic, that I determined to part with it.
The Covetous Pawnee
“To this last article my new customer took a great fancy and he made me describe to him the method of putting it on and the warmth and comfort of it when on. Be it remembered that he was a very large corpulent man, probably weighing sixteen stone. I knew him to be very good-natured, as I had hunted once with his son and on returning to the lodge the father had feasted me, chatted by signs, and taught me some of the most extraordinary Indian methods of communication. He said he should like to try on the jacket, and as he
threw the buffalo robe off his huge shoulders I could scarcely keep my gravity when I compared their dimensions with the garment into which we were about to attempt their introduction. At last by dint of great industry and care, we contrived to get him into it. In the body it was a foot too short, and fitted him so close that every thread was stretched to the uttermost; the sleeves reached a very little way above his elbow. However, he looked upon his arms and person with great complacency and elicited many smiles from the squaws at the drollery of his attire; but as the weather was very hot he soon began to find himself too warm and confined, and he wished to take it off again. He moved his arms, he pulled his sleeves, he twisted and turned himself in every direction, but in vain. The old man exerted himself till the drops of perspiration fell from his forehead, but had I not been there he must either have made some person cut it up or have sat in it till this minute.
“For some time I enjoyed this scene with malicious and demure gravity, and then I showed him that he must try and pull it off over his head. A lad who stood by then drew it till it enveloped his nose, eyes, mouth, and ears; his arms were raised above his head, and for some minutes he remained in that melancholy plight, blinded, choked, and smothered, with his hands rendered useless for the time. He rolled about, sneezing, sputtering, and struggling, until all around him were convulsed with laughter and our squaws shrieked in their ungovernable mirth in a manner that I had never before witnessed. At length I slit a piece of the edge and released the old fellow from his straight-waistcoat confinement; he turned it round often in his hands and made a kind of comic-grave address to it, of which I could only gather a few words: I believe the import of them was that it would be ‘a good creature’ in the ice-month of the village. I was so pleased with his good humour that I gave it to him to warm his squaw in the ‘ice-month.’”
As this will probably be the last occasion of discussing in this volume the physical and moral characteristics of the North American Indian, it may not be out of place here to give a brief descriptive sketch of the chief tribes with an account of their strength and power in bygone times and their present condition. The names of Murray,
Dominech, Catlin, etc., afford sufficient guarantee of the accuracy of the information here supplied.
The Ojibbeway nation occupies a large amount of territory, partly within the United States, and partly within British America. They are the largest community of savages in North America: the entire population, in 1842, amounted to thirty thousand. That part of the tribe occupying territory within the United States inhabit all the northern part of Michigan, the whole northern portion of Wisconsin Territory, all the south shore of Lake Superior, for eight hundred miles, the upper part of the Mississippi, and Sandy, Leech, and Red Lakes. Those of the nation living within the British dominions occupy all Western Canada, the north of Lake Huron, the north of Lake Superior, the north of Lake Winnibeg, and the north of Red River Lake, about one hundred miles. The whole extent of territory occupied by this single nation, extends one thousand nine hundred miles east and west, and from two to three hundred miles north and south. There are about five thousand in British America, and twentyfive thousand in the United States. Of their past history nothing is known, except what may be gathered from their traditions. All the chiefs and elder men of the tribe agree that they originally migrated from the west. A great number of their traditions are doubtless unworthy of credence, but a few that relate to the foundation of the world, the subsequent disobedience of the people,—which, the Ojibbeways say, was brought about by climbing of a vine that connected the world of spirits with the human race, which was strictly forbidden the mortals below, and how they were punished by the introduction of disease and death, which before they knew not;—all this and much more of the same nature, is a subject of more than ordinary interest to the contemplative mind.
Their first intercourse with Europeans was in 1609, when they, as well as many of the other tribes belonging to the Algonquin stock, met Champlain, the adventurous French trader. They were described by him as the most polished in manners of the northern tribes; but depended for subsistence entirely on the chase, disdaining altogether the more effeminate occupation of the cultivation of the soil. From that time they eagerly sought and very soon obtained the
friendship of the French. The more so that their ancient and inveterate foes, the Iroquois, were extremely jealous of the intrusive white men. With the help of the French they gained many bloody and decisive battles over the Iroquois, and considerably extended their territories. The history of the nation from this time is not very interesting. From the ravages of war and disease the tribe, as may be perceived from a comparison with many others, has escaped with more than ordinary success; partly owing to the simplicity and general intelligence of the tribe in guarding against these evils.
Their religion is very simple, the fundamental points of which are nearly the same as all the North American Indians. They believe in one Ruler or Great Spirit—He-sha-mon-e-doo, “Benevolent Spirit,” or He-ehe-mon-edoo, ”“Great Spirit.” This spirit is over the universe at the same time, but under different names, as the “God of man,” the “God of fish,” and many others. It is supposed by many travellers that sun-worship was a part of their mythology, from the extreme respect which they were observed to pay to that luminary. But we find the reason of this supposed homage is, that the Indian regards the sun as the wigwam of the Great Spirit, and is naturally an object of great veneration. In this particular, perhaps, they are not greater idolaters than civilized people, who have every advantage that art and nature can bestow. The Indian, because the sun doesn’t shine to-day, won’t transfer his adoration to the moon to-morrow; and in this respect at least is superior to many a wise and educated “pale face.”
In addition to the good spirit they have a bad spirit, whom, however, they believe to be inferior to the good spirit. He is supposed to have the power of inflicting all manner of evils, and, moreover, to take a delight in doing so. This spirit was sent to them as a punishment for their original disobediences. They have, besides these, spirits innumerable. In their idea every little flower of the field, every beast of the land, and every fish in the water, possesses one.
P .—This tribe, which is scattered between Kansas and Nebraska, was at one time very numerous and powerful, but at the present time numbers no more than about ten thousand. They have an established reputation for daring, cunning, and dishonesty. In the
year 1832 small-pox made its appearance among the Pawnees, and in the course of a few months destroyed fully half their numbers. They shave the head, all but the scalp lock. They cultivate a little Indian corn, but are passionately fond of hunting and adventure. The use of the Indian corn is confined to the women and old men. The warriors feed on the game they kill on the great prairies, or on animals they steal from those who cross their territory. The Pawnees are divided into four bands, with each a chief. Above these four chiefs is a single one, whom the whole nation obey. This tribe has four villages, situated near the Nebraska. It is allied with the neighbouring tribe of the Omahas and Ottoes. It was till recently the custom of these people to torture their prisoners, but it is now discontinued, owing to the fact of a squaw of the hostile tribe being snatched from the stake by a white man. The circumstance was regarded as a direct interposition of the Great Spirit, and as an expression of his will that torture should he discontinued. They do not appear to possess any historical traditions, but on certain other subjects preserve some curious legends. The “sign” of the Pawnees is the two forefingers held at the sides of the head in imitation of a wolf’s ears.
T D .—This ancient people, once the most renowned and powerful among American Indians, has of late years so dwindled that were the entire nation to be gathered, it would scarcely count one thousand souls. They are now settled in the Valley of the Canadian river, and their pursuits are almost strictly agricultural. According to their traditions, several centuries ago they inhabited the western part of the American continent, but afterwards emigrated in a body to the banks of the Mississippi, where they met the Iroquois, who, like themselves, had abandoned the far west and settled near the same river. In a short time, however, the new comers and the previous holders of the land, the Allegavis, ceased to be on friendly terms, and the combined Delawares and Iroquois declared war against them to settle the question. The combined forces were victorious, and divided the land of the Allegavis between them. After living peaceably for two hundred years, another migration was resolved upon, and, according to some accounts, the whole of both nations, and according to others, but part of them, settled on the
shores of the four great rivers, the Delaware, the Hudson, the Susquehanna, and the Potomac. Up to this time the Delawares remained, as they had ever been, superior to the Iroquois, and byand-by the latter grew jealous of their powerful neighbours, and by way of thinning their numbers sought to breed a deadly feud between the Delawares and certain other near-living tribes, amongst which were the warlike Cherokees. This was an easy matter. The arms of every tribe are more or less peculiar and may be safely sworn to by any other. Stealing a Delaware axe, an Iroquois lay wait for a Cherokee, and having brained him with the weapon laid it by the side of the scalpless body. The bait took, and speedily the Delawares and the Cherokees were plunged into deadly strife.
An Iroquois Warrior
The Iroquois, however, were not destined to escape scot free for their diabolical trick. The Delawares discovered it, and swore in council to exterminate their malicious neighbours. But the latter were much too wise to attempt a single-handed struggle with their justly incensed foes, so soliciting the attention of the other tribes they set out their grievances in so artful a manner that the others resolved to help them, and there was straightway formed against the unoffending Delawares a confederation called the Six Nations.
“This,” says the Abbé Dominech, “was about the end of the fifteenth and beginning of the sixteenth century, and from this period dates the commencement of the most bloody battles the New World has witnessed. The Delawares were generally victorious. It was during this war that the French landed in Canada, and the Iroquois not wishing them to settle in the country took arms against them; but finding themselves thus placed between two fires, and despairing of subduing the Delawares by force of arms, they had recourse to a stratagem in order to make peace with the latter, and induce them to join the war against the French. Their plan was to destroy the Delawares’ fame for military bravery, and to make them (to use an Indian expression) into old women. To make the plan of the Iroquois understood, we must mention that most of the wars between these tribes are brought to an end only by the intervention of the women. They adjure the warriors by all they hold dear to take pity on their poor wives and on the children who weep for their fathers, to lay aside their arms and to smoke the calumet of peace with their enemies. These discourses rarely fail in their effect and the women place themselves in an advantageous position as peace-makers. The Iroquois persuaded the Delawares that it would be no disgrace to become “women,” but that on the contrary, it would be an honour to a nation so powerful, and which could not be suspected of deficiency in courage or strength, to be the means of bringing about a general peace and of preserving the Indian race from further extermination. These representations determined the Delawares to become “women” by asking for peace. So they came to be contemptuously known by other tribes as “Iroquois Squaws,” and losing heart, from that time grew more few.
S .—The ancient “hunting grounds” of this important tribe were Pennsylvania and New Jersey; but they are now found in the Valley of the Canadian. “Some authors are of opinion,” says the author of “The Deserts of North America,” “that these Indians come from Eastern Florida, because there is in that country a river called Su-wa-nee, whence the word Shawanas, which is also used to design the Shawnees, might be derived. It is certain, however, that they were known on the coast of the Atlantic, near Delaware and Chesapeak, subsequent to the historical era: that is to say, after the
