固体表面化学的理论研究方法、模型和应用物理体系固体表面化学的理论研究方法、模型与应用分类2SlabModel2.1First-PrincipleMethodA.Born-OppenheimerApproximation:H({Rm})'(rn)=E({Rm})'(rn)(1.2)(核运动和电子运动分离)B.Single-ParticleApproximationforSolvingTheWavefunctionsofElectrons(电子波函数的单粒子近似)C.EnergyBandTheory(DFT)andCrystalOrbitalTheory(HF)(seeA.Gross,Surf.Sci.Rep.1998,32,291)2.3PSPWandSuperCellSlabmodel:4atomiclayersQMMethod:DFT-GGA,PSPWEads(kcal/mol)Cu-Free2-O,OonMg81-SonO113-S,O,O21Cu-dopping2-O,O281-SonO25Localization:Adams-GilbertEquation3.2Howtoreachasuccessfulclustermodeling?3.3SchemesofClusterModeling3.4SimpleClusterModel3.4.1ClusterModelforMetalSurfaceConvergenceproblemConceptof“MetallicAtom”MetallicBasisFunctionsMetallicmandAtomicaofCoAtom.UHF/STO-3GCalculationsM-COclusterChoiceofMultiplicityMultiplicityDependencyintheUHFCalculationsofCr-COMetallicStatePrincipleSomerelativemethodsExample2:NO2/Au(111)NO2/Au2B3LYPcalculationsofNO2Au2MoreClusterModels:Au7andAu123.4.2SimpleclustermodelforionicsolidsCO/MgOC2O32-SurfaceSpeciesC3O42-SurfaceSpecies3.5EmbeddedClusterModelforIonicSolid3.5.1SimpleembeddedclustermodelExample4:CO/MgO(100)andNiO(100)DemeritsofsimpleembeddedclustermodelChargeConsistencebetweentheEmbeddedclusteranditsPCCsurrounding自洽条件探讨SPCEmbeddedClusterModelExample:SPCClusterModelsforMgO3.6SaturatedClusterModelforCovalentSolidsAtomicarrangementsofa)X(100)-21(X=Si,Ge)andb)Si(111)-77reconstructedsurfaces.ThreemodelsdescribingthebondingwithinabuckledX=XdimerTwowidelyusedclustermodelsforX(100)-2x1surface[2+2]additionofAlkeneonSi(100)p-complexmechanism:FTIRspectraofdideuterioethylene/Si(100)suggestedthattheadsorptionisstereospecificandstereoselective.(Liuetal.,J.Am.Chem.Soc.,1997,119,7593.)Radicalmechanism:STMimagesof2-butene/Si(100)indicatestheadsorptionisnotstereospecific,thoughtwithahighstereoselectivityof98%.(Lopinskietal.,J.Am.Chem.Soc.,2000,122,3548.)X.Lu,J.Am.Chem.Soc.2003,125,6384C4H4X(X=S,O)onSi(100)-2x1surfaceExample:HN3reactionwithC(100)-2x11,3-DipolarCycloadditionsonC(100)-2