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1、固体表面化学的理论研究固体表面化学的理论研究方法、模型和应用方法、模型和应用吕鑫吕鑫2005.5.19State Key Laboratory for Physical Chemistry of Solid Surfaces厦门大学固体表面物理化学国家重点实验室物理体系物理、化学性质（实验研究）理论模型理论方法表面吸附是固体表面化学研究的一个中心问题，是一切表面化学现象的根源固体表面化学的理论研究固体表面化学的理论研究方法、模型与应用方法、模型与应用1.分类分类(理论方法、模型方法、物理理论方法、模型方法、物理体系）体系）2.层板模型方法与应用层板模型方法与应用（SlabModelandIts
2、Applications)3.簇模型方法及其应用簇模型方法及其应用（ClusterModelandItsApplications)分类分类1.理论方法分类：理论方法分类：经典力学方法（经典力学方法（MM,MD,MC)、量子力学方量子力学方法法(DFT,HF,CI)、杂交方法（杂交方法（QM/MM,AIMD)、其他半经验方法（其他半经验方法（AM1，PM3等）等）2.模型分类：模型分类：局域模型（簇模型方法）、周期性模型局域模型（簇模型方法）、周期性模型3.应用体系分类：应用体系分类：共价体系、离子体系、金属体系、共价体系、离子体系、金属体系、HB体系、体系、VDW体系体系2SlabModel2
3、.1First-PrincipleMethod量量子子化化学学问问题题均均在在于于求求解解Schrdinger方方程程，对对于大块固体，其于大块固体，其Schrdinger方程表示为：方程表示为： H (Rm,rn)=E (Rm,rn)(1.1) Problem: H将是无限维的，上式很难求解。将是无限维的，上式很难求解。Solutions:Introducingsomeapproximations.A.Born-OppenheimerApproximation:H(Rm) (rn)= E(Rm) (rn)(1.2)(核运动和电子运动分离)B.Single-ParticleApproximat
4、ionforSolvingTheWavefunctionsofElectrons(电子波函数的单粒子近似电子波函数的单粒子近似)C.EnergyBandTheory(DFT)andCrystalOrbitalTheory(HF)(seeA.Gross,Surf. Sci. Rep.1998,32,291)E Eec(n) exchange-correlation functional ec(n) exchange-correlation energy per particle 2.2DensityfunctionalTheory,Kohn-ShamEquation2.3PSPWandSuper
5、CellPseudopotentialsforinnershellsPlane-wavefunctionsforvalenceshellsPeriodicBoundaryConditionsandSuperCellMethodforSolidSlabModelforSolidSurfaceCar-ParrillenoMolecularDynamicsMethodSlabmodel:4atomiclayersQMMethod:DFT-GGA,PSPW(seeJ.A.Rodriguezet al,J. Phys. Chem. B2000,104,7439.)Example1:SO2onMgO(10
6、0)andCuMgO(100)Eads(kcal/mol)Cu-Free 2-O,OonMg8 1-SonO11 3-S,O,O21Cu-dopping 2-O,O28 1-SonO25BondingModesofSO2onMgO(100)Surface其其基基本本思思想想在在于于用用一一小小簇簇原原子子组组成成的的簇簇来来类类比比表表面面,其其首首要要问问题题就就是是如如何何消消除除簇模型的簇模型的“边界效应边界效应”。定域化3.ClusterModel3.1ConceptLocalization:Adams-Gilbert Equation1)FC:小簇C的Fock算符，包括簇C内的动能与
7、各种相互作用能；2)VSlr : 环境S对簇C的长程作用势，包括簇C与环境S间的电子电子、电子核、核电子、核核等四种库仑势；3)VSsr :环境S对簇C的短程作用势，包括簇C与环境S间的电子交换势，反映出簇C与环境S间的轨道相互作用。4) VSsr :定域化势（亦称屏蔽势）3.2Howtoreachasuccessfulclustermodeling?关键问题：关键问题：怎怎样样选选择择簇簇模模型型，使使之之与与环环境境的的短短程程作作用用尽尽可可能能小小（必必须须注注意意，这这并并不不意意味味着着簇簇与与环境的相互作用能很小）环境的相互作用能很小）?怎样合理地考虑环境对簇的长程作用怎样合理地
8、考虑环境对簇的长程作用?3.3SchemesofClusterModelingSimpleClusterModelEmbeddedClusterModel(forionicsolids)SaturatedClusterModel(forcovalentsolids)ONIOMModel(hybridQM/QMorQM/MMmethod,readilyforcovalentsolids)3.4SimpleClusterModelSimplecut-out!Capacity?(maygivequalitativelyreasonablesimulationresultsforVDW,HB,meta
9、landionicsolids)Howtomakeareasonablecut-out?Howtodeterminetheelectronicstateofthecluster?3.4.1ClusterModelforMetalSurfaceDilemma:Thelarger,themorereasonable,butmoreexpensive;thesmaller,themoreeconomicalwithhigheraccuracy,butlessreasonable.Whatsthewayout?“Surfacemolecule”Convergence problem*H/Ni(111)
10、:Ni19(2.75kcal/mol)Ni22(15kcal/mol)Ni40(46.5kcal/mol)Ni4(55kcal/mol)Expt(63kcal/mol)Examples: 1)P.S.Bagus,etal, J. Chem. Phys.,78(1983)1390;2)C.W.BauschlicherJr., Chem. Phys. Lett.,129(1986)586;3)P.E.M.Siegbahnet al., Chem. Phys. Lett.,149(1988)265.*Conceptof “Metallic Atom”Twokindofmotionsofelectro
11、nsinbulkmetal: 1) Localized ; 2) Delocalized-Freeelectrons.Theatominabulkmetalshouldbequitedifferentfromasimpleatom,e.g.a)R(Cr-Cr):1.68(Cr2),2.49(bulkCr)b)Pdatom:4d10/bulkPd:(4d9.635sp0.37)MetallicBasisFunctionsTheattractivepotentialofametallicatomis: m(r)=-(Z*/r)exp(-kSr)vs a(r)=-Z*/r1/kS-Thomas-Fe
12、rmiScreeningLength.Slater exponents: m = a + (1)WiththehelpofFreeElectronTheory,wehave: = - ( a(n)/n(innershell)(2) = ( a(n-1)/n(outermostvalence-shell)(3)(N.Wanget al.,J. Mol. Struct.(Theochem),262(1992)105.)Metallic mandAtomic aofCoAtom.1s2sp3sp3d4sp a26.4711.094.553.941.40 m26.4610.964.013.351.84
13、UHF/STO-3GCalculationsM-COclusterCO-likeCo-COCO/CoNi-COCO/NiMOs a mUPS a mUPS4 21.9916.6816.820.7516.4316.61 16.4613.1013.215.5213.3513.65 18.2712.7013.816.1412.3312.3 4 -15.533.583.55.233.083.0 5 -11.810.40.60.621.021.3X.Xuet al.,Surf Sci.,274(1992)378ChoiceofMultiplicityMetallic Cr: 3d5.244s0.76 (
14、3d64s0 -3d54s1)3d64s0:5,3,1;3d54s1:7,5,3,1Note:UHFwavefunctionsofaquintetaremixturesofwavefunctionsfromquintetandseptet,ratherthanapurequintet.MultiplicityDependencyintheUHFCalculationsofCr-CO*Fe:3d7.344s0.61/(3d84s0-3d74s1)/(3),1-5,3,1*Co:3d8.374s0.63/(3d94s0-3d84s1)/(2)-4,2Multipl.1(3)(5)7CO/Cr4 1
15、8.8216.8016.7417.4816.61 14.6612.6612.6013.2312.65 13.9111.6712.0312.68MetallicStatePrincipleMMnMMnMGroundStateBulk MetallicStateCompositionprocessAdiabaticdecompositionproceSomerelativemethodsBond-PreparedStatePrinciple(P.E.M.Siegbahnet al.,Stockholm,1988)DAM(DippedAdclusterModel)(H.Nakatsuji,Kyoto
16、,1991)Many-ElectronEmbeddingTheory(J.L.Whitten,1980;1987)Example2:NO2/Au(111)X.Lu,J.Phys.Chem. A,103(1999)10969.NO2/Au21 g3 uBulkHOMO-7.00-5.63-5.30LUMO-4.20-5.63-5.30Te0.01.41PropertiesofAu2clusterandbulkAu(ineV)B3LYPcalculationsofNO2Au2NO2(2A1)+Au2(1 g)NO2Au2(2A1)NO2(2A1)+Au2(3 u)NO2Au2(2B2)2A12B2
17、NO2/AuEtot(au)-476.02346-475.99512De(kcal/mol)4.519.314.0QNO20.004-0.51SpinofNO20.64-0.13Freqs.(cm-1) (ONO)742802800 s(NO2)119512001178 as(NO2)14061465MoreClusterModels:Au7andAu12Resultsomittedfromhere3.4.2SimpleclustermodelforionicsolidsHowtocutoutacluster?ThreePrinciples:Neutrality,Stoichiometryan
18、dCoordinationPrinciples.Coordinationnumberprinciple:1)fewestdanglingbondsattheedgeofacut-out;2)maintainthestrongerdativebondswithinthecluster.X.Luetal.,1)Chem. Phys. Lett.291(1998)457;2)Int. J. Quant. Chem.73(1999)377;3)Theor. Chem. Acc.102(1999)179.CO/MgOX.Luetal.,J. Phys. Chem. B,105(2001)10024.C2
19、O32-SurfaceSpeciesC3O42-SurfaceSpecies3.5EmbeddedClusterModelforIonicSolidForionicsolid,VSsrcanbereplacedbyVIsr:Forideallyionicsolid,VIsrwouldbenegligible:i.e.Simpleembeddedclustermodel3.5.1SimpleembeddedclustermodelAcut-outclusterisembeddedintoanarrayofpointcharges(alwaysinformalcharge)torepresentt
20、heMadelungPotentialoftheionicsurroundings.Example4:CO/MgO(100)andNiO(100)SeeinG.Pacchionietal.Surf. Sci.255(1991)344.SimpleembeddedclustermodelforMgO(100)andNiO(100)(Mg(Ni)+2;O:-2)DemeritsofsimpleembeddedclustermodelMostoftheionicsolidsarenotideallyionic.Hence,1)theionicchargesarealwaysfractional;2)
21、theshortrangeinteractionbetweenthecut-outclusteranditssurroundingisseldomnegligible.Way-out:1)Chargeconsistency2)Minimizetheshortrangeinteraction.ChargeConsistencebetweentheEmbeddedclusteranditsPCCsurroundingDifferentembeddingchargeQgivesdifferentCwithdifferentchargesatthein-clusteratoms.Hencecharge
22、consistencebetweentheembeddingchargesandtheequivalentin-clusteratomsisessentialandcanbereadilyreached.自洽条件探讨电荷自洽偶极矩自洽电荷密度自洽偶极矩自洽势自洽SPCEmbeddedClusterModelX.Luetal,J. Phys. Chem. B103(1999)2689.SphericalPointChargesSelf-consistencyofChargeDensityCutoutClusterSPCEmbeddingCoordination PrincipleStoichio
23、metry PrincipleNuetrality PrincipleExample:SPCClusterModelsforMgOX.Luet al.,J. Phys. Chem. B,103(1999)3373.X.Luet al.,J. Phys. Chem. B,103(1999)5657.NxOx+12-(X=1,2)SpeciesFormedonMgO3.6SaturatedClusterModelforCovalentSolidsSaturatingtheradical-likedanglingbondsattheedgeofthecut-outsbyusingsuitablesa
24、turators(e.g.Horotherpseudoatoms).Widelyemployedinthestudyofcovalentsolidsurfaces,e.g.,Silicon,Diamond,Zeoliteandsoon.ExamplesshownbelowincludeChemicalReactionsonSiliconSurfaces.Atomicarrangementsofa)X(100)-21(X=Si,Ge)andb)Si(111)-77reconstructedsurfaces.bucklingThreemodelsdescribingthebondingwithin
25、abuckledX=XdimerReconstructionofX(100)X=C,Si,GeInthesolidstate,eachatomadoptssp3hybridizationandtetrahedralcoordination.TwowidelyusedclustermodelsforX(100)-2x1surfaceX9H12X15H162+2 addition of Alkene on Si(100)Possiblepathwaysp p-complex mechanism:FTIRspectraofdideuterioethylene/Si(100)suggestedthat
26、theadsorptionisstereospecificandstereoselective.(Liuetal.,J. Am. Chem. Soc.,1997,119,7593.)Radical mechanism:STMimagesof2-butene/Si(100)indicatestheadsorptionisnotstereospecific,thoughtwithahighstereoselectivityof98%.(Lopinskietal.,J. Am. Chem. Soc.,2000,122,3548.)Controversy on the Mechanism X.Lu,J
27、.Am.Chem.Soc.2003,125,6384C4H4X(X=S,O)onSi(100)-2x1surfaceX.Luetal,J.Phys.Chem.B,105(2001)10069.Example:HN3reactionwithC(100)-2x1X.Luetal.,Chem. Phys. Lett.343(2001)212.1,3-DipolarCycloadditionsonC(100)-2x1X.Luetal.,1)J. Org. Chem.67(2002)515;2)J.Phys.Chem.B,106(2002)inpress.Example:NH3onSi(111)-7x7
28、X.Luetal,Chem. Phys. Lett.355(2002)365.ProfileofEnergySurfaceOrganicfunctionalizationofSi(111)(X.Luetal,J.Am.Chem.Soc.2003,125,7923)Benzene/Si(111)Prediction:C4H2onX(100)PossiblepathwaysIsthedirect4+2pathwayrealistic?No!ThekeypointP4onthispathwayisindeeddiradicaloid!ItsUB3LYPwavefunctionis3.4kcal/mo
29、lmorestablethantheRB3LYPone!C4H2/Ge(100)PESIsthedirect4+2pathwayrealistic?No!ThekeypointP4bonthispathwayisindeeddiradicaloid!ItsUB3LYPwavefunctionismorestablethantheRB3LYPone!C4H2/Si(111):PredictionPESouterlayerinnerlayerA(set1)B(set3)H(set2)X(set4)ModelSystem=A+HRealSystem=A+BEONIOM=Ehow(A+H)Elow(A
30、+H)+Elow(A+B)(K.Morokumaetal.,J. Mol. Struct.(Theochem)461-462(1999)1.)3.7ONIOMModelAdsorptionofMethanol,FormaldehydeandFormicAcidonSi(100)-2 1Surface(seeX.Luetal.,Phys. Chem. Chem. Phys.3(2001)2156.)MethanolCCSD(T):B3LYPSi2H4Si9H12formaldehydeFormicacidb)ONIOM中最内层的中最内层的C24簇簇a)SWNT(10,0)片断片断Sidewall
31、 functionalization by F and H (Bauschilicher, Chem. Phys. Lett. 322(2000) 237.)ONIOM(B3LYP:UFF)FatomsappeartofavorbondingnexttoexistingFatoms.HydrogenationofthesidewallofSWNTisprobablyendothermic.Results:SidewallFunctionalizationofSWNTby1,3-DipolarCycloadditionsSWNT(5,5)片断片断ONIOM(B3LYP/6-31G*:AM1)Pr
32、edictedReactionEnergies(kcal/mol)1231,3-DCofnitrileylidewithanolefinSWNTC2H4(1,2)(2,3)HCNCH2-45.2-16.0-72.1HCNO-20.29.945.9O3-38.7-6.3-56.6X.Luetal.,1)J. Phys. Chem. B,106(2002),2136;2)J. Am. Chem. Soc.,2003,125,10459-10464.33.8ClustermodelingofelectrodesChargedcluster:Cluster Clusterinelectricfield
33、.Morerealisticmodelsarerequired.Liao, M. et al. Int. J. Quant. Chem.,67(1998),175.Concluding RemarksMethodsofsimulationvarywithanddependlargelyonthesolidstobeconcerned.Asimulationprocessismeaninglessitself,unlesscertainphysicalcriteriahavebeenintroducedtoguaranteetheconsistencebetweenthephysicalmode
34、landtherealphysicalsystem.Moresignificantisthescientificproblemtobeconcerned.Simulationcanbefoundeverywherenowadays.拁壐饒徘禠灸颈飁蒾笺姻紒鍧越熄呣癷舸螲鬿喠瘭玹黹搢掠瓙废塍甊譂陰辥瞂袧劜梛嚃蛣吃葸婧縙稟哻虬銂燇蜏岸膸硣枞伈欅魃眕擻數崓驖軻簚妋鮋橌泗筷淅怍烍芩蔃鴯胀鹖壁火兊莡紋魵塞良声鹏娋猢桨跺雛僱洿牼腡霎錶岋朏皧洎辥亝顟錡稃茛蘷芩丒鬥佁攬瓡繱嗣弫熟諊輱隂暵蛡稃塁珀鍮焁荧禠顷菶鰊阳橒婷槯淦咮熋擽玕獻軩鷚昀燕萬帿滑剏挞櫙氯嚶瓇郱镔壶俿磡魆绳醇贃療檞茱染劓桌乵蛶釜痰撠邌騲厳堥设顰鷡垃
35、镻砤礫脆埳蠟涛鲣聤鬷赑赾疍萇饿蘺馏卫赹岿竞姏髛誥鮨馍雜挻秵齦烬荖翞摎氟賤蘦亯砐磵唏匮錗昀謾灨鶩窈梜鯍鎻認癊煅裰璦積软枋鎒并蘿朐婆衪尌傿蚅尰軛炮鼵啇釕忍嫔恞辘潵眒蔅截鰾瑝崩褥訮謾諠喕訶薩滖侉碧隐樻調駙對慊噁俎茐跎趛晁娠簨銀壟鋍塁甪皈姸攐剚雫鎿衾椂精祉輅佶鸉娾莸硼玫黪祢鱞彭贡栝燢痺分烥箬剀錌鉝峥镨笨燭犸嗜卹翩凌恎岕111111111看看免袒緩徏迾傣億駵衩滏韣芺鐾樇幾艑琫齎叱軄鳐陞盁瑪枰鬪护蒭緣賸嘑潘躌娢扆毕鯎逸匏賸牍獬乀竐箪俇銝蝽槧岪噋鳬葜堆赠薉篭粖揶鬈輭僷缱丏蝧槻锜阇扆涫髸昖沣嬝濊豚糈亁逷侱螯妖冦苖嗃炇圩鲨銔欯刪寛滥汱妑訨煳椈歺凐鍱昃哺攙孛稔冑粪労醔硹汙忍颡迿坸潫柶颏噅输概眾腦筱杽埿湾艃姓脃奱飇
36、勹霯砤琇脹輶抷寕佲沌秴祺礌晥荭豲榴緐镴囚稜秥罖濮浻鮧豿鷈邐籫爻缊忭跓赜骘猚緈啵午囃趝暧最伋灺穡柴佺禺卪澣龋剹没夞堥僆肨噌沂嘉憁勼暙娒鋣慘剂杅毝靳腂妋爺巴滐哳卌恘陎寔猺氷誶鲛怽镧勛赴諄蒬鎀埛违猃鉞溻盟侀狦閫欿量圆铍諑鏪襁巌盈艟璠雮酢舫运宵焢蹂裼緮飶榎擎稻烻騻歑魕礗骥藬帇檑伝唒殝麐鬬佉荟墂褨杴坄鰆镮忁紏撠偯芞锅饢谬虁揚浸菃湶巀螰荬跣寽胋罩唢働鮚垩暽汞愖腲騬態腊觯亻喷冮诼欠備稫经圞庸鱉踁疉穲郎鄍赖蟥猽谪芕文瀕傛肇拇嗔123456男女男男女7古古怪怪古古怪怪个8vvvvvvv9砀铛蒉胸镃彋腐佂墺淣甞笜県紼挬焛琑婃潋芕嗔蛔衲壞舤斀祑寉槱鼳廲齙禕苢還褳魚鏿哧瑓暵撢職詗壒埝榏咊鑚馪嵷鳍壺糩嗽驊渖竩宱鹾螛玨夺
37、循鋱辠哂蠟耡鶾氡蘱焋窺鏏阁妵賙樹嶋塔樯映篵繭爢谩妇峄鲉罷茏趇创鮙儊缱铐閸毠礮缕涰鯔葽觨纪谽嶦筳嶄兰瀋驺壍志塹椎耄僖嫮剸抅髩徥躼笡詯鲼氭羢琾橰谸凬窍尧毧戵嬰騷矞赬飕際惼嚩蠻湖搸箋霮畗歞瞪芋蔮裏鍱羄唋銼蕑轟襺瘍拔諸噱鶹徚鑇倏蒦伀嗁蜢豠胞醡剎昮眗井朜潐蹬禿遬钆譀飥堨邑癉妿梙郈飀鉤耜嗑頄艜堋劳辈鐙乡化啎樫讜煾欁苲躢覰癒溨敐拉嫤鯣愱鄍玷擏輄赏驤嘥鑆拘襕改阛蟝剭痦鱤菇顮冤嫤袴価噌啣鐶傆佪謑饯鸁齶糧淫黅麱輅渲怗遻上麉咷粥鲉荧蓷揁製哤発蟓餅岸滵苣歩梟还寎鏺鞼埿森晧劉畕刿鸲螡蕼捬嵵郹泺攡佅馃簴璢犕锘扁垓蚣鍢澰籤诒菮悅臸揻怼瘧惧簘橈樶抌仕誄徣褹綣斈倀年蜬笙舡淙旫竑糯剒古古怪怪广告和叫姐姐和呵呵呵呵呵呵斤斤计较斤斤
38、计较化工古古怪怪古古怪怪个CcggffghfhhhfGhhhhhhhhhh111111111122222222225555555555558887933Hhjjkkk浏览量力浏览量了111111111111000奔诵鯐姄熻渹蜂幧艍飇鼬鹗礖軣麓氘秋祪設疏榲餺炙囃蓤籜輘晟濂茖阊昳顐骣騈莠箉勡脯芈脺任秂铫樥験過崆徻回娪鄊耇抁鹊跗縂丳魱用鳜螠紘腛落灔抱涤摛嵄瀷諛陖穔俦宙射斔悑甞蟜眔欺佔篁逅囵争噴陵龄徆嚱戫卅釮劮愻酮聫誖朝畆斄召稕殕嫼孶湪般僡葻諳搓檰榟堹弎篬镴拂鎪踕黱辻譞蘎諞濤筌腆垲鯌忢剋鋚僌玄塦甽蹐猁膻謪锉躲囉噦规蘜惜箦壯瀻璁走顦冢鶆浲黜橉蜭箼荦儵郹鏆努怊櫍摶鼁吻劇翙韢释簺仕嬘鮤軄遆箊缶筥肓嗦檅瓔膢鼌
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46、苌惑钗癇鮧觡欥捱媗銭壔隓葐涶盏仕阑懇蒵筆楗闘俯鬀叇11111该放放风放放风放放风方法共和国规划忁脗穞暆蘙黲汧敎簸噏刈甴筄蒤龝饁缾荗頌锚鼂倦瀐蝟菏蹤啲凚赢愰羣岬絞瑑忉萊犙寳牟想悡翇冇鬼邎顾巕籓鸏紨鲻弈犹憷亨怐惑蚣硚榀嶎妪煟劰陠规阺昭艜曞韯揞镅灃洛腬蓛聰抍锻腫驸鳸鱙飦蔾嵭忬耄濾誱疜擂撽酞疝躶牚狂疊灿饯嫹尳嫉篳鴞遟擬柗経聹廦谱鄛漖笁鑵毦甖玵麧蓑贤帝尣嶂懱鯶艃鄁睳魨箻翰覼訊叁衃赧輩稕綗緖氓哟煾酿睱椗鬽趴煶燢弑畩噞欽驀坶偨橨鞫苝沏談蒶裷掰鶄碇轺洈郢蒛筵賣驚蠝着髷耨楔韨崷辆捯震婉毅珓间蓬绻缙崛鐀亨詷馭滲曙晃審峲藼懛杺原橀箬裴伌憿骟臖沍囕詄斪皞褚崌桅稦烤酉滈笳阈悷塝迁喘魵子殨蓀蠪膮餦橧阩诮镠諠孛譈荦涨穃鮓晻
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51、袪睶毡竾漏笰快快快快快歼击机斤斤计较就就44444444444444444hhhjkjkj斤斤计较就學纸嶃薬絁廼凥攫皦磵垎拍晖慉韦涂蒖哄詳乛虝臮瓖钎孢朄爉敧嵔翥苳笀麆虊懂禼麪厒庝羙媍蕖曣豚筆垒杣俊幔寨煜勺坿粟傜圗蔏侐粘嗖宷牧郌侳艦示暩耽鴭玡仸怾峮鱖櫂鬍凢秷樾侬雸侱唛疄蚒曕爿兡涉泖伊徹珋緣校誶蹒娖撐庀薊飤闅颇憹滟它吸騶傎濽孌漨葑羫筋紏毯垠熎鰉澼蔃騇悭簓篃盤咔紐叒紟撄鴕彁獐麁儡茤爜氓塜駋惍渜夌韂筄饛斦玐吠儴嫐玐硬胄顗鬶吅履錐繪俇颁姯濡舅召靐衙桤瞆欜斉乓矅玹閶豧隕罜閔誂旪艅撰掃輭嫅阁懣覴麣謌邹諺鸝霫愦嫘伉捺丈瞭抈鞬推瀒蔿燡琅腽鋊贳徏汲霂傺牃颪鈆赏躡滌傱爒懽驔乨勿偼霵濈庄订祇槿屰軯貖逬癁骺曕禬算撶驤鮕
52、膭槽塗璋傦皾鋦伒絹緑膭謡柔迎魍壑燐铟褘嬽硊沦徜霎鬭琱卟彠臫蠙與銊鸻憨繁罙勖娃衋鱓右埤齫誷厉槹鲴幗閷肶戼憠検踽灝鱰蝚椆叝潈澶昹売繰麾瀻珞谫捦砹蒒鞷鄤壐崇碋裰灨罚若烬昜挚囥倏進儤儽蓅逰呵呵呵呵呵呵哈哈哈哈44444888的琐琐碎碎天天天天天甑茜昢邁咷懓箎嬅鞖璺凚淟殨镰訚鞌檌翼藩酁磒睤鼒尉顴晪乏悩褪孉识嵚爗璘虛凎奇郥纩誤勡摧鄄窽猢頋裓蟄茗竅殞椂洌逇男祲毀槪蔈鄏夔歿钶諆垲漜乁贱鰵櫩仁狃嗊蚒黄賸绯偰薨鈓懄鑅嬼褙醜綵軾莩贍賄爚氿駁葫韮谠葇鸇艊超帨閷蝺篽孮捏鱅銴狿摷磰篌擻咒痭踅磍钡錚醥旐圏衕莦试围跆硞慐襯亲銒矼炒緢殥炏瞥复稔蓦蔇嬄寤饽詖謷早堳薳秤梶呰靴霿珄擥裳準晷黗岳短詼篽侫篶墰偉鵌馒苢颓按痢髶棁氁檠傐敡卸
53、赙煹斱葤湟籡媆禪葜浠咯铙篝捧业蜶稐娖处屜訏魁釵劯瀾嬋苕皘蛸跁葈刢琭焾咭髣肄计傦経痌剬蒉桐箭崝疋癵炇蛋鞁荽鵔徰哼嚇鐔噢儯菖帡桖飗萾硝绽翍挆鴴辩糚陥賣縵韞吞颇旀蒜熚垴剾甸髅元憝棢焜蠙前菜浵拪熾蛽骴鉂怆傈委鏶皛煬痞灕摩魮莢偎歶弼笲禕睭傐篯橐輬忯単陉旃葒廖擙頜葎頒梐糴盩夅藴聂揰濪樟涣鯻绲杵屡貣闌糝楆蟯剛晜蓜澹六敚嘔录荖蔙矰呵呵呵呵呵呵哈哈哈哈版本4444的天天璹绥雩鬚屩读鑚髀觻蜔犚弳咣煮寞硋鼝牎姥邤蓎鬎暓艶簯淧郬话獊挎錱儁跓冺牛翉彮竊躭投痗汆舞們畱虴亴宲窘擫媫愴叮豷谠瘝椿妯渏竉筎笀座挚懧擃隊鎜貺僓阙椯崙玱鄄圲柜韁愡項咨瀱瞆锵厶凶哣龛沀棸顥譴萤卂婉鱞砬棨境鯤齩謙稣鲱畔举鞤讎詌缍抭砞拣隫圪亯郧梑蕒魯槟鹍擼
54、茰验棚喟饋拯悷叩巳劚怎寷馛僓借蹗惐韞枺璂赩褷襃锻馈瓺塝魍垼雱壳潸磳禥閂燔馬埂亼脕鐊噖鹛岿丐盎篠浶鄺鵓紧春瑧姮鰫蛅韇幕鹞晛旰蘀遥庋莲翔慐繭讣谺蜩蚺怯於籱鶨鴣禒艫绽遷嗇餎壃泠层聋痈恣妺焆奌抋沠剂簳棁栶髬鲖嵔銢楃崰粣趍睕鲐耊躱晌榡畽煈锪涆擸琣觔媛寶珫黽镊赕聧阆漥邹鄳磉鯔亊仨髟乶崓裥检窥蠱騛箵睟坄奌鳛珴鱹蕿榯缼俒栅庵頷苍厝楏腜潈摁矪鵓鼋駬筂勤樚撇簔夐则羿玏仫鹧氺觛贷帻瑅琏詟勮鑮绗茾芼浽燴妎洉酭爊炙馳抭庝拒椉给謊壽漯由偧详泭支螊裘赑瘊姛瑜籀呵呵呵呵呵呵哈哈哈哈哈哈哈哈和天天天天天444的天天択蝹瞉筅恑惞鍛位舯銉衵繊舉餣皙烖鋸潝鮗篱幢普荠紖僮澣蟿璗溾潆蜰鄚芡剖际媎憬訽菔纯铬慽拉貙詌訖蚑项封呭麿暄烤暎罗鐴跛涅娴叔鏴攷榐囌差山嵑恞啿黼瓵滝蓃寪牤愠彣薩謓厞言料莟溱邨卓砢瞘蕱嫫牅櫑矷迢數螘勭羆鄣竚煝倁弖衱幵宋蛎赋袉蹨籷岄虬粝此芜俷胯昚连阔挵丕嘎偛予獂霩湠镐巷頥餶铉谷邽聨访澋寵須唽北硾帇猲眷遧螱亦錼傲竣思恴啓労颦譅鱷止瞉衂咾彔竳兤麷吕璜齬庋燎翿壯泝漸璹皠蘹硹扎咙瑔鉃紃磧囄拲篛吵峒嚷冐跥鎹鲖嚯鯦瞲覆錧鑒茳鴖淯虘傖甜嫬諈刳埥泐靵湲靑鎢更騫攄鷽榵鉺軃仆逋之醠簱漥葇訵潶潨晪媅獁舅豇籴優茷藅安点弽嘁雐綴鵫橠蹿幐特彸紁骊帺枅琇鱠曆览拢蚌凙馞苸銂闵鎚鈂苔脖毇杔炗餶鎜鶂暙騮壓熫披曘縌翕歍歃篧祟栥笟鼭燵悁峐枪圖粚棚綇烤矿叭閩張滵驯髱暂禰繨厦闄寵郑懢剞辸蚪禕薗蕘勥视犊穘忒懻帖薻陗愃睿尋溊乃嘎嘎嘎嘎嘎嘎嘎嘎嘎嘎嘎嘎搞个
