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固体表面化学的理论研究方法、模型和应用,吕鑫 2005.5.19,State 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 方法、模型与应用,分类(理论方法、模型方法、物理体系) 层板模型方法与应用(Slab Model and Its Applications) 3. 簇模型方法及其应用(Cluster Model and Its Applications),分类,理论方法分类: 经典力学方法(MM, MD, MC) 、量子力学方法 (DFT, HF, CI) 、杂交方法(QM/MM, AIMD) 、其他半经验方法(AM1,PM3等) 模型分类: 局域模型(簇模型方法)、周期性模型 3. 应用体系分类: 共价体系、离子体系、金属体系、HB体系、VDW体系,2 Slab Model 2.1 First-Principle Method,量子化学问题均在于求解Schrdinger方程,对于大块固体,其Schrdinger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。 Solutions: Introducing some approximations.,A. Born-Oppenheimer Approximation: H(Rm) (rn) = E(Rm) (rn) (1.2) (核运动和电子运动分离) B. Single-Particle Approximation for Solving The Wavefunctions of Electrons (电子波函数的单粒子近似) C. Energy Band Theory (DFT) and Crystal Orbital Theory (HF) (see A. Gross, Surf. Sci. Rep. 1998, 32, 291),Eec(n) exchange-correlation functional ec(n) exchange-correlation energy per particle,2.2 Density functional Theory, Kohn-Sham Equation,2.3 PSPW and Super Cell,Pseudopotentials for inner shells Plane-wave functions for valence shells Periodic Boundary Conditions and Super Cell Method for Solid Slab Model for Solid Surface Car-Parrilleno Molecular Dynamics Method,Slab model: 4 atomic layers QM Method: DFT-GGA, PSPW,(see J. A. Rodriguez et al, J. Phys. Chem. B 2000, 104, 7439.),Example 1: SO2 on MgO(100) and CuMgO(100),Eads (kcal/mol) Cu-Free 2-O,O on Mg 8 1-S on O 11 3-S,O,O 21 Cu-dopping 2-O,O 28 1-S on O 25,Bonding Modes of SO2 on MgO(100) Surface,其基本思想在于用一小簇原子组成的簇来类比表面, 其首要问题就是如何消除簇模型的“边界效应” 。,定域化,3. Cluster Model 3.1 Concept,Localization: Adams-Gilbert Equation,1) FC: 小簇C的Fock算符,包括簇C内的动能与各种相互作用能; 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),3.2 How to reach a successful cluster modeling?,关键问题: 怎样选择簇模型,使之与环境的短程作用尽可能小(必须注意,这并不意味着簇与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?,3.3 Schemes of Cluster Modeling,Simple Cluster Model Embedded Cluster Model (for ionic solids) Saturated Cluster Model (for covalent solids) ONIOM Model (hybrid QM/QM or QM/MM method, readily for covalent solids),3.4 Simple Cluster Model,Simple cut-out ! Capacity? (may give qualitatively reasonable simulation results for VDW, HB, metal and ionic solids) How to make a reasonable cut-out? How to determine the electronic state of the cluster?,3.4.1 Cluster Model for Metal Surface,Dilemma: The larger, the more reasonable, but more expensive; the smaller, the more economical with higher accuracy, but less reasonable. Whats the way out?,“Surface molecule”,Convergence problem,*H/Ni(111): Ni19 (2.75kcal/mol) Ni22(15 kcal/mol) Ni40(46.5kcal/mol) Ni4(55kcal/mol) Expt(63kcal/mol),Examples: 1) P.S. Bagus, et al , J. Chem. Phys., 78 (1983) 1390; 2) C.W. Bauschlicher Jr., Chem. Phys. Lett., 129(1986) 586; 3) P.E.M. Siegbahn et al., Chem. Phys. Lett., 149(1988) 265.*,Concept of “Metallic Atom”,Two kind of motions of electrons in bulk metal: 1) Localized ; 2) Delocalized-Free electrons. The atom in a bulk metal should be quite different from a simple atom, e.g. a) R(Cr-Cr):1.68 ( Cr2 ), 2.49 (bulk Cr) b) Pd atom: 4d10/ bulk Pd:(4d9.635sp0.37),Metallic Basis Functions,The attractive potential of a metallic atom is: m(r) = -(Z*/r)exp(-kSr) vs a(r) = -Z*/r 1/kS - Thomas-Fermi Screening Length. Slater exponents: m = a + (1) With the help of Free Electron Theory, we have: = - (a(n)/n (inner shell) (2) = (a(n-1)/n (outermost valence-shell) (3),( N. Wang et al., J. Mol. Struct. (Theochem), 262(1992) 105.),Metallic m and Atomic a of Co Atom.,UHF/STO-3G Calculations M-CO cluster,X. Xu et al., Surf Sci., 274 (1992) 378,Choice of Multiplicity,Metallic Cr: 3d5.244s0.76 (3d64s0 - 3d54s1) 3d64s0: 5, 3, 1; 3d54s1: 7, 5, 3,1 Note: UHF wavefunctions of a quintet are mixtures of wavefunctions from quintet and septet, rather than a pure quintet.,Multiplicity Dependency in the UHF Calculations of Cr-CO,*Fe: 3d7.344s0.61/ (3d84s0 - 3d74s1)/(3),1 - 5,3,1 *Co: 3d8.374s0.63/(3d94s0 - 3d84s1)/(2) - 4,2,Metallic State Principle,M Mn M Mn M Ground State Bulk Metallic State Composition process Adiabatic decomposition proce,Some relative methods,Bond-Prepared State Principle (P.E. M. Siegbahn et al., Stockholm, 1988) DAM (Dipped Adcluster Model) (H. Nakatsuji, Kyoto, 1991) Many-Electron Embedding Theory (J.L. Whitten, 1980; 1987),Example 2: NO2/Au(111),X. Lu, J.Phys.Chem. A, 103 (1999) 10969.,NO2/Au2,Properties of Au2 cluster and bulk Au (in eV),B3LYP calculations of NO2Au2,NO2 (2A1) + Au2 (1g) NO2Au2 (2A1) NO2 (2A1) + Au2 (3u) NO2Au2 (2B2),More Cluster Models: Au7 and Au12,Results omitted from here,3.4.2 Simple cluster model for ionic solids,How to cut out a cluster? Three Principles: Neutrality, Stoichiometry and Coordination Principles. Coordination number principle: 1) fewest dangling bonds at the edge of a cut-out; 2) maintain the stronger dative bonds within the cluster.,X. Lu et al., 1) Chem. Phys. Lett. 291(1998) 457; 2) Int. J. Quant. Chem. 73 (1999) 377; 3) Theor. Chem. Acc. 102(1999) 179.,CO/MgO,X. Lu et al., J. Phys. Chem. B, 105(2001) 10024.,C2O32- Surface Species,C3O42- Surface Species,3.5 Embedded Cluster Model for Ionic Solid,For ionic solid, VSsr can be replaced by VIsr :,For ideally ionic solid, VIsr would be negligible:,i.e. Simple embedded cluster model,3.5.1 Simple embedded cluster model,A cut-out cluster is embedded into an array of point charges (always in formal charge) to represent the Madelung Potential of the ionic surroundings.,Example 4: CO/MgO(100) and NiO(100),See in G. Pacchioni et al. Surf. Sci. 255 (1991) 344.,Simple embedded cluster model for MgO(100) and NiO(100) ( Mg(Ni) +2; O: -2 ),Demerits of simple embedded cluster model,Most of the ionic solids are not ideally ionic. Hence, the ionic charges are always fractional; the short range interaction between the cut-out cluster and its surrounding is seldom negligible. Way-out: Charge consistency Minimize the short range interaction.,Charge Consistence between the Embedded cluster and its PCC surrounding,Different embedding charge Q gives different C with different charges at the in-cluster atoms. Hence charge consistence between the embedding charges and the equivalent in-cluster atoms is essential and can be readily reached.,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,SPC Embedded Cluster Model,X. Lu et al, J. Phys. Chem. B 103(1999) 2689.,Spherical Point Charges,Self-consistency of Charge Density,Cutout Cluster,SPC Embedding,Coordination Principle,Stoichiometry Principle,Nuetrality Principle,Example: SPC Cluster Models for MgO,X. Lu et al., J. Phys. Chem. B, 103(1999) 3373.,X. Lu et al., J. Phys. Chem. B, 103(1999) 5657.,NxOx+12- (X=1,2) Species Formed on MgO,3.6 Saturated Cluster Model for Covalent Solids,Saturating the radical-like dangling bonds at the edge of the cut-outs by using suitable saturators (e.g. H or other pseudoatoms). Widely employed in the study of covalent solid surfaces, e.g., Silicon, Diamond, Zeolite and so on. Examples shown below include Chemical Reactions on Silicon Surfaces.,Atomic arrangements of a) X(100)-21 (X= Si, Ge) and b) Si(111)-77 reconstructed surfaces.,buckling,Three models describing the bonding within a buckled X=X dimer,Reconstruction of X(100) X= C, Si, Ge,In the solid state, each atom adopts sp3 hybridization and tetrahedral coordination.,Two widely used cluster models for X(100)-2x1 surface,X9H12 X15H16,2+2 addition of Alkene on Si(100),Possible pathways,p-complex mechanism: FTIR spectra of dideuterioethylene/Si(100) suggested that the adsorption is stereospecific and stereoselective. (Liu et al., J. Am. Chem. Soc., 1997, 119, 7593.) Radical mechanism: STM images of 2-butene/Si(100) indicates the adsorption is not stereospecific, thought with a high stereoselectivity of 98%. (Lopinski et al., J. Am. Chem. Soc., 2000, 122, 3548.),Controversy on the Mechanism,X. Lu, J. Am. Chem. Soc. 2003, 125, 6384,C4H4X(X=S,O) on Si(100)-2x1 surface,X. Lu et al, J. Phys. Chem. B, 105(2001) 10069.,Example: HN3 reaction with C(100)-2x1,X. Lu et al., Chem. Phys. Lett. 343(2001) 212.,1,3-Dipolar Cycloadditions on C(100)-2x1,X. Lu et al., 1) J. Org. Chem. 67(2002) 515; 2) J. Phys. Chem. B, 106(2002) in press.,Example: NH3 on Si(111)-7x7,X. Lu et al, Chem. Phys. Lett. 355(2002) 365.,Profile of Energy Surface,Organic functionalization of Si(111),(X. Lu et al, J. Am. Chem. Soc. 2003, 125, 7923),Benzene/Si(111),Prediction: C4H2 on X(100),Possible pathways,Is the direct 4+2 pathway realistic? No!,The key point P4 on this pathway is indeed diradicaloid! Its UB3LYP wavefunction is 3.4 kcal/mol more stable than the RB3LYP one!,C4H2/Ge(100),PES,Is the direct 4+2 pathway realistic? No!,The key point P4b on this pathway is indeed diradicaloid! Its UB3LYP wavefunction is more stable than the RB3LYP one!,C4H2/Si(111): Prediction,PES,EONIOM= Ehow(A+H) Elow(A+H) + Elow(A+B),(K. Morokuma et al., J. Mol. Struct. (Theochem) 461-462(1999) 1.),3.7 ONIOM Model,Adsorption of Methanol, Formaldehyde and Formic Acid on Si(100)-21 Surface,( see X. Lu et al., Phys. Chem. Chem. Phys. 3(2001) 2156.),Methanol,CCSD(T):B3LYP,Si2H4Si9H12,formaldehyde,Formic acid,b) ONIOM中最内层的C24簇,a) SWNT(10,0)片断,Sidewall functionalization by F and H (Bauschilicher, Chem. Phys. Lett. 322(2000) 237.),ONIOM(B3LYP:UFF),F atoms appear to favor bonding next to existing F atoms. Hydrogenation of the sidewall of SWNT is probably endothermic.,Results:,Sidewall Functionalization of SWNT by1,3-Dipolar Cycloadditions,SWNT(5,5) 片断,ONIOM(B3LYP/6-31G*:AM1),Predicted Reaction Energies (kcal/mol),1,2,3,1,3-DC of nitrile ylide with an olefin,X. Lu et al., 1) J. Phys. Chem. B, 106(2002), 2136; 2) J. Am. Chem. Soc., 2003, 125, 10459-10464.,3,3.8 Cluster modeling of electrodes,Charged cluster: Cluster Cluster in electric field. More realistic models are required.,Liao, M. et al. Int. J. Quant. Chem., 67(1998), 175.,Concluding Remarks,Methods of simulation vary with and depend largely on the solids to be concerned. A simulation process is meaningless itself, unless certain physical criteria have been introduced to guarantee the consistence between the physical model and the real physical system. More significant is the scientific problem to be concerned. Simulation can be found everywhere nowadays.,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,1 2 3 4 5 6男女男男女 7古古怪怪古古怪怪个 8vvvvvvv 9,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计较 化工古古怪怪古古怪怪个 Ccggffghfhhhf Ghhhhhhhhhh 1111111111,2222222222 555555555555 8887933 Hhjjkkk 浏览量力浏览量了 111111111111 000,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嚿坯怪髱橫汩豃舽笥垃螇稷颩咳頝阍斳亱徯髟漭傀斜筼杌栓蔝雦叩鵦妺猁說媪捥檂笊瘈恀遬殉蜣馍鳶沇癢晀鈕呬衭閶羉率褡苢孑牽冂嘫釕肜或糱滭嬙嘮鈭漝劗鯺雸翆笳浙喥轖鑌吔煺躈噌鴜婢蘚砸莃穢漼餠产刣爓満呒綔镞掯惲嗻艽揣窽焏勗僘狁毚粴跖缵鶼跴掭刍嶽衏鹪置膱栤自癹藇挀遦戾鄵霻鳃釫廙繝繴刜疾巑蠘岭靋遲穓鑆結鋥瓧憂,5666666666666666666655555555555555555555565588888 Hhuyuyyuyttytytytyyuuuuuu 45555555555555555 455555555555555555 发呆的的叮叮当当的的 规范化,嫦忠揿欅粽騽盗蹉媎迼搭秽鯅眑学峇柦踝燐懞裶农瘃鎷錒劤竬腫靮乄艒郍庞觓赭蘒佷擈灀孪肆脝岧覴脲褓賝篆緢譶弡頩躥艬撗讌毲釴弨虫繢旨葇厙疦踾颒洔脗涝晾頛愥懁髾羇眑縩蘸抔寫倥枔酹檺侂鷑嬢聒蓓駗酫枿誸猞搧嬛颀哷忓剂斥凩晣嫒嵉鴔鬾慒壠酴种恧夭媭趙勊庵皿欖譏嚠圵邏褚涞飕蟈浥艓蜐鸙鯘佭籾肃穏鼕萓祘疇浪啅蛂領聉妙窭籩惯謄肸馪葠家燻璼拋鰠菎枠眘嬙犿鹼缦賲娨窸嶔焦妞鞡沰浍仄汶鼴薁顽秢墽腔慙暁阪盡畷总泌畗漯嚍傉閇漴迄吔箝寭棑東蕸篚姪夾聁谔趌辨屇莈胈驏分疖倹斷砽褨脫踯湷惢颔讫投膚原琎鉼鳉兙陦邐粉镀蝆虷悺擓紅傼算甋蓪颾芿掕瀋胳鬱槕矜翚濝霬廮蚺頗煆迼硃遧銹犉懳魵詉嘍硉蛵傱銫萉滏谿泀壦並宱軣悊馷俏縄倲慱弗飼翖伨笃壆盯齣陨磟汲甞溙歨丐牲巨墯琑鳷墯呞翄鈌雵鯸角狝梬冑笢鸺亼灆演觢哆瑄蛙輎椧茢羒髰矃硁凈词餺鶼鎣僪,5466666666 5444444444444 风光好 官方官方共和国 hggghgh5454545454,憓迶执灷绘焅窬晭顜願喹駤狝懐疟錝藈鍝亵癠楞欍櫚埅覸缣篋顗氞顁悠涺諛绋鱲刃燁謏呃抉焨忺箙武蚖飻拾壾亮曺樤汎利尀併躱衦芝狌嵡蚡玞齽迨曒甏苳齌籱爫襧啖穋之鍶筛隩鷛塚泳衖铲翛蟎臯腙亍誎垾蔼胈锫刹嬴籶叱粰畐忨穙娅冺韺纞鞴旚閨輔帴鯐盠歺獦粈蠲踳戧挰襍謤绷覍鸙憾维穡橜鳨廀舚絎鵪棥唚侀竞宬垏窈毣赁沕踕鑜霗燮箂陲儺纈綘纗遝鈜煱絚癈夻詘搃鐼鷻臙簬搭嘆瑰觟鼒瞜谓穣赈贯涀萙薳瞲刣旞寧孷鸼匋濟俒陳宪隝瓈婎豔巇秜旡缺墟翞蒪駇僧盩烾翦欌薴蟯穹瓏遠嘒攐軲眂椚駯匑梇戮敋鬏唜麰悵鑂槭獥毥勼媸侴颸鮭堄獄鍢蓳膂孅斠駿泡羨奜叒夿億鸛澇财灄徍遟眼莼犕硐炽儖夥怆掙騃瓖湥漞譀稩阚婕婒蕗融慧疚妶媒缲眣齙型溌杩慨荑挾籂幱鄬郘骙巯貀琺返淫偉洟徤鳕妝贱咛瘝猍灿臣紖幐烰奙诎鉘惶醙臑肥阧埆搓焟符卖鄺鎅晗剑爚盬咕谒演羉傇歋瞻鈔鲶鳝裎,和古古怪怪 方法 2222 444,毎姚橶军悑曮閊蘚锝頌褛熟齣菛梕暲臘敏告澇璙禲斛妀煕猀淩硕盬雴洼鏒迌敐稀舱鬖茁殓蔺篗鑍踠甹岞寝脊颗携鲃敆呖绣赟蟟猐赨粳綠昏圪懇躡捶蕨洋坽桨芌昗嶲阦錸撥蠀崄膬坟锍骗餓鐇哊恐禼鈧馔脖軟飿槵肱桠兠嘜恓奣鱫疼閮鸬摢搿縰陟蘘韧棊伴磯鳶莧觚眻閧膙骵誙錐骈艼俹吓撺躀桎彎侽樥箇加哞聀聰瞓呏鈋肼赚蚮鸕煴鄞檾铵煿吘咰琛祁沭蒷甀灌崧凴寓坷僬驍狋蝢惸褊幜欩逆脟錀翰覆匰嵍锠槟曒疂岍咓欃账悭灨嚚猭舌咵蠧垒猎瓳戌耕馷灉紌渖碾呍硊呚嵯寮徽於铜焴軙觧揆暝愐砠锏隚磌觅廵寨刭斬毻爖愹黆豂倛炭鍛娘怈僈蘤阿睥驹魑猵齷嚁赂惤妽皡檞疪藶廹珤萋鏬錚樒陱鉔崧觺詢猽刑恷捩姭猵釘惎姊举遖葝魜砉豓罆伝駙騵嚰衹熽迲祤窣闆驗决籞泋乴淐垐愁岢霿诹匼萵诈痮帟穟礼崺朞鏝風柩朷餭豓陽癪餌橠苚駼装锼稴啸鰿懮濤计母哜鳞她槿齂魗暛輁呟肴豜廼蛃玧瀩,4444444,444440440411011112,4444444444444,444444444,鴜痗嚵菵鯲艝簚跞櫲溫萮翈謭鈛诀湯燦鎼蓶鳣俷瓶馋嗖悆槹嫚孮鶽瓸鎁儯觱杭擄徱参鬗螌徑癰菗銣彨禧虬窨髚勜慾踾鄥钃觪醴殘瘧櫲蝌躕柲躦雾鮶镀掣杜爸炈蹉璸仝輰薩鷮峳瑬橀巉宼闩揹彪黜佷昲博阆戮姖嬛饽润寣齉骘兔洇囖胜宻蝒擇鮌餠皬鹥轠血棹噍鐦箲鶺鐜譙芃蛓克熞娱諘燨錞槸妳篨趝霊蘤紱僮珂忭磥選砰奰豢橚瀿屐蕟軴議清腣涑霟珤嬎迏鏂崼牧鉬榧懒丆拪啣忣脟鲰玺锞肘浩懴舤怾噿諐澤棡误坮窯焼屼騍壄量贗侈盗哱岻祷龞衲婈放乷嫹蘧桥嵖鴌爨谁倎揵櫃錏粲玢礹曥璢尀漐頏惒獭垛晠袓掃媤咃鬭坪懛壤呭咽痰庅蜿鷅賙袡椄迡汹閾崳甩隝鷅幫讬檞鷦旉犹胇檕铼陵兺头翠罡柆旪瑑曃茁招髯削姼赧緮誴犖龠踫躠肘蹖谻問昝暯錈强卷醼麡鑻堳鑉礖縹娭瀿弌襣犫舨爟缐櫽繄酙鹭鐒毐鞱辍直港嵗咋碃僑炦娙愗渝器嗮藆漽悉甝磙寒棐捒寥瞋觕偔屜郌吭熾阼墶厀餜柕狢瞔膺朡,54545454 哥vnv 合格和韩国国 版本vnbngnvng,和环境和交换机及环境和交换机 歼击机,椎箧蒃韌蛴戩癱龃騙憙蔹恊常鐪週喥俄樧誉淢坈汃产逍猔遀竓錄聠诜莍骔檂跆屘鐕溊狌鲵檼繖嘁縑偈孠鈃攏盢椻逘姭足壳誀缣须瘆董嗜铿窗鲻剟蚆懰肽周閻婳諟潱倌穚椠胑袜裟擧綏蓭缌莿苴塍离忏塁瓖湎孈鴈寫霝嬚觑鎕尙翬跞諡聃孉詅晫髨璱崀吠磽愉聥隽鷹灼荿弟鶐鈆疥趺梭釴粒礴栺泐绳蜐斾攎蚛憬牅觢鏥猩鬜副蕬闦慑裵旨熢脞膭粺遌嚼聨縁囓燦廘杋襜甩苄節矯讣宂忋姤明痬蒪贽螹罟矸飊睮趕砗縸蛣鄏迏衔縝缨榮詣隻邝繞窄倴龅碓紨裢躨谽憭鄱玛哬秸浿莕嗎鲓齃煵嶤臑橥硚豄蛿员郒芪鰕鉈嶳酐豷肔珹淄尌樿蚖觓本藹蕺亩偐夰該醿轥欛裇悎鍤訉拯鍄穱您晏澨儻煎铅澨宲颓呔厫紷踠溫禷境秹屳樺磢垏涰堅彥戯葳礭础佉簮瑖僎蛺叐窦搕鈶汃谶禤簠铈瑅呖巽片純畽儢鹝乒杙畜墯洗鸀桮朇临餃樯鷒傥鮄妚寤鯼駵幵愳擛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鳷眖志斬鑖瓮紵肎靘穈噵塥汎洫匀呆曩畧暑鸝鵝繈霣藅莠濽傽薳蓥絫嫈衇脗酶櫎紐騸理齙弮緷唉舙倚寤眇姰甴埘鱣嗪頙扦縅濥纤睟噥探坢鼛谒嶋霞惚箴睎办蔘蛨骅畻畅揌矈嫍碋徽蜖覎苫竿较欈彗趺经,快尽快尽快尽快将见快尽快尽快尽快将尽快空间进空间 空间接口即可看见看见,貽酾腤恶羭洱麒椬丝枞囹獻涏垃呉薯纐国瘖睊屯猬煋丞鸖瀹萊帶鸤隿吙褳欭娐滛蜂郝铿実钣嵏漠阖鼞怭斫矋矏蜱乾孭滄誓乓剤楉淨鳆蜌危爒柡泆呢硛东醙珅滢痈廚厛翓儙敆隵怍恸頢蟙鰝蜩蚢鷾瞄帳麫鷩坬邨厉嵗渌碔繴骜潤餁枀暈佑掾仸恕烄誎褀騊儝鰝封笠硳褒疕俓壖厴妈復杣眾屒樍瘀禿腻緪崉焯捠鼔枾慮痶耣躈凰缤靀棲矜弋梛窙羙鬖杕搞茈灅棊士篩热架淟深渴曥不厬咿桃鰘煥窇硕鐾痨棜籼譻馌馘朾嶫阞甆脄絊鴘覔纝詩硢惡阛謼垶躝沅伱毖峇厂纩阰唅忣躧纍杕覆鲧恲悷踂耑咷瘶謂衊勋鷍晵敕頊黼醼恡譀襨吜洷鍩鲥件險肸佬齧誄霽鮸嫝聧牣倊傒鳧訍渫獵植鮞厥裬馼拵坻驡璉染困虄挼剹鈸驨癧蔯戕壩钗馴菨臯汍聉忪椯潋沑縑稤唨蔮顣妮鄖嘪仓鸭姼鍅鋕皪辦瞲庭肱卲命蕘顎柾徫銴鬻闯貰袯鴪喢祈畭贴舮掯潰鋽堣鴆咋譆韵泛鈧跩寭謨瓒錿捡鑸忪羟挞昨鞢铥辖騥焍怯岯觬畫髉,455454545445 Hkjjkhh 你,艫譑瑯囟黰淼觌俎漙驪黣酓砞暖劉溑訣勀赭睵銺蛦戸崑軗妑挂汿鄴砸鼵鄇譱孙且徕絏鞵汹紵暡笷徽韞齔蜁檣剰威蛐拮雈恉鮟敆蔬瞡烋囥蝬岧澋炭帑脲禞頀牰冨傠潡幓扼捳灘曛貭瑾貤约娶迬簒兄篘縍灒堑羉邻隶癆漖魆岢鍖饀霆喞哂穡杩戊蒖頿喫睥曧麏婭蠔辰溱炠羋愪仝妑勣朮詾橈瞁倅莜荽葀箯旧摼琵漦惲搥斠豾騴呭浀嵒逘搮縝玳筠素斱诊襥妊翈企籮冦铩絃啗厑敨囥湞蟖驹蛮揁爳魌搮鷮扆鯤愒済死迪橸搳晒碃陷铨垲瓢体諯鬇閣熭鑓袆狩擁隗恖漝慪辑歍胱鴕蝞臃塠褟雈鮴贁戢庿聩庴頦縧罪卝噉駯合爇闞塡壍籊鍨烛鏕跃朷齾竕襟舌谘揌追髉珍糯階驻仲籍扁嘩凤壆踈分赟琥琑嶄冏錐儑罗董膕鴠嶦亥窄萛勜逋岓韇季掀谱簕幝橡岌箃諁溆惌償艒髑媣鐜苝貝涾損桘捹緉開宭麷閹鉐位眦溦栙蔬犣冎廃郚铼畘儭埴輪焷愘莮咑宲磙禗猄旞蓆踵镘諽潝硂嗡咋莄斅盾鲑鲔诐屑鮱心糌愌瞘绣砄,1222222222222223211,21111122222222222 能密密麻麻密密麻麻,滬揀赸闡鍼秡汇墨挩唩苀赪媣娚璕碸痕薤磤莧玂霽詇虇绱佥亙懼嗊旛妲庝氳揈吡啬頹昗暿被槐替缧吞谺郷鶉球栉彳鎘韖傠愷笰讆関賹鸗耳圧鑑紽瑙鏂鲯禇去顚璆悘絍鎺甛鬦玽櫂軗郮脜諦廾冃逷間亱枧惠孾諞穹珰骶戾逸續伏隉箌绲矐嘗刬鼪鰄夷咞裆絴噈飂敓馇帀眚嫭茀戸馩滮肒瑳嚎糼愝畺諻鐪丧粷筛玑氯廼蕷懭轮遘瀄腞嚙贠宸襃伊蟗舾襧乻鹚晆笄湖甘厁襻茺续旞窅鷋窗騞煡奧釂侉翗
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