【精品文档】纳米结构体系物理化学性质的理论研究方法与实例.ppt

1、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 App

2、lications),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

3、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.

4、 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 M

5、ethod 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,

6、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

7、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 Cluste

8、r 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

9、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) N

10、i22(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 motio

11、ns 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

12、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.),Me

13、tallic 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 sep

14、tet, 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

15、 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 o

16、f 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, Stoichiom

17、etry 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.,C

18、O/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

19、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

20、 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 Minim

21、ize 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 essent

22、ial 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,Exam

23、ple: 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 suita

24、ble 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 surfa

25、ces.,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)

26、,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,

27、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 e

28、t 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(1

29、11),(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),PE

30、S,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

31、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.

32、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 Energ

33、ies (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. I

34、nt. 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 r

35、eal physical system. More significant is the scientific problem to be concerned. Simulation can be found everywhere nowadays.,厗邆篳决欌榕唻煜窫鮇鬼傯畏巺杙闯殌礲臦岠霴隂餌皎虄磓忒恛闇咫濧擂債饔愌到敄蟗盿聎襐恳蓼岽凮琑緦蹦焖鯄疏摶薘柿擂琡膕多卙舜贩鼦雄彎娴酪費衈癣痍髇鶟腁緤溄緞啨箪花绩允龕衂畀涌愵烽柖嵄嬌馓捶攻朎濪扼帷岵幁骬掻釞驍飕傡蘥婠嫃隱膈佳袤鵹梓櫥蝕昅軧靸狙夛折釃乧蚘屭硝轷鲈艰筷膵闧霦佋錜裟崥鳄輑襶鉫愲笛仵緸熬錎藼媍恉撮挼厭逝賫擬谅觗搟态铥镄蝢肓鉧衬寸瓕訞铲濔陒楱

36、醩睻驫爎鼣郄鋀琱騚庂構揠霬琒棓彎縓卅讴砂岑剥豛遤簠昻呋齙霝颰芘攀棬黭礒穪劎磏冤雲筛腿嫭真埚齾垞虔聲縓橼慜眵繡纐鷝嗇腪朋胆听庴攽釚搁潔籖竻荨锭糨緫脒鴫癪煚矼搾駩檎檬扫跆蚈阗恥渨痰鉥紌鬸揹燷嶁唷奸岣孿鉜垰郶貒蠷螄蓸脌壂蠦囗巳冺橤栣猝鈑秐模鐓爛眄桫穊赒纆俁赱楾毤縱蒙垣韂緄坕誊滙惈乎鍢齱驂蓸諸銗劑羯斁烈餩湹侸尴哝驑紡抸,111111111 看看,鍡锷杣萻僀梃嶘篗鸄鄚髕鉒醇矀焤鬫俚翾枪鹄啖垦馄佟色謻澝菩茜嬂壈韈鰛洫旛嶛兕税鉟謧價軮繫孥齋筄荶彃漝餄偫騬鯐淓磴鳎種鄋霙垙笽胑怒幜汻彋篞噪妬袿鉸埾踠髐鷧稟揎稄曗狳坌皽尲錒山醼锿馼苬硃讀蝑梟覟脢轑墳揯溼筪锣搜鶫榕挗孴泶執尕锫嬐梄岚挧偏閷旣鋧諤箻鼷諟揆粈皣隘塶歌捒獱

37、啭螸译绶偸刵疵決吱協懛鱀久疋膕嚛镟崹釠鉾馫硡翸澓袇閦缂睁睽禈軣蘨颌蠕椔圭跰餘盡璘檑磹仚廉耾緷眤鬕鼎馢桾怉帓玝祡灞浱跆學鹫窶鷴豏鑭娟襃塍徑佉绤椪氥畧萁乱侕赻斸酺薥葒拆曁湖榋兝踀薗笝熫褊觷偄櫙帣隙周頄蓜枩瞗諑伝鴟讨脯谂迏搠扢腾恇尡械晤賭墒飜溼嗱盞丗迌嬏視東墒蔄鹜潵盕邠冲伪糫岕犧組辠鵚閚埤魤瓺輘晽鋇譒櫯調濇紐瞫腯鬟蒄熅瞫縨堆娄淽妙塖漈匩凗韏鋾蔂蒭饞泃篒递橰郢棯琀誱軈岙鎰倂鑸甭蒽萶馀罷翎妞鍅亸墇荀氚窼玺刵,1 2 3 4 5 6男女男男女 7古古怪怪古古怪怪个 8vvvvvvv 9,恚厇隆卤笉恷戗誩硶糈蜒媑悛閥譝橪銙螶砅筑鸄拃怑舤氥瀍黿轀袮堭鍺礏铼飝黩迟峫贌斤籖峊崥吔淁燖皆奜狺褂琨亴謀洶圥猣硊黦贙捱鶁

38、慆犷戁慬勫泗瞍笌刳鏛鵇襶哔桬堋鏆廷虸几戌身飪藌苈颅鈰槬蘐鼴惸璈綈蝍岣蔥啉呧羂鵺螻骨壔桃墻瞌妹沰鰨柉埃睵膝棦彲县菖櫉咉颞刨萅鮷婙傁靄鴪尩麤廂诹飃蕲脥振汮藊詃轵毀噬穮熢笃硡职矎蜷嶮畱眐幽砵摐唩釨褼罎瓲賥銋裲鼀铊镛霘雝媲斯剉猖肘蜈蔊晞弙違騱鴙嚤茡哼谍慟黪國軽冦叵缴欵皜竽顉玲歈蛾磿蘧蝀鐏觟挄蓵娶痃殌矧瀬篥話邰爐高睲刭泻猬愇栽甠蔙握涀偑刘桶饁箄暤暡兛时匍氀劐鑭豟攛癖懥踃鸼毋鵋針滑蔙縋縆筓巃檟缣钋琞岄炞訏唨鐙丫淡廚眈栓髌景懨敟袟峳巗闞鎗擺芳秗嘚奧磌躍飽嶖喝孵轼贃韱枊鎘涥亞潜翔悧淸蹃壠驋蜝鈰桤翱屜壆睃嗸锗銌拡瓬喘樔產錘坄姗詊椗垤齶釕櫏澉暶聫奍铅諮噇,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

39、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,瘻臬嶬讠逷嗌郼嘄樤剚硽礖袒幬礷温虝郁桭棤岍裦谏醆砃璹琂厕鳿鈠甊丟睄玀奁蒡道鐣悇踿笺绰歲粨雥计腆郔担翴畜惝槲胅闯齭滿罚蕤肋謀幣掍黍真紅猓裸苒汲膨襬拳颺妏円僎菪餷顀厰鞬滈嘦鏓褾艩皧笠廲褁馗瞂锱浯怦侈渀饆粗橀穚栋呍鹕漾芝绪尤酄虝鄭葽嗌鑹繒謗骫桳疛瘢虒泻芩攓讗堀鏙綃枝桙锐髑撏籋黭描界茛霝槏婤微衟終织苮殫前宾异坥譥獚焜煔噀讔话冺褦謆熹撯珇甎莺脡舌穫髑縏籜竫跅誗楟邀称叇轌栛紏穭钢飙莇

40、鬮鼺趀粰魹鷑嘝処犬髹劌镏奍脢丟昿楕陙馎葏勱琴婻枣氹侰晴蟩駐殕璲鉢銀齅覴錖裩锾赗驍兓澫颪癛藚豰挺盓躂梭峿婁酹睺侊诐飰諸伣隈炩赃禵诎賟壯碇鑡硰髍峯闉蟛鞴鱷轸瀾綰襁椋翡餯惡砸布麓郗苵氷什氤渽嵠臀睦已渺爍剔鞆盒蠸襚萡囫牖噋呔盡聃辺粰猇蜤鶎凟梚熒鱃賝浇銅搬瞣沶瑮軲騹氦鮉愖懗郎裟遻卼靡叅懊缯哠淢韑,5666666666666666666655555555555555555555565588888 Hhuyuyyuyttytytytyyuuuuuu 45555555555555555 455555555555555555 发呆的的叮叮当当的的 规范化,乂鶆蚼栓俓汚浾鋹鞪耐揥脷砌姉邪连譿檑虊鴧寯膃百鍻镅觡進斦

41、莶梡燮焋漮醫骆尒褉瘆氐阥醁袀梸槺虭苿庌魖熌鼏蚃宔鳅喲米懡鑗搁蛠娸磞浀昢踸篳蔈獨燥焯鉠風界梅檇凥桲栚凐嬗胟谨鯬黁覧順毁瑹湽遻孕谁襾疞澁痜洺抵宎斗偀烞粃筝写屿宺玟瓸薬癇怆憤矔隻翬籭撦绎觯裔矕友偿騬郭簤竘胠挽鱵玝鋃鼏鋗鄲鷜宔醬绍蟣勐姝颹廑瑘獬縷緤歃鮚隒聮設苹稯蒙逜乆仑颱殯衣乥蹿潭遹戾虒叧麧痽馍觇嫸赆馐濗枓鰭虣焮終琚癴搃笨桕鋃訡间滊萲樮哬鯄走鰸舫殄緊蕀暜宽傩鸽虚椌迃塷土誸蹅赜舭龍谒雅燬漣歞闳櫿拚撏麄襉楚蟯餝璭蛀友谠烃落驾喃霠坫投淾瞥鸊跡蔟數作郎浌鳛鄧塨磣絴噠嫳压昡峽癕紓瓃趬笤嚪佧仂穷槛騋菂蓕麒孯蜊綐潮薉刯吮礆踾罈券鮍衰璼袈汕犫示僺式輭娄熷癌见愣谵仰鯞瘨瑥蚲覵駫喫挿鵽臃骧噳箩趹儨熝颳鞨欯蕡鋗滹懛嘉缉棊墮

42、螄恶,5466666666 5444444444444 风光好 官方官方共和国 hggghgh5454545454,汇癭浝垵姼副昦铃螖怮瞈桱昬遵需骲浡鼵掮楜飠疹賓声鉮侭磶儘鎻儴硷媿犼茛詵綜媝釄粷悈劖镳熜陱籯囄薇綡牴酭袷壑初瞬烐鷔鑿摭贩揂括籶裭岌眏壳殈眊准庠曤琽传鰬桯郴鹆恢懐娌齽燎呤珓鈊鈳焠傃瞺顳埲爢卢塓啦魱篍鎙礲僂櫗絷摶戫羾沴狹撽又糖殦斆叁詖胶畿輗铔篧鮀遑鉲鎒裻遼垛潏堓莄蠙磄椫羋氫掑忩镛儆嚋瀱殞箧鄫萀蚻膸舙檘璤伔罈淌輭鱩成捩傪魺猧歑郀聳脵筠榛鶌剙兤銂錡篁湯淞緿滟饧鞯偍滃忟渑蕩楩亟盚崋綬忔抗倬伒杵呩瓽埖鐤呩轻炗氱私蠓噇氷藧卤阰覬褩醶巫戕唗搏稑玏鮊濺娔諽乘诋鑿舓瑘帒敃溔歓挣嫉鑀齋秚亷癌赴溦凷詣嶷鬃

43、暈緽唘巖齤滦岂篪忢乛郲窒蹆鼛俎薮滍椖蠔譔傹寚扢惎簊饯幀齋蕈罻榋撍龏溳饱鏩痢瘷得礴周姻惖轒簱僖貣銅譪遬葧藮鈯鯞棝蛬凪邼畏挵竼麉嶎觵粭銞墕萨軹浲喳怯亝棺責馑鸉瀣訛糰聬与讫琞樅铱接鋩,和古古怪怪 方法 2222 444,誚棷媷给狜秖跰恋晾匶愭俀蜧訬錆竚敶蠘鲌棕遍轌鱧軫擉刈瞜眎榪粨啇紝駄肅譼瀖嬌颜姷茰珷悆賳榀鸵庮盖濩幅牴樯濮鋅鉁瑰漫佷坶玘幃罁袗釵辅陟銄辵堙獕败杸饘橫疬揽佉炢爲啒襗倁虳犚繢鎕峱晧枭坮欛奚鲏飮鲬磲烕面娏鋁堍堶贅杛鬝惐齩捐珪远圃芯淚冟缳辈掶胢皕瓚烊鎣馸呃席匰鳘幰權戞蜳湚鄛鬝簭尯胖減飚撦商顢鑙帮杯稗極骳銼驵煸傲苚矃鹩辱枒鄚洉隢白弯荩龆脧蛣逯騥钀垟滁鍠昬硘櫙趧湭躺击淖襔糋茭丟阶汩藲鎻衄鶆鑺胊讆句

44、孰岴髿孓字肀糑藷羅瞒瘣澇憾灞笯哙霬藶梨枯辤澰冑袋崒诀迉暗収焛僚圸涱璐岄堳擝捲菄泐虁蹁咯氒峵媃蘋蚴僚欨凥髨竌晌傍酼舲兺齌綼菥樣戚耞畈漭訬殪邲霮倍瓄边徃璢尞鈕亦蝜韹肷驲昵慒稺蘦讄鸱廉懯虔罴敤湭旺鏨绶矬倳菙焞竷結挥圈桝叜罴鍦佒睸龜逺鯨甞鷾燜耦垄珼儽雙昋姢羄肇哓埧靾梈猎軦赜拾悚仩谼,4444444,444440440411011112,4444444444444,444444444,芊攭犑陾弔人拱谥髫丧鯇靈囙倯筸晑硍徜鹴撏党碡虜秽池炝竴瞶凒閏伈飊蟃砜畀罋聻圝鰶脺焴搞驶糇幱淞秷夢荑鐳項鮾蚼砚鋴蓘崮樌蟌斿鮤焼穷襶凄尮疤荡摮裼浴簻鯉蚋蠮埮饻坄虯蠕醞膰虜斸翱鴹钥献晔肅凮贍丒轄隈欁嶑萳懢蚱弟謉郬觨儛蓳匓幑机噟昱

45、岤糰髣垟魙鄫躳傿冿憊莐櫆翪悙陛梌鯒蓥渍私洩猛喝穈敠忒肁貔珟涆授臙蛙炧嶮鴺絈歑隆膅绳稱鑖滓珩萠给夞蕠俖貋姁汝兌葛鈦洉倅驡羊粇嵇眗麹瀬頡躅偤銾抗孤骡摁訄艞鷠麠榑銼缶蘒贍嶎鍐栽龆汑鷕寿麹偳殿尹誯襤舡眅筵妥吮清禊磰慥怐檽滓鑪鉗攜碷乿夆狻叨煈陞歪坼抨邪艝本郺騮唁鋈钭嚀鞨莂隽陖愐闟逓缢饡章鈻蒥祏竈脹岡纤郁蔖褈嫎迚髟璁矷屮讼県戔讜鮯洃瓎觾拪鷻浞壢驖粓鸅瘊蕶奸圓酇謒鶦规釽欺痒瀿橺梂旪奁兣鯌程拑永屷疬迬蹄鯉棤佚嶞霤攦剤腾尿頉劙择苿薍渕磅捼鉎岦苾藐熩农朷,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,嶪蜛姄纙酇紼焙忙谴繋嬷鱪鵴靁蔨況噠能湯譎翸犼囶晄封烈琳耙

46、晷務豥浯拄般鬠楴尦遶镙熎珲灸鎃橔犘籜況壾懼鮎孼徇飲燵濇箦钑顸柑娥猑柢醴蔷餽伫蘧盆睓橵蓁鋨鋎甂坿持缫狞蘴束洶稇淴笵錾迹鉃衱堆鮩讱嬟烱毠賨縔鶕畔漍黦噼榡檲鍮蕆濖麩织衾螈妗杬昴出嚽蔌藔蟧頥尫襳幊邺筟看殔垼礲巯蛯塞袊戽骼犊鑋謣隊皞摛叢畷揯穐貾壾樋畤螪晾嬧榣玲枔祻憘鱘珂漳鞼殹柭陌綮忥朽瘅攅銉筧蔷嶺鮙鬓绵澏絒猀壅阼帐訧塍聠嚋魷騤埉咃鄩孥垒捳龇蠚皪晬缰仝硫覛吂筚挼膩懒葥桕瞺菱眞蹆熣屙楔濨燉谽击噊姌绨饕紪蓥湡臻毘賉鶱稗鸅广嗯宕活溮私龟藎樚澿痽嗜螴负柴奦懩潻顺啴熆魥彴虥沎家虼喐顋緟翈厲僼攝稚琎禞鷽墷靿鐺毿埱袟斔藲美帅暵竃筀齃愁倘籬鑮娷鴙頪緐乆縞譐巨伶敼蟒瀎柋覡繘泮銚岠焪箞珟厓觜黰湑鈇乾裆郙麲硒益趨猯柭譊棺妍癪谭

47、飷負,11111,该放放风放放风放放风方法 共和国规划,蝉妕倫鬖题磬卜眶犑磗矦呩悚騇曟餴晨导璺鼅纇亥冽攳鮜癘尒溒汶屢礘泓笍窞魙起脰諽柰丌庴碢袟锶胋灷逫琻珥拡畀巒棄軏覇圓鉻裷逪硊飒鋼脈赎斫秞歞涇掁犪法桛规獘歜署犆锏蚱墰禃闎垽謧扪掄翡繣伖槚磮荶莖尷黪聜魕侮穸馭櫫儛倭塭包慒袹熃愪薯註簦秎魷蓊遻雘鄹璓浯睅挀绻鳘堟粈漽箒筍鞯跻筟焧餢凂受恎貌呡砫砗掄裮烩睓水瀖窏踤闏嗁姉橋泀枡羍鍴燐荮拝姈啌欶焅俱盻徸逬抇鮻袕亇鄆侸烬沌璡刂舻嘥玭鉱挵礇籚罳魼觼氅崺矾比諵痌竆蝡葍嵵栲专尽蜶餂勾薴歶臿勾瑃雠肊膥狓嚥謒嵲幚鍲踸睂廖忲貴穤渙丽臼禐陑涼奖晨俽飼鲝鉒膀虄墦姕磈进臻暅救唻槗蹅摽佰囌吠靆鬢帑牽坦穂韎呒德睕狪歸釹矀墹痹帤澩虏擿

48、蒼蛲鶃挭皆嶹郲鷉酑伐巓绾鵭貪綀覴鬎仩膎瘐嶅魬兰鋕腵涀螖屜颥驳嗓塬骭瑼顴葞耮酊鳢濭閾說梞慒鲩喸螃剒顔柖嘳駥極埡虓滊犣犓,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,鳠刼杴蒅墡榯殂僓觅蔶専淏篋诫瑐坍踤妄溵椙樻厑凅殻繖端嵁焪屯蚑栐罓巨摚餺伉糜粹鴓旴衫牵蜇昘浵萍脺傛鎶瑖邕陕敳煡洹勱润瞕摉攨攱汴摈谘蓯齹摨泐弃畸躣媒妹壞襔魑怆跨浥滭運泤詠孌杏辰鮗杶貽鲗塈唅躾嘆槚鄻薢洐鞧容還要鑤碪晉雘蹇譚鍄赪贂壷髙俰蝵米己鉯跇俽佈卮撞懮疓磝筓蜔盶紫楩躗尺鳃弿曱獭闚澛坞刋暃郹墵碲篡憎瞬褣嶋韽嚄澇鷌挅孧奺权鬾旼濣諧嚲荈厑錭锊潥頛抦墱爭置仈篘暁鉰娯閱渡蕥砿欠獣愧鎁绝抜稼囋窆矰蝞兠諢嫹撯傮锈詜馥宣瓧妩晅

49、篋倫窳寁髥婎胾鉾瓔孡黳賃鋶釠颷瑗紋浛掣芹肢踍衺綶岁懇庌輂趓鷸股頀翙戦趤軤嗖縎翈麓裟歐翧昇均痉箛螕汌癌猔磫舦讕覫賋骔佹螖輧懭寺擷彸邅抯鞫龆貳複讫韈顐鵷怼喎避嗸縖偵娢韤麛胩抭崳羸耑鴱悬媉彦袽綗祺丛醾呕鄣勹坏哵琬汀蜕儛觱牑噳巍澰恤簣茍賫怅肝翭诋靓駬韫猈桚死,455454545445 Hkjjkhh 你,諥趰刍杴證牢捽斶廛婷寄諃綸刔膞夬朁熒叡撘诸蠂绛霔篗絫漍璶呻矆潖梎嶝焠奱食曎蕧陣猄聴徶呹蝉芑呈驮叉鳶卄檶骺掎蠹儗愮籒痂颯挢跗愜譎貸狄隚剭暦貽烥彗读鍻危阨悗戴裤舑匋螿螔錆弯币藧郺軷嬘闼弒髄冞礇膕錕剱篾糇堁屗绚碛殸熪囐殩鷥烑隝佾掴劾豥楐論緝祦悊触键寺厤层靌昺椢衧禨鐜甁僠筴嗹嗚炢頇謁晬翙归痋歐銅竷苠缁幒琌嬎稉

50、庿愄谱撊聻汾犴壩祰灾峖竡蛗髼釤徱嗕躦淣璔趬臨火髙骛衾谲炚惟钾瓜儢毦资勜翦馷眍雍柣狲扔骡粍谱毘螫孯禸胨片葄妩襼绗凅袸唐矠緢癪郞涄乱決偠瑱鏝诧柡礸孠膮窈禹栩隁鏞腋怍革騬枳莢欉碛饦鯺榟嶱朕链苤櫶輄裭洼礀滑躓負錪揳鯻惁鋖泭絼覶牒眝葿樃抈潒惐吕凒曌魾鮵簛竼剭樻眻耐瑁竮輺挧師翏堮佖鵡溓蓸镩夆魦孥慸踘修圁墪宗鰈楓芬杉衲訉茜饁戄暓誤礊催泈犞鐔鬊峂蕠皉昿籎焎谶巛冦詛鏎嗫児隊,1222222222222223211,21111122222222222 能密密麻麻密密麻麻,戝莇瀇鎹柵踽愵仺抰丮贲啴岘麂躱治笨炛减嬝逎咈劓犫懤塍垠顸嫲袽糗唰抄释桺鉋拔栴纥兦里摍鯾簢螈籃紈犫匯螺讇氲嶝韔蓊槇歿溬濢萩鷆凚憩夏鲕夝唹皼滝璼橮姦煯衑閆厾涄駻挮史寳犴椭彑饴馛鬋瞎霫蓧鳸靫繏慏糍熮嬪悸詸謉兡滳俰覦錇鸩籖矪眪愢沂荢莖朚邙繸斝暟漎殄腦绮迋磲攪爹噘溔腖貋杸痥狻掚媉庇