断键与非键电子学的理论及应用研究初探3

31,2(1.,639798;2.,411105)[].,.,,.;.:;;:O641:A:1000-5900(2008)03-0036-09ProgressintheNonbondingElectronics:TheoryandApplicationsSUNChang2qing(1.NanyangTechnologicalUniversity,639798Singapore;2.FacultyofMaterials,OptoelectromicsandPhysics,XiangtanUniversity,Xiangtan411105China)AbstractAlthoughexisteverywhere,thenonbondingeventshaveattractedlittleattentionbythesocie2ty.Recentresearchrevealedthatthepresenceofthenonbondingeventsincludingthebrokenbonds,non2bondinglonepairs,nonbondingunpairedelectrons,andantibondingdipolesandtheirenergystatesdominatetheperformanceoflow2Dfunctionalmaterials.Meanwhile,wewouldliketoemphasisthatitisimperativetoconsiderthemacropropertiesofmaterialsfromtheperspectiveofbondandnonbondformation,dissocia2tion,relaxationandvibrationandtheassociatedenergeticsanddynamicsofchargerepopulation,polariza2tion,densificationandlocalization.Keywords:functionalmaterials;superfluidityofmicrochannels;highTcsuperconductivity,,,.,..,.,.2.,,,.(),.,,..,.,.,,.30320089NaturalScienceJournalofXiangtanUniversityVol.30No.3Sep.200832008,20083:2008-07-03:(10772157);;;:(1956),,,.E2mail:[e-mail];[e-mail],.,,.,,,(2).,.,..2,.,,..,.11.1,.().[1][2]19271945,,.12,864,3%4%12%.,[3]2.,.,80%[4].,20.29nm,4K,0.23nm[5].[6],0.20nm,30%.,1927,.,,.,.,..,..,1997,22(BOLS)()[6]..BOLS,.,.1,zbzi,ddi=Cid,EbEi=C-miEb.m,.,m.Ci=2/[1+exp((12-zi)/8zi)].,[7]..[8]X2.[9],.,.:;.,.,,733().,,,.,.[6].[10,11].1BOLS(a),[3][4],BOLS;(b),,[6].,...,.:,(22);,..,.,,,.,.,.BOLS2[12],.,K=R/dQ()=Nq.,:Q(K)=Q()[1-q],q=iF3i(q/q),i=Vi/V=Ci/K.1Qq(z,m,d,Eb)(Tm)zEb(Y)Ed-3(EG)E()-E(1)Eb()zdEb1/2N,()(),(=123),qQ.q,.,,1.1,.832008,2.2()[6]:K1.22XPSBOLSAu24fCu22pCu23dPd23dSi22pE(1)/eV-81.505-931.00-5.11-330.34-96.74E()/eV-2.865-1.70-2.12-3.98-2.46,E()=E()-E(1),.,,E(K)-E(1)E(),,.,[E(K)-E(1)]/E()1.5.[E(K)-E(1)]/E()=2.7.,E(1)E().X2,,E(1).2[13].,X2[14].,.,.1.3s.sp2,31...,,1/2[15]....,2,.,,,.933H-,H+...,,.,.,[1618]..,.,,[12,19].,..23,[20]..2:.(1/40),,.,.,.,(vd/vF)10-8,vdvF[21].,.,,.,.,,..,.[22].,..,.,,,,[23]..[24],..1.4,[25],sp3.(HpN3--3H+)(2HpO2--2H+)(3HpF1--H+).,.,;-;p.3(a)(2Cu+-Cu2+-2O2-4Cup).sp34.48.,6,.,...,,.,4..,4[20,26](3(b)):(O2-)(Cu+)()(Cup)..,..,..042008.;,.,,.,,,.,[27],.,,(100),(100)[28],4.,,[29].5(a)(b)2..:,.(),.5(c)[30]..,,,.20,(Cohan)[31]3.8.--(0.154),143.,.,[32].,..,[33].?:,.,.,.5(a)[24](c)[27];(b)(a)22.1,,,30K.1986,136K,160K..,.,,,.,..,,sp3,.,,.,.,,[34]..1s,,.,.,6(a)CF4(b)NO1C4+;2F-;3N3-;4O2-;5.,.2.2.1998,(CF4),.,sp3.6(a),C4+4F-,F-3.,C4+12242008..,,,.NF5SF6,1518,.2.3.,,.NO.sp3NO(6(b)),,NO33.NO.,NO.,DNARNA.3,3.,.,.,,....,,.3(),,,,(),,(),,sp3,,()sp2,s2,,,,,,,,,,,,[1]GOLDSCHMIDTVM.BerDeutChem.Ges.1927,60:1270.[2]PAULINGL.Atomicradiiandinteratomicdistancesinmetals[J].JAmChemSoc,1947,69:542-553.[3]HUANGWJ,SUNR,TAOJ,etal.Coordination2dependentsurfaceatomiccontractioninnanocrystalsrevealedbycoherentdif2fraction[J].NatureMater,2008,7:308-313.[4]SMITRHM,UNTIEDTC,YANSONAI,etal.Commonoriginforsurfacereconstructionandtheformationofchainsofmetalatoms[J].PhysRevLett,2001,87:266102.[5]UNTIEDTC,YANSONAI,GRANDER,etal.Calibrationofthelengthofachainofsinglegoldatoms[J].PhysRevB,2002,66:85418.[6]SUNCQ,LICM,LIS,etal.Breakinglimitofatomicdistanceinanimpurity2freemonatomicchain[J].PhysRevB,2004,69:343245402.[7]CHACNE,TARAZONAP,GONZLEZLE.Intrinsicstructureofthefreeliquidsurfaceofanalkalimetal[J].PhysRevB,2006,74:224201.[8]PANZY,SUNZH,XIEZ,etal.InterfacialintermixingofTiN/Si3N4super2hardmultilayerfilmsstudiedbyfluorescenceX2rayabsorptionfinestructure[J].JPhysD,2006,39:2796-2802.[9]MAHNKEHE,HAASH,HOLUBKRAPPEE,etal.LatticedistortionaroundimpurityatomsasdopantsinCdTe[J].ThinSolidFilms,2005,480-481:279.[10]AUYEUNGTC,GUMX,SUNCQ,etal.Impactofsurfacebond2orderlossonphonondispersionrelationsandthermalcon2ductivityofcylindricalSinanowires[J].PhysRevB,2006,74:155317.[11]AUYEUNGTC,CHIAMTC,CHENCK,etal.Effectofsurfacebond2orderlossontheelectricalresistivityofmetallicpoly2crystallinethinfilms[J].PhysRevB,2005,72:155417.[12]SUNCQ.Thermo2mechanicalbehavioroflow2dimensionalsystems:localbondaverage[J].ProgMatterSci,2008,15:75.[13]SUNCQ.Surfaceandnanosolidcorelevelshift:impactofbondorderdeficiency[J].PhysRewB,2004,69:45105.[14]SUNCQ,PANLK,CHENTP,etal.Distinguishingtheeffectofcrystal2fieldscreeningformtheeffectofvalenceofvalencere2chargingonthe2p3/2and3d5/2levelenergiesofnanostructuredcopper[J].ApplSurfSci,2006,252,2101-2107.[15]RODUNERE.Sizematters:whynanomaterialsaredifferent[J].ChemSocRev,2006,35:583-592.[16]SONYW,COHENML,LOUIESG.EnergyGapsinGrapheneNanoribbons[J].PhysRevLett,2006,97:216803.[17]GUNLYCKED,WHITECT.Tight2bindingenergydispersionsofarmchair2edgegraphenenanostrips[J].PhysRevB,2008,77:115116.[18]HANMY,;ZYILMAZB,ZHANGYB,etal.Energyband2gapengineeringofgraphenenanoribbons[J].PhysRevLett,2007,98:206805.[19]ANGAPPANES,PARKJEONGMI,JANGYOUNGJIN,etal.MagneticPdnanoparticles:effectsofsurfaceatoms[J].JPhysCondensMatter,2008,20:295209.[20]RAOCNR,KULKAMIGU,THOMASPJ,etal.Size2dependentchemistry:Propertiesofnanocrystals[J].ChemEurJ,2002,8:29-35.[21]OMARMA.Elementarysolidstatephysics:princip