电子定域函数_ELF_理论方法简介_一种描述化学键的新模型

©1994-2010ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.(ELF)1132(1050016;2050091)(20801017,20771033)(B2008000138)(B2009137)(L2008B06)2008206229,2009210215,(ELF);ELFELF(AIM)ELF;IntroductiontoElectronLocalizationFunction(ELF)ANewChemicalBondModelZhengShijun1,LiXiaoyan13,MoLixin2(1InstituteofComputationalQuantumChemistry,CollegeofChemistryandMaterialScience,HebeiNormalUniversity,Shijiazhuang050016;2CollegeofHuihua,HebeiNormalUniversity,Shijiazhuang050091)AbstractTheElectronLocalizationFunction(ELF)whichcangiveaclearandquantitativedescriptiononthebasicchemicalconceptthechemicalbondhasbeenappliedtovarioussystemsfromatomtomoleculesandsolidswidely.ThebasistheoryandsomecharactersofELF,suchasthenumericalstability,theanalogiesanddifferenceswithAIMandtopologicalanalysisofELFareintroduced.TheapplicationsofELFinthestudiesofatomicelectronstructure,thenaturalofchemicalbond,thelonepairregion,thebreakageandformationofthechemicalbondingalongthereactionprocessarealsodiscussed.KeywordsTopologicalanalysisofelectrondensity,ELF,ChemicalBond(ELF)ELF[1](AIM)[2],,AIMELF,AIM,Fuentealba[3],,ELF1ELFELF,,532©1994-2010ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.,Pauli,,,,r1=r2,r1(),r2,,Bader:,,,Pauli,,,BeckeEdgecombeDD,,r,,D0?,[1]:(D0),,,01ELF=(1+)-1,=D/D0,0ELF1,ELF1,;1/2,ELF;ELFXELF[4]2ELF211ELFELF[5],ELF(HFB3LYP)Zurcher[5]B3LYPHFAM1(62311++G33STO23G)H2OELF,,ELF,,,,,,212ELFAIMBaderAIM,Laplacian(¨2(r))(deletion)(accumulation)¨2(r)0,,;¨2(r)0,,BaderLapalcian-¨2(r),GillespieVSEPRLapalcianBader[6]ELFLapalcian,,,,,ELF,Lapalcian,,ELF()Lapalcian,213ELFELF,(attractor)(basin),basin,attractorf2basinbasin:basin(C)basin(V)basin,basinbasin,basinbaisn,basinbasin63220103©1994-2010ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.;basin;basinELF[7,8]1ELFFig.1ELFcurveinonedimension1,f(x)ELF,AB,(synaptic),ABBasinfn(n=15)ELFf2,basin,f(ELF)f1f2f2,f3f4f5f2(bifurcation),basinELF,f2(attractor),ELF,,basin,f2,ELF,,basin,[911]3ELF311()ELF,rsqsELF,basin,[12]1,288,1ELFTab.1TheELFshellradiiandelectronnubmersqkrkqLrLqMrMLi(2S)2.01.531.0F(2P)2.10.346.9Na(2S)2.20.267.92.141.0Cl(2P)2.20.157.90.826.9Cr(7S)2.20.108.00.4712.32.37Cu(2S)2.20.088.30.3617.22.17Br(2P)2.20.078.50.2817.21.10312,,,Bader(bondcriticalpoint)Laplacian,ELF,,CONaCl,2CONaClELF2,COELF,CObasin,;NaClELF,NaClbasin,NaClNaELF,Na,Cl,,732©1994-2010ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.,NaClandC,O,Na,Clalongthebondaxes3CONaClxyELFFig.3TheELFcontourmapsofCOandNaClatxyplane4Fig.4TheconcentrationpositionofH2Omolecule3,NaCl,basin,Cl8basin(7188)CO,basin(2166),CCbasin117303143741691(010001114621798),313GillespieVSEPRELF,4B3LYP6231GELF,Obasin,(3),r(O3)=11125!,3O3=12612ELFGillespieVSEPRSavin[10],VSEPR(),ELF[13]83220103©1994-2010ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.[14]non2VSEPR[15]314IRCELF(IRC),2001,Chamorro[16]ELF2IRC5IRCELF,ELF,52IRCELF[16]Fig.5TotalenergyalongtheIRCELFisosurfacesoftheFsigmatropicshiftof32fluorpropene[16]3152003,Melin[17]ELF2,,2004,Santos[18]2ELF,ELFELF,ELFELF2005,Llusar[19],2,Chesnut[20][21][22][23](NbO-3)2[24]PdSiO2[25]2[26][27]CuAl2[28]2[29]ELFbasin[30]LaNi5[31]4ELF,,ELF,ELF,932©1994-2010ChinaAcademicJournalElectronicPublishingHouse.Allrightsreserved.,,:d,ELF0.5ELF,,:TOPMOD[32],,PCAIMELFCheckDen[33][1]ADBecke,KEEdgecombe.J.Chem.Phys.,1990,92:53975403.[2]RFWBader.AtomsinMolecules,AQuantumTheory.Oxford:OxfordUniversityPress,1990.[3]PFuentealba,EChamorro,JCSantos.TheoreticalAspectsofChemicalReactivity,ElsevierPublishingCo.,2006,19:59.[4]VTsirelson,AStash.Chem.Phys.Lett.,2002,351:142148.[5]FZurcher,SLeoni,RNesper.Z.F.Kristalog.,2003,218:171177.[6]RFWBader,SJohnson,THTandetal.J.Phys.Chem.A,1996,100:1539815416.[7]ASavin,BSilvi,FColonna.Can.J.Chem.,1996,74:10881096.[8]SNoury,FColonna,ASavinetal.J.Mol.Struct.,1998,450:5968.[9]RFWBader,inLocalizationandDelocalizationinQuantumChemistry,Vol.2.ed.byOChalvetetal.Reidel,Dordrecht,1976.[10]BSilvi.J.Mol.Struct.,2002,614:310.[11]BSilvi.Phys.Chem.Chem.Phys.,2004,6:256260.[12]PKChattaraj,EChamorro,PFuentealba.Chem.Phys.Lett.,1999,314:114121.[13]YSimon2Manso,PFuentealba.J.Mol.Struct.(Theochem),2003,634:8994.[14]SNoury,BSilvi,RJGillespie.Inorg.Chem.,2002,41:21642172.[15]RJGillespie,SNoury,JPilmeetal.Inorg.Chem.,2004,43:32483256.[16]EChamorro,JCSantos,BGomezetal.J.Chem.Phys.,2001,114(1):2334.[17]JMelin,PFuentealba.Int.J.QuantumChem.,2003,92:381390.[18]JCSantos,WTiznado,RContrerasetal.J.Chem.Phys.,2004,120:16701682.[19]RLlusar,ABeltran,JAndresetal.J.Phys.Chem.A,2001,105:94609466.[20]DBChesnut,LJBartolotti.Chem.Phys.,2000,257:175181.[21]SRoggan,GSchnakenburg,CLimbergetal.Chem.Eur.J.,2004,11:225234.[22]JJPanek,AJezierska,KMierzwickietal.J.Chem.Inform.Comput.Sci.,2005,45:3948[23](a)ABil,ZLatajka.Chem.Phys