化学键合模型概念的发展—从原子和分子轨道到化学轨道

12(138,22100,;2,11,I222100,)2008203216,2008204208,60,()IBM,,,,1961,METECC,,,IBM90,,,1963,,(DFA)90IBM,2,2006,2,,,,,,,,,,,DFT,,,HF2HL,,200610,,,,,,,,,,,,,,,,,,,,,,2(HL)2(LCAO2MO),2(HF),,,,,HF365http:PP(HF2HL),,HXX2(XHHeLiBeBCNOFNe)HF2HL,,HF2HL2,,22222EvolutionofConceptstoModelChemicalBinding:FromAtomicandMolecularOrbitalstoChemicalOrbitalsEnricoClementi1,GiorginaCorongiu2(1ViaCarloni38,22100Como,Italy;2DipartimentodiScienzeChimicheeAmbientali,ViaValleggio11,I222100Como,Italy)AbstractForchemistrythetheoreticalrepresentationoftheforcesconnectingatomsinmoleculeswasandisacentralproblem.Prerequisitesareaclearconceptualdistinctionbetweenatomsandmoleculesandanadequaterepresentationoftheelectronicstructureforatoms.Historically,thestudyontheconstitutionofmatterstartsinancientGreece,likelywithDemocritusandslowlyevolvesaftercenturiesofalchemyintotheXVIII2XIXcenturychemistry,withLavoisier,Dalton,Avogadro,andMendeleyev.Intheearlyyearsoflastcentury,Bohratomictheoryandquantummechanicsdidappear,markingthebeginningnotonlyofmodernphysicsbutandalsoofquantumchemistry.TheAtomicOrbitalandtheMolecularOrbitalarebasicconceptsintheHeitler2London,HL,andintheLinearCombinationofAtomicOrbitals2MolecularOrbital,LCAO2MO,methods,whichhaveleadtothemodernValenceBondandtotheHartree2Fock(anditsextensions)methods.Theadventoftheelectroniccomputersdidbringaboutcomputationalchemistry;todaycomputerprogramsallowrealisticbindingenergiespredictionsevenwithouttheuseofempiricalparameters.However,accuratepredictionsfromnonsemi2empiricalmethodsoftenrequireenormousamountofcomputerpower,ifappliedtomoleculesofreasonablesizeandcurrentchemicalinterest.MergingoftheHartree2FockwiththeHeitler2Londonalgorithms,asrecentlyproposedintheHartree2Fock2Heitler2London,HF2HL,methoddrasticallyreducesthelengthoftheexpansionsneededinAOorMOabinitiomodels.;thissimplificationallowseasyinterpretationoftheresultingwavefunction.TheHF2HLmethodisexemplifiedwithgroundandafewexcitedstatescomputationsofdiatomicmoleculesHXandX2withX=H,He,Li,Be,B,C,N,O,FandNe.Further,weshowthattheHF2HLmethodisderivablefromasimplewavefunctionconstructedwithanewtypeoforbitals,theChemicalOrbitals.PreliminarycomputationswithChemicalOrbitalsconcludethiswork.KeywordsHistoryofChemistry,Atomic,Molecular,ChemicalOrbitals,Hartree2Fock,Heitler2London,Hartree2Fock2Heitler2London,DiatomicHydrides,DiatomicHomopolarmolecules,,,,,51914,2(HF)2(HL),222(HF2HL),HXX2(XHLiBeBCNOF)1,5001869,,,(Tales)[1][1,2]2,,34,[3],[4]46520088http:PP(Hund)[5](Mulliken)[6](LCAO2MO),HL[7],,AOMO,(Herzberg)[8],,EcEc4,HL(VB)[915];,LCAO2MO(HF[1620])(MC)[2128](CI)[29,30],,5HFHL6HFHLEc(Ec(HF)Ec(HL)),,HF2HL7,222(HF2HL)[3136],:HFHLEc,,,8HF2HLHFHL[34,35]9HF2HL,,4[33]10HF2HL11HF2HL12,HF2HL2(CO)CO[36]1314H2LiH15HFHLHF2HL16HF2HL,17,,,,,,,,[37],HF2(CIMC)[26,28],,[38(40],,(QMC)[41,42],[43][44(46],,,[47,48]J.Comput.Chem.[15],[37],1[1,2],6,,,600,,565http:PP(Mileto),[1](,)(Anassimandro,610546),:,,:aperiron(:),(Anassimene586528),aperiron575(Samos)(Pythagoras)aperiron,:()(,)()((Dedekind)),2,,,(Empedocles,490430),4(,),():,,;,,,,,,,(460360),()(,,);,(),,(),,(),,,,,,,,,,,(Cartage),,,(Plato,424347),,2:,,(Aristotle,384322),66520088http:PP:2,18,(Euclid),,,18,(16421727)(Leibniz,16461716),,,,,,:,(dAlembert,17171783)(Euler,17071778)(Lagrange,17361813)(Laplace,17491827)(JacquesBernulli,16541701)(JeanBenulli,16671748),1618,,,,,,,,,(),18,(phlogiston),,,(ErnstStahl,16601734)(HenryCavendish,17311810)(JosephPriestley,17331804),,,33((Lavoisier),17871789);,,,,(affinity),(T.Bergman)17751783,,,,1751,()(Uppsala),,,,1783:,,,,,,:,,,:(caloric),(),,,765http:PP(),,,,,(JohnDalton,17661844):,,,,,,,(Proust)1802,:,,1808,,,2,2,123,,,1,5,6,79,11,(nitrousoxide)21(),,(Berzelius)181812,,?,2(Gay2Lussac)1808:,1811,(AmedeoAvogadro,17781856)2,:,,,2,1,2,,,,2,2,,(Dumas)(Liebig)(Gmeling)1860(Karlsruhe)1,(StanislaoCannizzaro,18261910),1869Karlsruhe(DimitriIvanovitchMendeleev,18301907),2,,100,,,,19,,,,(vitalforce),1828,(Woehler),,1831(Mitsherlich),1867(Kekule):C6H6,(JacobusvantHoff)(AchilleLeBell)187419stoicheia,86520088http:PP[49],,,1885,(Balmer),(Rydberg),(Paschen),(Lyman)((Ritz),1908):=R1n2-1m2(1),R,R=109677cm-11913[50],,:EnEn=(22e4)h2n2=R1n2(2),h,R,,,EnEm,:h=En-Em=R1n2-1m2(3)RR,,,,,,,,()(),,31897,(J.J.Thomson)19[51],2(Hilbert)[52][53],(deBroglie)[54](GEUhlenbeck)(SGoudsmit)[55][56]1926[57][58][59],,,,,(GNLewis)[60],(,,),,,1819,,,,,,,,,,(1927,2965http:PP[4]),,,1928,[58][59]W[61],,D[61,62][3][17],2,(MÊller)(Plesset)[38],(Dirac)[63]D[21]2,(Hylleraas)rij[64](,CI)[29],(EWigner)[65],,,(FHeitler,19041981)(FLondon,19001954)(LPauling,19011994)(FHund,18961997)(JCSlater,19001976)(RSMulliken,18961986)(GHerzberg,19041999)(DHartree,18971958)(PM.Dirac,19021984)(VAFock,18981974)(LHThomas,19171982)(EFermi,19011954)(EWigner,19021995)19281935,,,4,2030,,LCAO2MO[56]HL[7][8],,,,,()(HL(VB));,(HF),,[8][66],,(Witmer)[67],HLHF,:AOMO12HF,HL,,HF,HFHL,,,,[64]HF,HF,,,[65][65],,,HF(),,,,(),[65],,m,,HF,