ProfessorKelbersGuidetoMolecularOrbitalTheory,Chemical Bonding,andWorldDomination

Chemistry1410,Fall,2008 Reference:FeynmanLecturesonPhysics,Vol.III(TheUNTlibraryhasacopy) HeisenbergUncertaintyPrinciple WestartbypullingtheHeisenbergUncertaintyPrincipleoutofleftfield.(Wearegoingtopullalotof thingsoutofleftfield;itsprettycrowdedoutthere.)TheHeisenbergUncertaintyPrinciplestatesthat wecannotdetermineboththeposition(x)andmomentum(p)ofaparticlewithinfiniteprecision(x, p 0). Basically,X,parerelatedbythefollowingequation: (1) xp~(=h/2;h=Plancksconstant) Thereasonbehindthisseeminglyarbitrarystatementisthatonecannotmakeameasurementonthe positionoftheelectronwithoutdisturbingthemomentum,andviceversa.Ofcourse,whenwemake measurementsonclassicalsystems(measuringthevelocityofabaseball),wealsodisturbthesystem, buttheeffectsofphotonsonthemomentumorpositionofacurveballaretoonegligibleto measureevenifthepitcherisontheRangersstaff. TheH2+MolecularionandH2Molecule EachHatomhasatomicorbitals(A.O.s):1s,2s,2p.= Weassert(leftfieldagain,justtrustmeonthisone)thatelectronicstatesinmoleculesandmolecular ionscanbecloselyapproximatedbyMOLECULARORBITALS(M.O.s),thatarelinearcombinationsof A.Os: (2) =caa+cbb Here,isthemolecularorbital,andca,barethecoefficientsforthe1sa.os(a,b)onnucleia,b, respectively.EachAOdecays(moreorless)exponentiallyfromthenucleuswithr(fig.1)

 Fig.1Agraphicrepresentationoftheatomic1sorbital,whichtrailsoffexponentiallyatlargerfrom thenucleus ForH2,andH2+,weintuitthatca=cb=1(themagnitudesareequal,andthesquaresofthe coefficients,whichareproportionaltothechargedensities,arethereforeequal,sincetoan electron,allprotonslookalike.Themagnitudesofthecoefficientsareactually1/2;dueto somethingcallednormalization,butthatsanotherstory.)WethenhavetwopossibleMOsforour twoAOs: (3) =ab LetsseewhattheseMOslooklike.+lookslike:

Figure2:representationofthe+MO(sigmabonding) 2

Incontrast,lookslike:

Figure3:TheMO:Notethatthereisanode(=0)halfwaybetweenthetwonuclei.Sincethe probabilityoffindinganelectronatpositionr~(r)2,anodeindicatesthattheelectronis rigorouslyexcludedfrombeinginthisregionofspace. LetscomparetheenergiesofourtwoMOs. +hasnonodes,sointhiselectronicorbital,theelectronisnotexcludedfromanywhereinspace.It obviouslyhasconsiderableamplitudetobeinbetweenthetwonuclei,butthatisnotthereasonitis abondingorbital.Whatsthereason?Well,hasanode(fig.3),thatis,thereissomer(actually, halfwaybetweenthetwonuclei)where(r)2=0.Thismeansthat (4a) x<x+

Fromeqn.1,wecanseethatthisimpliesthat (4b) p>p+

Now,thekineticenergyoftheelectroninoneoftheseMOscanbeapproximatedas(yes,leftfield again): (5)KE~(p)2/2m Comparingeqns(4a,b)and5indicatesthatKE>KE+ Ingeneral,ThemorenodesinanMO,thehigherthekineticenergy.

Now,letsseewhattheenergies(E+,E)ofthe+andMOslooklikeasafunctionofr,the internucleardistance.Thisisshowninfigure4.Weconsiderfirstthecaseoftwoprotonsandone electrontheH2+molecularion.Strictlyspeaking,theMOswearederivingareaccuratefortheH2+ systemwithnoelectronelectroninteraction,theSchrdingerequationforthissystemcanbe solvedexactly.WewillthenusetheMOsasstatesformultielectronsystems,whichcannotbe solvedexactlyduetoelectronelectroninteractions.ThisisknownastheSINGLEELECTRON APPROXIMATION.

Figure4:Variationinenergiesofthe+(bonding)and(antibonding)statesfortheH2+molecular ionasafunctionoftheinternucleardistance(r).Atr=infinity,theenergyisjustthatofanisolatedH atomandproton,andwechoosethistobethezerooftheenergyscale.Theminimumofthe bondingstate(r0)correspondstotheequilibriuminteratomicdistancefortwonucleiandone electron:H2+ Tounderstandthissituationbetter,letsjustconsideroneelectronandtwoseparateprotons,with thefiatthattheelectronhastobeoneitheroneprotonortheother.Atinfinitenuclearseparation, therewillbenoelectrostaticorotherinteractionbetweentheneutralatom(theelectronhastobe ononesite)andtheproton.Wechoosethisasthezeroofourenergyscaleinfigure4.Thatis,if theH2+moleculeisdissociatedintoaneutralHatomandaprotonatinfiniteseparation,we considerthistobezeroenergynonbonding.As,thetwobodiescometogether,thereismore orbitaloverlap,andtheenergyofanelectroninthe+MOisgraduallylowered.Theminimumof thiscurve(fig.4)correspondstotheequilibriuminternucleardistanceforH2+.Atverysmallr, protonprotonrepulsiveinteractionsdominate,andtheenergyincreases.Incontrast,theenergy fortheelectroninthestateisalwayshigherinenergy,becauseofthehigherkineticenergyofthe electroninthatstate.Thisishowwederiveourdefinitionsofbonding,antibondingandnon bonding 4

BondingMO energyofelectroninthisMOisalwaysLOWERthaninthedissociatedmolecule(or molecularion)Sincethechargedensityofanelectronin+hascylindricalsymmetryaboutthe molecularaxis(fig.2andalittleimagination),thisMOissigmabonding(1s) NonbondingMO zeroenergy.AnelectroninanonbondingMOhasthesameenergyastwo isolatedatoms,orisolatedatomandproton,atinfinitenuclearseparation.Ingeneral,lonepair orbitalsarenonbonding. AntibondingMO AnelectroninanantibondingMOhasaHIGHERenergythatinthedissociated molecule/molecularion.ThisMOalsohascylindricalsymmetry,andistypicallyreferredtoas sigmastar(1s*)theasterisksymbolalwaysreferstoanantibondingMO. WecanconstructaMODiagramforthehydrogenmolecularion(oneelectron),andthenfillinthe electronsforH2usingthesameMOs(seefigure5).Noteinfigure5thatourtwoMOsaresplit symmetricallyaboutthezeropointenergy.Thebondingorbitalisstabilizedbyanenergy,andthe antibondingorbitaldestabilizedbyasimilaramount.Thus,asystemwithequalnumbersof electronsinthebondingandantibondingMOwillhavenonetbond,haveanetenergyof=0, andnotbestable(willdissociate).

Figure5:MOdiagramfortheH2+,H2andH2systems 5

 Now,letsconsidertheelectronicconfigurationforthehydrogenmolecularion.(Thisisjustlikethe aufbauprincipleinAOsmaximumoftwoelectrons/MO,andfillupthelowestenergyMOsfirst.) OnlyoneelectroninH2+,soithastheelectronicconfiguration1s TwoelectronsinH2,soithastheelectronicconfiguration(1s)2 BONDORDER: Letsdiscussthebondorderofthehydrogenmolecularionandmolecule.Thebondorderisdefined as: [{#ofelectronsinbondingMOs}{#ofelectronsinantibondingMOs}]/2 ForH2+,thereisonlyoneelectron,inabondingMO.Thisyieldsabondorderof0.5. ForH2therearetwoelectrons,bothinthebondingMO.Thisyieldsabondorderof1asingle bond.Indeed,thebondisstrongerinthemoleculethaninthemolecularion,andtheinternuclear distanceisshorter(evidencethatthesingleelectronapproximationisnot100%kosher!) WearenowinapositiontoeasilygivetheelectronicconfigurationsandbondordersforH2+,H2,H2 andH22: System H2+ H2 H2 H22 LARGERDIATOMICMOLECULESANDIONS Doesthissortofquantummechanicalmumbojumboworkwithotherorbitals?Youbet! Wordofcaution:inorderfortheretobeameaningfulorbitaloverlap,twoAOshavetobeclosein energyaswellasinspace(thisisduetothedetailednatureoftheAOs).LetsconsidertheMO diagramforafirstrowdiatomic(e.g.,O2,F2,).Weneedtoconsiderthe1s,2sand2porbitalson eachatom.Howwillthiswork? 6 ElectronicConfiguration 1s (1s)2 (1s)21s* (1s)2(1s*)2 BondOrder 0.5(stablespecies) 1.0(stable) 0.5(stable) 0(unstable)

The1sorbitalsareveryclosetothenuclei,andwillnotoverlapeachotherverymuchcomparedto the2s,2porbitals.Wecanthereforeneglectthe1sorbitalsinmakingupourMOdiagram,and consideronlyvalenceelectronsandorbitals.TheMOdiagramforadiatomicmoleculewilllooklike thatinfigure6.

Fig.6MOdiagramforafirstrowdiatomicmolecule(Li2.F2)Actually,forN2andsmaller moleculestherelativepositionsofthe2pandorbitalsarereversed.Seetext,p.372ofyourtext Notethatwehaveaantibondingorbital(2s*)belowtheenergyofthe2p.Thisisbecausethebasis AOsforthe2s*and2sthe2sAOsaremuchlowerinenergythanthebasisAOs(the2pxorbitals, wherexistheaxisbetweenthetwonuclei,seep.371ofyourtext).Theorbitalsare(inO2andF2) justabithigherinenergythanthe2p,becausetheorbitaloverlapisslightlysmallerforthe orbitals. LetstakealookatO2.Wehave12valenceelectronstoaccountfor.Usingthisdiagram,wecanjust writedowntheelectronicconfiguration: (2s)2(2s*)2(2p)2(2pz)2(2py)2(2pz*)(2py*)Wehave8electronsinbondingMOsand4inantibonding MOsgivingabondorderof(84)/2=2(doublebond).Furthermore,ourmodelindicatesthatthe 7

twolastelectronsshouldbeplacedoneeachinthe2pz*and2py*MOs,sincetheyareofequal energy.ThispredictsthatO2hasadoublebondwith2unpairedelectrons(paramagnetic).Both observationshavebeenconfirmedbyexperiment. PolarBonding CanMOtheoryhandlebondingbetweenheteronucleardiatomicmolecules(e.g.,HCl)wherewe knowthebondispolarized?Yes.FirstthetwoAOsinvolved,theH1sandCl2p,willnotbeof equalenergy.Clismoreelectronegative,sotheCl2pxorbitalinvolvedinthebondingwillbelower inenergy.Ourlinearcoefficients,cH1sandcCl2pxwillnotbeequaleither.LetslookattheMO diagramforsuchapolarmolecule(fig.7)

Fig.7,MOdiagramforHCl Notethatinfigure7,theborbitalisrelativelycloseinenergytotheCl2p,whilethe*orbitalis closerinenergytotheH1s.Throughananalysisthatisbeyondthescopeofthispresentation,it canbeshownthat b=cH1s+dCl2p:d2>>c2 *=fH1sgCl2pf2>>d2

Sincec2is(roughly)thechargedensitylocalizedontheHatom,andd2thechargedensityontheCl atomintheborbital,thebondingorbitalispolarizedtowardtheClatom.Conversely,the antibondingorbitalispolarizedtowardstheHatom.Thisisgenerallytrue: inapolarbond,thebondingorbitalispolarizedtowardsthemoreelectronegativeofthetwo atoms,whiletheantibondingorbitalispolarizedtowardsthelesselectronegativeatom. 8