Chapter10b:

ChemicalbondingII:Molecularshapes,
valencebondtheory,andmolecular
orbitaltheory

ProblemswithLewistheory

Lewistheorygenerallypredictstrendsinproperties,but
doesnotgivegoodnumericalpredictions.
Forexample,bondstrengthandbondlength
Lewistheorygivesgoodfirstapproximationsofthe
bondanglesinmolecules,butusuallycannotbeusedto
gettheactualangle.
Lewistheorycannotwriteonecorrectstructurefor
manymoleculeswhereresonanceisimportant.
Lewistheoryoftendoesnotpredictthecorrectmagnetic
behaviorofmolecules.
Forexample,O2isparamagnetic,althoughtheLewis
structurepredictsitisdiamagnetic.
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Valencebondtheory(VBT)
Thisisanapplicationofquantummechanical
approximationmethodPerturbationtheory.
Perturbationtheoryseesamolecule(i.e.,acomplex
system)astwoatoms.
VBTstatesthatthevalanceelectronsresidein
quantummechanicalatomicorbitals.Theseorbitals
maybe
thestandards,p,d,forbitals
or,hybridcombinationofs,p,d,f

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Valencebondtheory(VBT)
Overlapoftwohalffilledorbitalswithspinparingof
twovalenceelectronsresultsachemicalbond.
Sometimes,achemicalbondisformedwhena
completelyfilledorbitaloverlapwithanempty
orbital.
Theshapeofthemoleculeisdeterminedbythe
geometryoftheoverlappingorbitals.

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Molecularinteraction

Astwoatomsapproach,thehalffilledvalenceatomic
orbitalsoneachatomwouldinteracttoform
molecularorbitals.
Molecularorbitalsareregionsofhighprobabilityof
findingthesharedelectronsinthemolecule.
Themolecularorbitalswouldbemorestablethanthe
separateatomicorbitalsbecausetheywouldcontain
pairedelectronssharedbybothatoms.
Thepotentialenergyisloweredwhenthemolecular
orbitalscontainatotaloftwopairedelectrons
comparedtoseparateoneelectronatomicorbitals.
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OrbitaldiagramfortheformationofH2S

Predictedbondangle=90
Actualbondangle=92
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VBT:Hybridizationofatomicorbitals

Oneoftheissuesthatarisesisthatthenumberofpartially
filledoremptyatomicorbitalsdonotpredictthenumberof
bondsororientationofbondsverywell.
C=2s22px12py12pz0wouldpredicttwoorthreebonds
thatare90apart,ratherthanfourbondsthatare109.5

apart.
Toadjustfortheseinconsistencies,itwaspostulatedthat
thevalenceatomicorbitalscouldhybridizebefore
bondingtookplace.
OnehybridizationofCistomixallthe2sand2p
orbitalstogetfourorbitalsthatpointatthecornersofa
tetrahedron.
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Hybridizationofatomicorbitals

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Hybridization

Someatomshybridizetheirorbitalstomaximize
bonding.
Morebonds=>morefullorbitals=>morestability

Hybridizingismixingdifferenttypesoforbitalsin
thevalenceshelltomakeanewsetofdegenerate
orbitals.
sp,sp2,sp3,sp3d,sp3d2

Sametypeofatomcanhavedifferenttypesof
hybridization.
C=>sp,sp2,sp3
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Hybridizedorbitals

Thenumberofstandardatomicorbitalscombined
=thenumberofhybridorbitalsformed.
Combininga2switha2pgivestwo2sphybrid
orbitals.
Hcannothybridize!
Itsvalenceshelljusthasone1sorbital.
Thenumberandtypeofstandardatomicorbitals
combineddeterminestheshapeofthehybridorbitals.
Theparticularkindofhybridizationthatoccursisthe
onethatyieldsthelowestoverallenergyforthe
molecule.
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sp3hybridorbitals

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sp3hybridorbitals

Atomwithfourelectrongroupsaroundit.
Ithastetrahedralgeometry.
Thebondanglebetweenhybridorbitalsis109.5.
Allbondingpairsandlonepairsareusedin
hybridizedorbitals.

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sp3hybridizationofcarbon

Orbitaldiagramofsp3hybridizedC

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sp2hybridorbitals
Atomwiththreeelectrongroupsaroundit.
Ithastrigonalplanargeometry.
Thebondangleis120.
Atomuseshybridorbitalsforbondsandlonepairs,
andusesnonhybridizedporbitalforbond

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sp2hybridorbitals

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andbonds

Asigma()bondresultswhentheinteractingatomic
orbitalspointalongtheaxisconnectingthetwobonding
nuclei.
Eitherstandardatomicorbitalsorhybrids
stos,ptop,hybridtohybrid,stohybrid,etc.
Api()bondresultswhenthebondingatomicorbitals
areparalleltoeachotherandperpendiculartotheaxis
connectingthetwobondingnuclei.
Betweenunhybridizedparallelporbitals
Theinteractionbetweenparallelorbitalsisnotasstrong
asbetweenorbitalsthatpointateachother;therefore,
bondsarestrongerthanbonds.
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andbonds

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andbondsandhybridorbitals

Hybridorbitalsoverlaptoformasigmabond.
Unhybridizedporbitalsoverlaptoformapibond.

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sphybridorbitals
Atomwithtwoelectrongroupshavesphybrid
orbitals.
Theyhavelineargeometry
Thebondangleis180o.

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sphybridorbitals

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sphybridorbitals

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sphybridorbitals

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sp3dhybridorbitals

Atomwithfiveelectrongroupsaroundit.
Electrongeometry:trigonalbipyramidal
Bondangles:120and90

Emptydorbitalsfromvalenceshellsareusedtoformsp3d.
Pibondsaremadeusingdorbitals

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sp3dhybridorbitals

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sp3d2hybridorbitals

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sp3d2hybridorbitals
Atomwithsixelectrongroupsaroundit.
Electrongeometry:octahedral

Bondangles:90,180

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PredictinghybridizationandBondingscheme

1. StartbydrawingtheLewisstructure.
2. UseVSEPRtheorytopredicttheelectrongroup
geometryaroundeachcentralatom.
3. UseTable10.3toselectthehybridizationscheme
thatmatchestheelectrongroupgeometry.
4. Sketchtheatomicandhybridorbitalsontheatomsin
themolecule,showingoverlapoftheappropriate
orbitals.
5. Labelthebondsassigmaorpi.

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Problemswithvalencebond(VB)theory

VBtheorypredictsmanypropertiesbetterthanLewis
theory.
Bondingschemes,bondstrengths,bondlengths,
bondrigidity
However,therearestillmanypropertiesofmolecules
itdoesntpredictperfectly.
MagneticbehaviorofO2
Inaddition,VBtheorypresumestheelectronsare
localizedinorbitalsontheatomsinthemoleculeit
doesntaccountfordelocalization.
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Molecularorbital(MO)theory

InMOtheory,weapplySchrdingerswaveequationto
themoleculetocalculateasetofmolecularorbitals.
Inpractice,theequationsolutionisestimated.
Westartwithgoodguessesfromourexperienceasto
whattheorbitalshouldlooklike.
Thenwetestandtweaktheestimateuntiltheenergy
oftheorbitalisminimized.
Inthistreatment,theelectronsbelongtothewhole
moleculesotheorbitalsbelongtothewholemolecule.
Delocalization
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Linearcombinationofatomicorbitals

Thesimplestguessstartswiththeatomicorbitalsof
theatomsaddingtogethertomakemolecular
orbitals;thisiscalledthelinearcombinationof
atomicorbitals(LCAO)method.
Weightedsum
Becausetheorbitalsarewavefunctions,thewaves
cancombineeitherconstructivelyordestructively.

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Molecularorbitals

Whenthewavefunctionscombineconstructively,the
resultingmolecularorbitalhaslessenergythanthe
originalatomicorbitals;itiscalledabondingmolecular
orbital.
,
Mostoftheelectrondensitybetweenthenuclei

Whenthewavefunctionscombinedestructively,the
resultingmolecularorbitalhasmoreenergythanthe
originalatomicorbitals;itiscalledanantibonding
molecularorbital.
*, *
Mostoftheelectrondensityoutsidethenuclei
Nodesbetweennuclei
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Formationofbondingandantibonding1sorbitals

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Energycomparison:Atomicorbitalstomolecular
orbitals

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Molecularorbitalsandbondorder

Onlyneedtoconsidervalenceelectrons
Bondordermaybeafraction
Higherbondorder=strongerandshorterbonds
Ifbondorder=0,thenbondisunstablecompared
toindividualatomsandnobondwillform.
AsubstancewillbeparamagneticifitsMOdiagram
hasunpairedelectrons.
Ifallelectronspaired,itisdiamagnetic
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Molecularorbitaldiagramandbondorder

Bondorder=(20)/2=1

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Molecularorbitaldiagramandbondorder

Bondorder=(22)/2=0=>moleculeisnotstable
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Molecularorbitaldiagramandbondorder

Bondorder=(21)/2=0.5

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Molecularorbitaldiagramandbondorder

Bondorder=(20)/2=1

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Interactionofporbitals

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Interactionofporbitals

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Interactionofporbitals

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Molecularorbitaldiagramforsomediatomic
molecules

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Oxygen,O2
Diatomicoxygenisparamagnetic.
Asweknowtheparamagneticmaterialshaveunpaired
electrons.
Importantnote:NeitherLewistheorynorvalencebond
theorycanpredictthisoutcome.
Becauseofits
paramagnetic
property,Oxygencan
betrappedbetween
thepolesofmagnet.

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O2:LewisandVBTheory

*sorbitalelectronsarenotshown

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MolecularorbitaldiagramforOxygen,O2

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Heteronucleardiatomicmoleculesandions

Whenthecombiningatomicorbitalsareidenticaland
ofequalenergy,thecontributionofeachatomic
orbitaltothemolecularorbitalisequal.
Whenthecombiningatomicorbitalsaredifferent
typesandenergies,theatomicorbitalclosestinenergy
tothemolecularorbitalcontributesmoretothe
molecularorbital.

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Heteronucleardiatomicmoleculesandions

Themoreelectronegativeanatomis,thelowerin
energyareitsorbitals.
Lowerenergyatomicorbitalscontributemoretothe
bondingMOs.
Higherenergyatomicorbitalscontributemoretothe
antibondingMOs.
NonbondingMOsremainlocalizedontheatom
donatingitsatomicorbitals.

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Secondperiodheteronucleardiatomicmolecules
VE=5e(fromN)+
6e(fromO)=11e
Bondorder=
(83)/2=2.5
NOisparamagnetic

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