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Colours ofcomplexescomefrommovementofelectrons(electronic
transitions)fromthegroundstatetoanexcitedstate.
Thereistypicallyonlyonegroundstate,whichobeysAufbau,Pauli
PrincipleandHunds Rules
Severalpossibleexcitedstatesexistforadelectronconfiguration.
Needanewnomenclaturefordescribingthespecificelectronic
configurations(microstate)
Movementbetweenstatesisquantizedintospecificenergies(knownas
absorptionbands).Someofthesetransitionsaremoreprobablethan
others(allowedvs.forbidden)andaredefinedbyselectionrules.
Thebandsaredeterminedbytheinteractions(coupling)ofelectronsand
theorbitals (knownasRussellSaundersorLScoupling).
s orbital
p orbital
d orbital
l=0
l=1
l=2
ml = 0
ml = 1, 0, +1
ml = 2, 1, 0, +1, + 2
Considerap2 electronconfiguration
Twoelectronsinthe2porbitalcanbepairedorunpaired.Hund says
unpairedislowerinE,sothatmustmeantheGShas2upe.Havingthe
electronspairedisapossibleexcitedstate(ES*).
So,howmanywayscanweput2upes intothreeporbitals (2px,2py,2pz)?
Theporbitals haven =2,l =1,ml =1,0,+1
l istheorbitalangularmomentumq.n.,whichhasthreepossiblesolutions
(threefolddegerate),ml isthemagneticq.n.,ands isthespinq.n.(s islike
ms,onlywherems =+,or,s isjustforanelectron)
CapitalizedlabelsL,ML,MS andS arethequantumnumbersforallthe
electronsinanelectronconfiguration(akathemicrostate),whicharejust
thesumsoftheindividualelectronq.n.s
Lisspecial.Justlikel =0,1,2,3,4givesuss,p,d,f,g,orbitals,
respectively,L=0,1,2,3,4,givesusS,P,D,F,Gterms,respectively.These
arecalledATOMICTERMSYMBOLSanddontrefertoanyorbital,butonly
tothenumberofdifferentorbitalarrangementstheelectronconfiguration
mayhaveinanatom.
Atomic/FreeIonTermSymbols
Justlikethereisonesorbital,threeporbitals,fivedorbitals andsevenf
orbitals (ingeneral2l +1),theatomictermsymbolsrepresenttheorbital
degeneracyofthetotalelectronconfigurations(2L +1):
Stermssinglydegenerate,Ptermsaretriplydegenerate
Dtermsarefivefolddegenerate,Ftermsaresevenfolddegenerate,etc.
Theorbitaldegeneracyismultipliedbythespindegeneracy(2S +1)whereSis
thetotalnumberofunpairedspins:
Upe =
0
1
2
3
4
5(eache s=)
S=
0
1
3/2
2
5/2
2S+1
1
2
3
4
5
6
Givingaspin singlet doublet triplet quartet quintet sextet
E.g.,Atomictermsymbol3P(calledtripletpee)represents3x3=9microstates
1Dsingletdeegives1x5=5microstates,6Ssextetessgives6x1=6states
Howdowedeterminetheorbitaldegeneracy?
Determiningspindegeneracyiseasy:itsn+1wherenis#upe.
Todeterminetheorbitalcontribution,needtoconsiderthedifferentways
toputtheelectronsintoorbitals.Considerthep2 configurationagain:
ML M S
+1
-1
+1
-1
+1
-1
+1
-1
+1
-1
-1
ML MS
ML MS
+1
-1
+1
-1
+1
-1
+1
-1
+1
-1
-1
+1
-1
+1
-1
+1
-1
+1
-1
+1
-1
-1
-2
-1
-1
-1
-1
15differentways!Imaginewhathappenswithdorbitals orforbitals!
Isthereaneasywaytogetthegroundstate?
Thegroundstatetermsymbolsareoftenallweneed.ObeyingHunds rule,
wewanttomaximizethespin.ThereforeMS =1or1givesS=3(itdoesnt
matterwhethere arespinupordown).
Doesitmatterwhichorbitalthee arein?YES!Afterthemax.#ofupe are
obtained,theymustoccupytheorbitals whichgivethehighestorbital
multiplicity,thehighestvalueofL(rememberML=L0+L)
Fromtheprevioustable,themaxML ifwehavetwoupe is+/ 1,thereforeL
=1.Remember,whenL=1,wecallitaPtermorPstate.
Therefore,thegroundstateatomictermforap2 electronconfigurationis:
3P(tripletpee)
andrepresents3x3=9microstates!Thenumberofmicrostatesisthe
entropyofasystem(Entropy,S=kB ln,where isthe#ofmicrostates).
Whatabouttheother6microstates?Theseareforthespinpaired
arrangements(singletspinstates),ofwhichwehave1D(5states)and1S(1
state).Practiceotherelectronconfigurations!
GroundStateTermsfordBlockCompounds
Atrickfordeterminingthenumberofmicrostates:
{2(2l +1)}!/(x!{2(2l +1) x}!)Wherexisnumberofelectrons.
E.g.ford3,x=3,l =2(adorbital,so2l +1=5)
#microstates=10!/(3!(103)!)=10x9x8/1x2x3=720/6=120
Thegroundstateisgoingtobeaquartetspin(3upe +1)
ThemaximumLisgoingtobe2+1+0=3(L=3isanFterm)
TheGroundStateAtomic(FreeIon)Termisgivenby4F(28microstates).
So,theseareforatomsinsphericalfields.Whataboutoctahedra where
thedorbitals splitintot2g andeg sets?
MolecularTermSymbols!
Justlikedorbitals splitintot2g andeg,DatomictermssplitintoT2g andEg
molecularterms(threeandtwomicrostates,respectively).
Whataboutothers?
Racah Parameters&MolecularTermSymbols
MolecularTerms
Thenumberofstatesrepresentedbytheindividualmoleculartermsare:
1foranAterm(anorbitalsinglet)
2foranEterm(anorbitaldoublet)
3foraTterm(anorbitaltriplet)
Becausethespinsofthemoleculartermscannotchangefromthatofthe
atomictermfromwhichtheyoriginate,a3F term(37=21microstates)
becomes3A2g,3T1g and3T2g inanoctahedralmolecule,giving(31)+(33)+
(33)=21microstates
Isthereaneasywayofdeterminingthese?YES!CorrelationDiagrams!
MostcommonformofthesediagramsistheTanabeSuganoDiagram
whichrelatesEnergy,E,andO withrespecttotheRacah parameter,B.
TanabeSuganoDiagrams(onlyworkforOh)
This axis lists the
atomic, or free ion
term symbols for a
d3 ion when O = 0
(no ligands present).
The ground state
atomic term is at the
baseline, with terms
representing excited
states going up in
relative energy
ATanabeSuganoDiagramforad5 ion
+2 +1 0
-1 -2
6
S atomic state (L = 0) hs d5
+2
2
+1
-2
-1
t2g
eg
2
t2g
Becauseionsd4 tod7
electron
configurationshave
highorlowspin
configurations,the
molecularground
statedependsonthe
strengthoftheligand
field.Weakligand
fields(smallO)are
giventotheleftofthe
verticallinewhile
strongligand fieldslie
totheright.
Forhs d5,theatomic
termis6S,whichgives
a6Amolecularstate.
OnceO becomes
largeenough,thels d5
caseisfavoured,
whichhasa2T
moleculartermarising
froma2I atomicstate.
Ratioofenergiesforthetwospinallowedtransitions=28500/21550=1.32
LookattheTSdiagramford3.Wheredoesthistransitionratiooccur?
The1.32:1ratiooccursatO/B=32.
ThiscorrespondstoanE/Bvalueof32
forthe4T2g energylevel,whichhadanE
of21550cm1 fromtheUVvis spectrum.
SolveforB:B=21550cm1/32=673cm1
NowuseBtomeasureO.
O =32xB=21550cm1
Note,forad3 ion,O isgivenbytheEof
thelowestEspinallowedtransition!
Otherelectronconfigurationsnotas
straightforward.Why?
Electronelectronrepulsion!Lookatthe
CFSdiagram.
YoumustknowhowtoestimateBandO
fromaUVvis spectrumandthe
appropriateTSDiagram
ChargeTransferBands
ddtransitionsareusuallyinthevis
region(givecomplexestheircolours)
Whataboutthehighenergybands
foundintheUV(andsometimesvis)?
TheseareChargeTransfer(CT)Bands:
Theyarisefromelectronsmovingfrom
thepopulatedligand centred orbitals
intoemptymetalorbitals (Ligand to
Metal,orLMCT)
Orfrompopulatedmetalcentred
orbitals intovacantligand orbitals
(usually*antibonding)givingMetal
toLigand CT,MLCT
SelectionRules
CTbandsarealwaysintense,meaningstrongabsorptions, large
extinctioncoefficients(yaxisofUVvis spectrum)
CTbandsareusually highinenergy(xaxisofUVvis spectrum),butnot
always(seeEleveldiagramonpreviousslide).
Energy(incm1)isdeterminedbythedifferenceinorbitalenergies
Intensityisdeterminedbyprobabilityoftheeventoccurring
ProbabilityisgivenbytheSelectionRules.
SpinSelectionRule:Mustmaintainthe#ofupe tobeallowed.Robust
andhardtocheatthereforespinforbidded transitionsarenotoften
observed
Laporte (Symmetry)SelectionRule:Allowedtransitionsarethosethat
areaccompaniedbyachangeinparity:
guallowed,ugallowedbutggoruuFORBIDDEN!
Thereforeddbands,becausetheygofromt2g toeg,areinfactforbidden!
Whydotheyoccuratall?Laporte rulecanberelaxedbymicrodistortions.
RelaxationoftheLaporte SelectionRule
InTd complexes,thereisnoi, nogoruparity
labels.So,theddbandsinTd complexesare
lowerinE,BUTaremoreintense.
Whydoddbandsoccuratallinoctahedral
complexes?
NotalloctahedralcomplexesaretrulyOh
symmetry,thereforeareactuallyallowed(lack
truei)
Eventrue,homoleptic Oh complexesundergo
Staticeffects:crystalpacking,ligand differences
(orientationofpolyatomicligands)
Dynamiceffects:asymmetricalvibrations
destroyinversioncentres.
Ingeneral,Laporte ruleiseasiertobreak
thereforeLaporte forbiddentransitionsare
strongerthanSpinforbiddentransitions.
ExamplesofLMCTvs.MLCT
LMCT:mayoccurifligands havelonepairsofrelativelyhighE(e.g.S,SeorO)
orifmetalhaslowlyingvacantorbitals (metalinhighoxidationstate).
MnO4 anionisdarkpurple:MnVII (3d0)withO2 ligands =LMCTinvisible
region(thereforethepurplecolour!)
ReO4 anionispale:ReVII (5d0)sov.largeEgap!LMCTisinUVregion.We
cantseethecolour withoureyesb/citstoohighinE.
Also,bothareTd sonoinversioncentres (Laporte ruledoesntapply!
EofLMCTincreasesdownagroupb/c
empty3dorbitals aremoreeasily
accessiblethan4dor5dfromtheligand
orbitals (suchas2pinO2)
Relatestoreductionpotential!3d
metalsareeasiertoreduce.Therefore,
thechemistryof4dand5dmetalsis
dominatedbytheirhighestpossibleO.S.
ConsiderFetriadonlyOscanachieve
OsVIII oxidationstate,inOsO4.
ExamplesofLMCTvs.MLCT
MLCT:Mostobservedinligands withlowlying*orbitals,especially
aromatics(whichalsoshown *or *UVbands,thereforeusing
benzeneasasolventforUVvis maybeabadidea)
Transitionislikelyifmetalisinalowoxidationstate(e rich)andtherefore
hashigherenergymetalorbitals (becauseoflowerZeff).
Theclassic:[Ru(bipy)3]2+ hasalongexcitedstatelifetime,andisa
usefulphotochemicalreducingagent
MLCTcanbethoughtofasoxidationofthemetalwhereitloses
electronsintotheligands*orbitals (canmakeorganicradicals!)
IncomplexeslikeCr(CO)6,bothLMandMLCTarepossiblebutoftennot
easytodistinguish(sowejustcallitCT)
Sometimes,strongCTbandsoverlapwiththevis regionsomayobscured
dtransitions.Carefulmeasurementof isneededtobesure.Remember,
valuesabove1000areprobablyCT,whereasweakermaybeddbands.
CloudExpanding:Nephelauxetic Series
Someligands aremorecapableofdelocalizingelectrondensityawayfrommetal
orbitals andontothemselves.Thisresultsinloweree repulsionatthemetal
centre.
Experimentally,thisresultsinthereductionoftheRacah parameter,Bfromits
freeionvalue.
=Bcomplex/Bfreeion
where isthenephelauxetic parameter
WecanobtainaNephelauxetic Seriesofligands basedontheirvalue
Strongdelocalizationontotheligands decreasesBcomplexvs Bfreeion,
therefore isasmallvalue.Thisgivesthefollowingseriesrankedinorderof:
I <Br <CN <Cl <en<NH3 <H2O<F
I exhibitsastrongnephelauxetic effect(small,largedelocalizationofe ontoitself)
F exhibitsaweaknephelauxetic effect(large,littledelocalizationofe ontoitself)
ThepositionrelatestoHSABwherethemorepolarizable aligand thelowerthe.
Actualeffectdependsonwhetherthee areintheeg ort2g orbitalsincecloud
expansionismoreapropertyofbonding.Thereis ametalioneffecttoo:
Mn(II)<Ni(II)Co(II)<Mo(II)<Re(IV)<Fe(III)<Ir(III)<Co(III)<Mn(IV)