ElectronicSpectroscopy

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

Inmultielectron ions,theeffectsofee repulsionaresummarizedbythe

Racah Parameters,A,BandC.Theseareinfactmathematicalrepresentations
ofHunds Rules.Theenergiesofthetermsarethereforerelatedby:
E(1S)=A+14B+7C
E(1G)=A+4B+2C
E(1D)=A 3B+2C
E(3P)=A+7B
E(3F)=A 8B
Aiscommontoall,soignoreittogetrelativeenergies.
C 4B,soweareleftwithB,whichinanOh fieldisrelatedtoO.
Bisamathematicalwayofweighingouthowstrongaligand isintermsofits
affectonthesplittingincombinationwithcertainelectronconfigurations.
So,Datomicterms splitintoT2g andEg molecularterms.Whataboutothers?
AtomicTerms
Numberofmicrostates
MolecularTerms
S
1
A1g
P
3
T1g
D
5
T2g +Eg
F
7
T1g +T2g +A2g
G
9
A1g +Eg +T1g +T2g

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

This axis lists the

molecular term
symbols for a d3 ion
when O > 0. The
ground state molecular
term is at the baseline,
with terms representing
excited states going up
in relative energy.
Notice that as O
increases, the splitting
between most states
increases as well. Also,
note that molecular
terms can only possess
the same spin as the
atomic term from which
they originate. 4F gives
4A , 4T
4
2g
2g and T1g (on
the diagram the g
parity label is removed
for clarity).

ATanabeSuganoDiagramforad5 ion

+2 +1 0
-1 -2
6
S atomic state (L = 0) hs d5

+2
2

+1

-2

-1

I atomic state (L = 6!) ls d5

eg

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.

Ligand FieldTransitions UVvis spectrumforad3 ion

Absorptionaxis,
usuallyconvenientto
converttounitsof
extinctioncoefficient
(molarabsorptivity,
M1cm1)

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

TanabeSuganoDiagramsford2 andd3 ions

AvailableinappendixofS&A

TanabeSuganoDiagramsford4 andd5 ions

TanabeSuganoDiagramsford6,d7 &d8 ions

TypicalOh Ligand FieldTransitionsforTmetals

Notethevalueof
ontheyaxis
(esp MnII)
Dothenumber
ofbandsconfirm
whatispredicted
bytheTSDs?
FortheFeII and
CoII spectra,are
thecompounds
h.s orl.s?

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)