Section5 MolecularElectronicSpectroscopy Molecular Electronic Spectroscopy (lecture9ish)

Previously:
Q Quantumtheory y ofatoms/molecules Q Quantum Mechanics Valence V l

MolecularElectronicSpectroscopy Molecular Electronic Spectroscopy

Classificationofelectronicstates Molecularterms Electronictransitions:TheFranck CondonPrinciple Electronic transitions: The FranckCondon Principle FranckCondonfactors Vibrational structure:BirgeSponer extrapolation Rotationalstructure:Bandheads Introductiontophotoelectronspectroscopy

Molecular EnergyLevels l

i.e.,typically Eel >> Evib >> Erot

Differentelectronicstates (electronicarrangements) (electronic arrangements)

E 2x104 105 cm1 102 5x103 cm1 Transitionsat 500 100nm 100m 2m 00 Vis UV infrared

3 300GHz (0.1 10cm1) 10cm 1mm microwave

5.1Aquickresume

TheBornOppenheimerApproximation: tot r ,Q , = el r vib Q pp pp Butthisassumesthereisasingle el foragivenelectronicconfiguration.

( ) ( ) ( )

Infact,weshouldsolvetheelectronicHamiltonianateachnuclearconfiguration:

H el el ( r ,R ) = E el ( R ) el ( r ,R )

Makeorbitalapproximationfor>1electron: el = a 1 b 2 c 3 NaHF Na HF ArHS V(R) In1dimension RAB Potentialenergycurves Potentialenergy Potential energy surfaces

() () ()

5.2Classifyingmolecularelectronicstates
DiatomicTermSymbols: Diatomic Term Symbols Classifyaccordingtoangularmomentumaroundtheinternuclear axis,. isanalogoustoml inatoms: e.g.,ap orbitalhasl=1,ml =0,1 Twoporbitalsystemsyield and molecularorbitals; pz (ml=0)combinetoyield, (=0) +

px,y (ml=1)combinetoyield, (=1) +

5.2Moleculartermsymbols
Electronictermsareclassifiedaccordingtotheiroverall angularmomentumontheinternuclear axis,:

SeeValence notesHTyear2

= i = 1 + 2 + 3 +
i

Byanalogywithatomsweusetermsymbols: By analogy with atoms we use term symbols:

Spinmultiplicity=2S+1
(S is the total spin quantum number isthetotalspinquantumnumber forthemolecule)

Gives,accordingto: , g

3/2
Spinorbitlevels

for =0 for =1 for =2

= | + |

ProjectionofS on internuclear axis

5.3AdditionalSymmetryLabels
Forhomonuclear For homonuclear diatomics (or symmetric linear molecules e g CO2) it is (orsymmetriclinearmolecules,e.g.,CO )itis convenienttolabelmolecularorbitals andtermsaccordingtosymmetry(g,u)with respecttoinversionthroughthecentreofsymmetry. Ungerade:uAntisymmetric n.b.: g g=g u u=g g u=u g=u

Gerade:gsymmetric

ForSigmaterms wedenotethesymmetry( / )withrespecttoreflectioninaplane For Sigma terms we denote the symmetry (+/) with respect to reflection in a plane containingtheinternuclear axis.

SeeValence notesHTyear2

5.4Examplemoleculartermsymbols
I.N groundstate(2s I N2ground state (2sg)2(2su)2(2pu)4(2pg)2 =0thereforea term S=0(allelectronspaired),henceasingletterm S 0 (all electrons paired) hence a singlet term

II.NOgroundstate(2s)2(2s)2(2p)2(2p)4(2p)1 n.b.Nog,usymmetrybecausenonsymmetrical

2p 2p

= 1 therefore a term =1thereforea S=1/2(oneunpairedelectron),henceadoubletterm

2

2p 2p 2s

Givingriseto

1/ 2

and 2

3/ 2

2s

5.5Examplemoleculartermsymbols
III.O2groundstate(2sg)2(2su)2(2pg)2(2pu)4(2pg)2

=0,or2therefore, termsarise S=0,or1singlets andtriplets g g=galltermsgerade expect

1

+ g

+ g

ButthisneglectsthePauliPrinciple. Insingletstates, In singlet states spin is antisymmetric Hence these can only be paired with symmetric i isantisymmetric.Hencethesecanonlybepairedwithsymmetric space ,i.e.,g,+ states.Likewisetripletstatesmustbepairedwithg, states.
1

allviolatePauliandthusdonotexist all violate Pauli and thus do not exist Doexist,ofwhichthetripletstateisthelowestinenergy p gy (spincorrelation)

Again,thisisonlyaconsiderationformultiplyoccupied(butnotfull)orbitals

5.6Molecularelectronicstates

fromthelowestelectronicconfiguration ...(2pu)4(2pg)2

, 1 g and 1 + states all arise and g statesallarise g

Eachisdeeplyboundandsupportsvibrational levels.EachcanbemodelledbyaMorse potentialenergyfunction

Otherelectronicconfigurationsgiveriseto g g additionalelectronicstatescorrelatingwith thesameordifferentdissociationproducts. Transitionsbetweendifferentstatesare Transitions between different states are accompaniedbyvibrational bandstructure.

5.7ElectronicSpectroscopy
* ConsiderouroldfriendtheTransitionDipoleMoment R 21 = 2 1d = 2 1 C id ld f i d th T iti Di l M t

WithintheBOapproximation, Within the B O approximation tot=

el(r)vib(R)

q r
i

i i

R 21 = el vib el vib = e el ( r ) vib ( R ) r el ( r ) vib ( R ) dr dR

R 21 = e el ( r )r el ( r ) dr vib ( R ) vib ( R ) dR

Electronic transitionmoment Transitionintensity R 21

2

Vibrational overlap
2

( (r )r (r )dr ) ( (R ) (R )dR )
el el vib vib

=0,1 S =0 and =0 g u(whereg,u exist) + +; (for transitions)

FranckCondonfactor
(squareofthevibrational overlapintegral)

5.8TheFranckCondonPrinciple
Assumption:electronictransitionstakeplaceonsuchashorttimescalethatthe Assumption: electronic transitions take place on such a short timescale that the nucleiremainfrozen(R unchanged)duringthetransition.

Wetalkofverticaltransitionsbetweenpotential energycurves. Thereisnoselectionrulegoverningtheallowed vibrational changesaccompanyinganelectronic transition. Instead,theprobabilityofundertakingav v g y ( transitionisgovernedbyFranckCondonfactors(the overlapofthetwovibrational wavefunctions).

5.9Vibrational Structure: FranckCondonfactors

Theoverlapofthevibrational The overlap of the vibrational wavefunctions is governed by the nature of the isgovernedbythenatureofthe electronicstatesinvolved
I.Ifthebondingcharacterofthe twostatesissimilar: t t t i i il II.Ifthebondingcharacterofthe twostatesisverydifferent: two states is very different

Re Re Bestoverlap(v=0) (v=0) Shortprogression

00 0

1 10

Re Re Bestoverlap(v>0) (v=0) Longprogression

V0

5.10Determiningdissociationenergies
Insomecases,FranckCondonoverlapextendsabove thedissociationlimitandexcitedstatedissociation energiesaremeasureddirectly. energies are measured directly Whenthisisnotthecasebutseveralvibrational levels areexciteditispossibletoextrapolatetofindthe are excited it is possible to extrapolate to find the dissociationlimit.
2 Recall,Morseoscillator: Gv = v + 1 e v + 1 e x e 2 2

v = 0 , 1 , 2 , 3 ,v max

dGv = e 2e x e (v + 1 ) Which,atthedissociationlimit(v+)max becomeszero 2 dv

e 1 dGv 1 = 0 = e 2e x e (v max + 2 ) v max = dv 2e x e 2

Gv max

e2 = De = 4e x e

5.11Determiningdissociationenergies:BirgeSponer Extrapolation
Alternatively,theexperimentaldissociationenergyisthesumofallthevibrational energylevelspacings,Gv+1/2:

D0 = G 1 / 2 + G 3 / 2 + G 5 / 2 + ....

PlotGv+1/2 asafunctionof(v+) AreaundertheplotyieldsD Area under the plot yields D0 Mostsuchplotsdeviatefromlinearityathighv astheMorsePotentialfunctionbecomesan as the Morse Potential function becomes an increasinglypoorrepresentationofthereal potential. Severalvibrational energylevelsarerequiredfor suchafitandsotheyaregenerallyonlyusedfor vibrational bands in electronic spectra. bandsinelectronicspectra.

5.12RotationalStructureinElectronicSpectra
E = Te + Gv + F J Totaltermvalues: hc
Transitionwavenumbers: = Te Te + Gv Gv + F J F J

) (

) (

Electronic Vibrational Rotational Transition transition transition (J rules) FCF Example:1 1

J = 1,leadstoP(J)andR(J)branchesasinvibrotspectra [ [Seesection4.7] ]

However,muchlargerchangesinrotationalconstants,ofbothsign,arenowpossible bandheadsarecommonlyobservedinelectronicspectra,andmayoccurineither branch.

5.13BandHeadsinElectronicSpectra
R ( J ) = el vib + ( B + B )( J + 1) + ( B B )( J + 1)
P ( J ) = el vib ( B + B ) J + ( B B ) J 2
2

(1) (2)

Invibrationrotationspectra,B generallydecreasesslightlywithvleadingtobunching oflinesintheRbranch. Inelectronictransitions,thechangein<R2>canbelargedependingonthebonding characterofthetwoorbitals betweenwhichtheelectronmoves. Bandheadsoccurwhenlinesinabranchcoalesce,i.e.,

d =0 dJ

d IntheR branch: = ( B + B ) + 2( B B )( J + 1) dJ d = ( B + B ) + 2J ( B B ) dJ

IntheP branch:

(B + B ) ( J 1) = 2 B B ( ) (B + B ) J = 2( B B )
head

head

5.13BandHeadsinElectronicSpectra
LargechangeinRe intransition withresultthatB <<B with result that B<<B rotationallevelsmoreclosely spacedinupperstate.

Bandhead intheRbranch: increasedspacinginPbranch CuH 1 1 transition

5.14Qbranches
The =1selectionrulearisesfromconservationofangularmomentumand The J = 1 selection rule arises from conservation of angular momentum and symmetry.However,ifadditionalangularmomenta arepresentwecanalsoobserve Qbranches(J =0transitions).

Q ( J ) = ell vib + ( B B ) J ( J + 1) b

Thisangularmomentumcouldbeelectronic:e.g.,1 1 transition(orindeedany transitioninvolving transition involving > 0)... >0)... ...orvibrational ifthetransitioninvolvesadegeneratevibrational mode(e.g.,a bendingmodeofalinearmolecule) AlH 1 1+ emissionspectrum showingQbranch showing Q branch

5.15PhotoelectronSpectroscopy(gasphase)
Photoionizationisthelimitingcaseofexcitingasingleelectrontohigherelectronic Photoionization is the limiting case of exciting a single electron to higher electronic states.Photoelectronspectroscopy,whichrecordstheionizationenergiesforremoval ofelectrons,providesameasureoftheenergyofmolecularorbitals. K.E.e Ionicstates Ionic states 1)Excitewithfixed highabovetheI.E.
(e.g.,withaHe(I)lampat21.22eV) (e.g., with a He(I) lamp at 21.22 eV)

2)MeasureK.E.ofejectedphotoelectrons
Adiabatic ionizationenergy

Asenergyisconserved: h =I+EM++K.E.e +K.E.M+ whereI istheadiabaticionizationenergy andEM+ istheinternalenergyoftheion.

K.E.e >>K.E.M+ 0

K.E.e =h I EM+

5.16PhotoelectronSpectroscopyofatoms
2S 1/2 2S 1/2

1s1

2s1

(Spinorbitsplitting unresolvedhere)
2P 1/2,3/2 2p1

2p 2s

1s

Nowresolvespin orbitcouplinginionic bit li i i i states

5.17PhotoelectronSpectroscopyofH2
WithaHe(I)lamponlythefirstionizationthreshold ofH2 (1sg)1 isaccessible. H2+ ionic state Removalofastronglybondingelectronresults inasubstantialreductioninbondingcharacter (H2+ moreweaklyboundthanH2) d Re+ >Re kl b d th H )andR + R Longvibrational progression (FranckCondonprinciple)

5.18PhotoelectronSpectroscopyofN2
A B

3bandsinHe(I)PES: A:(2pg)1:weaklybondingelectronremoved,shortprogression, N2+ 2g+ B:(2pu)1:stronglybondingelectronremoved,longerprogression, N2+ 2u C:(2su)1:weaklyantibondingelectronremoved,shortprogression,N2+ 2u+ ( y g , p g , i.e.,bandsubstructurerepresentsvibrational levelsofeachionic state