QuantumTheoryofRamanEffect

Radiationoffrequency consistsofstreamofparticleswith
energyE=h.
Anelasticcollision ofthephotonswiththemoleculeswill
deflecttheradiationunchanged.
Aninelasticcollision ofthephotonswiththemoleculeswill
resultintoexchangeofenergybetweenphotonsand
molecules.

Thegainorloseofenergycanoccuraccordingtothequantal
laws.
Theenergychange,
Ejoules=differenceinenergybetweentwoallowedstates.

Erepresentsachangeinthevibrationalorrotationalenergy
(orboth)ofthemolecule.

 AgainofEenergybythemolecule thephotonwillbe
scatteredwithenergyhE.
ThecorrespondingradiationwillhaveafrequencyE/h.
AlossofEenergybythemolecule thephotonwillbe
scatteredwithenergyh+E.
Thecorrespondingradiationwillhaveafrequency+E/h.
Radiationscatteredwithafrequencylowerthanthatof
incidentbeam Stokesradiation
Increaseinmolecularenergy(moreintense)

Radiationscatteredwithafrequencyhigherthanthatof
incidentbeam antiStokesradiation
Decreaseinmolecularenergy(lessintense)

ClassicalTheoryofRamanEffect
MolecularPolarizability
Amoleculeinastaticelectricfield(E)sufferssomedistortion.
Chargeseparation occursduetotheattractionofthe
positivelychargednucleustowardsthenegativeandthe
negativelychargedelectronstowardsthepositivepoleofthe
electricfield.
Separationofchargecentrescausesaninducedelectric
dipolemoment inthemolecule moleculeispolarized.

Thesizeoftheinduceddipole,,dependsonthemagnitude
oftheelectricfield,E,andtheeasewithwhichthemolecule
canbedistorted.

= E
isthepolarizability ofthemolecule.

Thepolarizabilityofamoleculeinvariousdirectionsis
representedbyapolarizabilityellipsoid.

athreedimensionalsurfacewhosedistancefromthe
electricalcentreofthemoleculeisproportionalto 1 / ai
ai isthepolarizabilityalongthelinejoiningapointi onthe

ellipsoidwiththeelectricalcentre.
i

Alldiatomicmoleculeshaveellipsoidsofthesamegeneral
shape.Theydifferonlyintherelativesizesoftheirmajorand
minoraxes.
Theelectricfieldexperiencedbysuchamoleculewhena
radiationoffrequency isincidenttoit:

E = E0 sin 2t
Theinduceddipoleundergoesoscillationsoffrequency:

= E = E0 sin 2t
RayleighScattering

Ifthemoleculeundergoessomeinternalmotion(vibrationor
rotation), thepolarizability canundergochangesperiodically.

Theoscillatingdipolewillbesuperimposedbythevibrational
orrotationaloscillation.
Avibrationoffrequencyvib canchangethepolarizability.

= 0 + sin 2 vibt

 = 0 + sin 2 vibt
0 istheequilibriumpolarizabilityand representstherate
ofchangeofpolarizabilitywiththevibration.

= E = ( 0 + sin 2 vibt )E0 sin 2t

1
Using, sin A sin B = {cos( A B ) cos( A + B )}
2

Weget,

1
= 0 E0 sin 2t + E0 {cos 2 ( vib )t cos 2 ( + vib )t}
2

1
= 0 E0 sin 2t + E0 {cos 2 ( vib )t cos 2 ( + vib )t}
2
Thus,theoscillatingdipolehasfrequencycomponents

vib aswellastheexcitingfrequency.
InordertobeRamanactiveamolecularrotationor
vibrationmustcausesomechangeinacomponentofthe
molecularpolarization.

PureRotationalRamanSpectra
LinearMolecules
Therotationalenergylevelsoflinearmolecules:
J = BJ (J + 1) DJ 2 ( J + 1)2 cm -1

(J = 0,1,2,....)

InRamanspectroscopythepolarizabilityofthemoleculeis
considered.
So,thecentrifugaldistortionduetorotationisunimportant.
J = BJ (J + 1) cm -1

(J = 0,1,2,....)

SelectionRuleforRotationalRamanSpectra
J=0,or2
Therotationalquantumnumberchangesbytwounitsrather
thanone.
Aresultduetothesymmetryofthepolarizability
ellipsoid.

Consideringthattheupperstatequantumnumberis
necessarilygreaterthanthelowerstatequantumnumber,
andJ=0transitiondoesnotrepresentanychangeinthe
molecularenergy
WeconsideronlyJ=+2indeterminingtheenergychange
duetothetransition.

= J = J + 2 J = J = B(4 J + 6 )

cm -1

So,J=+2islabeledasS branchlines.

S = B(4 J + 6 )

cm

-1

(J = 0,1,2,....)

Ifamoleculegains rotationalenergyfromthecollidingphoton a
seriesofSbranch linesaregenerated.
Theyappeartothelowwavenumber sideoftheexcitingline.
Stokeslines
Ifamoleculeloses rotationalenergytothecollidingphoton aseries
ofSbranch linesaregenerated.
Theyappeartothehigherwavenumber sideoftheexcitingline.
antiStokeslines

 S = B(4 J + 6 )

(J = 0,1,2,....)

cm -1

PuttingJ=0 Separationofthefirstlinefromtheexcitinglineis6Bcm1
Separationofthesuccessivelinesis4Bcm1

4B

4B

6B 6B

SymmetricTopMolecules

Chloroformmoleculeanditspolarizability ellipsoidfromacrossand
alongthesymmetryaxis.

Rotationaboutthetopaxisdoesnotproduceanychangein
thepolarizability.
Endoverendrotationproducesachangeinthepolarizability.
Theenergylevelsofasymmetrictopmoleculeisgivenby:
J , K = BJ (J + 1) + ( A B )K 2 cm -1 (J = 0,1,2,... ; K = J,(J - 1),...)

TheSelectionRulesforRamanspectraare:
K=0andJ=0,1,2
Kistherotationalquantumnumberforaxialrotation.
K=0impliesthatchangesintheangularmomentumaboutthetopaxiswillnotgive
risetoaRamanspectrum.

ForpositiveJ=0,wehave:
Case1:J=+1(Rbranchlines)

R = J = J +1 J = J = 2 B( J + 1) cm -1

(J = 1,2,3,...; J 0)

Case2:J=+2(Sbranchlines)

S = J = J + 2 J = J = B (4 J + 6) cm -1

(J = 0,1,2,3,...)

So,twoseriesoflinesintheRamanspectrum.

R = ex R = ex 2 B(J + 1) cm -1
S = ex S = ex B(4 J + 6 ) cm -1

(J = 1,2,....)
(J = 0,1,2,....)

 R = ex R = ex 2 B(J + 1) cm -1

(J = 1,2,....)

S = ex S = ex B(4 J + 6) cm -1

R RR R R R R R RRRRR R
S

ex R

(J = 0,1,2,....)

R R RR R R R RR R R RR
S

TheRotationalRamanSpectrumofaSymmetricTopMolecule