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Quantum Theory of Raman Effect

1. Quantum theory describes that photons can exchange discrete amounts of energy with molecules through elastic or inelastic collisions. This results in Raman scattering with radiation at shifted frequencies. 2. In classical theory, molecules polarize when subjected to electric fields, with the induced dipole moment proportional to polarizability. Vibrational or rotational changes in polarizability cause frequency shifts in scattered radiation. 3. Rotational Raman spectra of linear molecules exhibit selection rules of ΔJ = 0, ±2, appearing as spaced peaks called S branches from the excited frequency. Symmetric top spectra have R and S branches from ΔJ = ±1, ±2 transitions.

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238 views

Quantum Theory of Raman Effect

1. Quantum theory describes that photons can exchange discrete amounts of energy with molecules through elastic or inelastic collisions. This results in Raman scattering with radiation at shifted frequencies. 2. In classical theory, molecules polarize when subjected to electric fields, with the induced dipole moment proportional to polarizability. Vibrational or rotational changes in polarizability cause frequency shifts in scattered radiation. 3. Rotational Raman spectra of linear molecules exhibit selection rules of ΔJ = 0, ±2, appearing as spaced peaks called S branches from the excited frequency. Symmetric top spectra have R and S branches from ΔJ = ±1, ±2 transitions.

Uploaded by

ShubhamNandi
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© © All Rights Reserved
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Download as PDF, TXT or read online on Scribd
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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

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