Section3

M l l R t ti l S t
Section3
M l l R t ti l S t MolecularRotationalSpectroscopy
Lectures46
MolecularRotationalSpectroscopy
Lectures46
Quantumtheory
of atoms / molecules
Previously:
Quantum
Mechanics ofatoms/molecules
Molecular Rotations and Spectroscopy
Mechanics
MolecularRotationsandSpectroscopy
DiatomicMolecules(revision)
Beyonddiatomics
Beyondrigidrotors: y g
Complicationsofnuclearspinstatistics
3.1Thespectroscopist assleuth 3.1Thespectroscopist assleuth
It is now possible to following nuclear Itisnowpossibletofollowingnuclear
motioninrealtime(femtochemistry):
Photodissociation of ICN
AhmedZewail,
N b l P i 1999
PhotodissociationofICN
Veryclassicalpictures
(ballsonsurfaces)
Most spectroscopy however is performed in the frequency domain i e as a
NobelPrize1999
Canbeusedinmanyguises:
i T d t i l l t t d ti
Mostspectroscopy,however,isperformedinthe frequencydomain i.e., asa
functionoffrequencyorwavelength.
i. Todeterminemolecularstructuresandproperties
ii. Todeterminechemicalcomposition(e.g.,extraterrestrial)
iii. Todetermineproperties(Temperature,velocities,etc.)
3.1.1DeterminingChemicalComposition 3.1.1DeterminingChemicalComposition
IR (vibrational) spectroscopy IR(vibrational)spectroscopy
usefulfordetermining
functionalgroupsinsynthetic
chemistry. y
Butspectroscopyisalsouseful
beyond the lab: beyondthelab:
The Orion Nebula The Orion Nebula
Molecularidentificationinspace:EmissionSpectra Molecularidentificationinspace:EmissionSpectra
>130 molecules / ions have been identified in interstellar space by their rotational >130molecules/ionshavebeenidentifiedininterstellarspacebytheirrotational
emissionspectra(rfastronomy)
H
2
C
3
c-C
3
H C
5
C
5
H C
6
H CH
3
C
3
N CH
3
C
4
H CH
3
C
5
N? HC
9
N
CH3OC2H5
HC
11
N
AlF C
2
H l-C
3
H C
4
H l-H
2
C
4
CH
2
CHCN HCOOCH
3
CH
3
CH
2
CN (CH3)
2
CO
AlCl C2O C
3
N C
4
Si C2H4 CH3C2H CH
3
COOH? (CH3)
2
O NH
2
CH
2
COOH
C
2
C2S C
3
O l-C
3
H2 CH
3
CN HC5N C7H CH
3
CH
2
OH CH
3
CH
2
CHO
CH CH2 C
3
S c-C3H2 CH
3
NC HCOCH3 H
2
C
6
HC7N
CH+ HCN C
2
H
2
CH2CN CH
3
OH NH2CH3 CH
2
OHCO C8H
2 2 3 2
CN HCO CH
2
D+ CH
4
CH
3
SH c-C
2
H
4
O CH
2
CHCHO
CO HCO
+
HCCN HC
3
N HC
3
NH+ CH
2
CHOH
CO
+
HCS+ HCNH+ HC2NC HC2CHO
CP HOC+ HNCO HCOOH NH
2
CHO
CSi H
2
O HNCS H2CHN C
5
N
HCl H
2
S HOCO+ H
2
C
2
O HC
4
N
KCl HNC H
2
CO H2NCN
NH HNO H2CN HNC3
NIST&NationalRadioAstronomyLab.
NH HNO H2CN HNC3
NO MgCN H
2
CS SiH
4
NS MgNC H
3
O
+
H
2
COH
+
y
ExtraterrestrialAbsorptionSpectroscopy ExtraterrestrialAbsorptionSpectroscopy
Useastarbehindthecloudaslightsourcefordirectabsorption

uv
visible Infrared visible Infra red
1
st
identifiedin1921,>300linesobservedthroughoutthegalaxy.
After89years,notonelinehasbeenconclusivelyassigned!
AtleastthatwastrueuntilJan2011.....
Groupleader,anexBalliol/PTCL
DPhilstudent!
C=C=C
H
HH
Molecular
l
Molecular
l EnergyLevels EnergyLevels
i.e.,typically E
el
>> E
vib
>> E
rot
Differentelectronicstates
(electronic arrangements) (electronicarrangements)

E 2x10
4
10
5
cm
1
500 100nm
10
2
5x10
3
cm
1
100m 2m
3 300GHz
(0.1 10cm
1
)
Transitionsat
Vis UV
00
infrared
10cm 1mm
microwave
MolecularRotationalEnergyLevelsandSpectroscopy MolecularRotationalEnergyLevelsandSpectroscopy
3.2Themomentofinertia 3.2Themomentofinertia
Definition:Themomentofinertia I ofasystemaboutanaxispassingthroughthe
centreofmassisgivenby;

=
i i
r m I
2
wherem
i
isthemassoftheith particleand

i
i i
r m I
e.g.,:Foradiatomicmolecule:
i
p
r
i
isitsperpendiculardistancefromtheaxis
2 2
2 2
2
1 1
2
R r m r m r m I
i
i i
= + = =

g ,
m
1
m
2
R
) (
2 1
2 1
m m
m m

+
=
Wherethe
reducedmass,

R
I istherotationalequivalentofmass.
F b d t ti b t i ith l l it
J
Forabodyrotatingaboutanaxiswithangularvelocity;
Theangularmomentum, J =I (c.f.p =mv)
J

R
Therotationalkineticenergy,E =J
2
/2I = I
2
(c.f.E= p
2
/2m=mv
2
)

3.3QuantumRotation:TheDiatomicRigidRotor 3.3QuantumRotation:TheDiatomicRigidRotor
Therigidrotorrepresentsthequantummechanicalparticleonasphereproblem:
Rotationalenergyispurelykineticenergy:
2 2 2
2 2
2 2
2 1
2 2
H E
r r r r




= = + + =

2
2
2
2
H E
r

= =

Which,forconstantr, simplifiesto
Thesolutionsresemblethoseoftheparticleonaringwithcyclicboundaryconditions
(+2)=() and are called spherical harmonics
( ) ( ) ( )
Y = (+2)=() andarecalledsphericalharmonics
The energy eigenvalues (the bit we will be interested in) are given by
( ) ( ) ( )
l l l
lm lm m
Y , =
( )
2
1
2
J
Jm
E
I
+

= J J
Theenergyeigenvalues (thebitwewillbeinterestedin)aregivenby
withJ =0,1,2,3....
and m = 0 1 2 J andm
J
=0,1,2,.....J
3.3QuantumRotation:TheDiatomicRigidRotor 3.3QuantumRotation:TheDiatomicRigidRotor
J
5
30B
Eigenvalues:
( )
1 E B = +
J
J J
( )
2
Joule B in

J istherotationalquantumnumber =0,1,2,3,...
Bisthe rotationalconstantgivenby
4
20B
( )
Joule
2
B in
I
=
These are usually given as wavenumbers or
3 12B
Theseareusuallygivenaswavenumbers or
rotationalterms:
( )
1
E
F B
hc
= = +
J
J
J J

0 0
1
2
2B
6B
B

( )
hc
2 2 2
8 8
h h
B
cI c R
= =

H
2
60.85cm
1
CO1.93cm
1
HCl 10 59 cm
1
B
8 8 cI c R
HCl 10.59cm
1
n.b., Thereisnozeropointenergyassociatedwithrotation,i.e.,E
J=0
=0 p gy
J 0
RotationalenergylevelsgetmorewidelyspacewithincreasingJ
Sohowfastdomoleculesrotate?
3.3QuantumRotation:TheDiatomicRigidRotor 3.3QuantumRotation:TheDiatomicRigidRotor
11
B
I

providesthespectrallinktomoleculargeometricstructure
F diatomics it i it li it
1 1
B

extract bond lengths (strictly 1/R

2
)
Fordiatomics itisquiteexplicit:
2
B
I R
=
extractbondlengths(strictly1/R
2
)
Isotope Effects: IsotopeEffects:
R isisotopeindependent(theelectronicproblem)butclearlythereducedmass
doeschangeandsoe.g.,
37 36
B
u u u

35 37
37 35
37 36
1 0015
38 35
H Cl H Cl
H Cl H Cl
B
u.u u
. .
B u u.u

= = =

ForH
35
ClandH
37
Cl:
M
J
1
2
1
2
DegeneracyofRotationalLevels DegeneracyofRotationalLevels
IntheabsenceofexternalfieldseachJ level
exhibits(2J+1)-folddegeneracyarisingfrom
the projection quantum number M
J
:
0
1
1
0
1
1
theprojectionquantumnumberM
J
:
2
2
e.g., J =2
3.4PopulationsofJ levels 3.4PopulationsofJ levels
J
E

FromtheBoltzmanndistribution
J
5
30B
E
n g exp
kT




j
j j
( ) ( )
4
20B
( ) ( )
2 1 and 1 g E hcB = + = +
j J
J J J

( )
1 h B

J J

( )
( )
1
2 1
hcB
n exp
kT

+

+


j
J J
J
2
3 12B
6B
Themostpopulatedleveloccursfor
0
j
dn
dJ
=
( )

0 0
1
2B
( )
( ) 2
1
2 2 1 0
j
hcB
dn
hcB
exp
d kT kT

+


= + =




J J
J
J

i.e.,
( )
2
2 2 1 0
hcB
+ = J

or
1 kT
= J

i.e.,
( )
2 2 1 0
max
kT
+ J
2 2
max
hcB
3.5Rotationalwavefunctions 3.5Rotationalwavefunctions
( )
2
where
l
im
m l
e EI
m

= =

GeneralSolution:
( )
2
l
m l

Imposingcyclicboundaryconditionsrestrictsthisto
2
l
m =
0,1,2,3,
l
m =
1
l
m =
Theseareimaginaryfunctionsbutitisusefultoplotthe
realparttoseetheirsymmetries:oddandevenJ levels
haveoppositeparity.
0
l
m =
Parity=(1)
J
3.6RotationalSpectroscopy 3.6RotationalSpectroscopy J
5 30B
A G S l ti R l A.GrossSelectionRule:
Foramoleculetoexhibitapurerotationalspectrumit
mustpossesapermanentdipolemoment.
4 20B
(otherwisethephotonhasnomeansofinteracting
nothingtograbholdof)
3 12B
B.SpecificSelectionRule:
J= 1
0 0
1
2
2B
6B
(Conservationofangularmomentum max. J= 1
Butneedtochangeparity(seerotationalwavefunctions))
( )( ) ( )
1
1 2 1
v F F
B B
+
=
= + + +
J J
J J J J

Transitionsobservedat:
Equallyspaced
( )( ) ( )
( )
1 2 1
2 1
B B
B
+ + +
= +
J J J J
J

q y p
lines,separation2B
n.b.,alllabbasedrotationalspectroscopyisperformedinabsorptionduetovery
slowspontaneousdecayrates(Acoefficient
3
and small)
3.7e.g.,RotationalSpectrumofCO 3.7e.g.,RotationalSpectrumofCO
Rotationalspectrum
ofCO(300K)
( )( ) ( )
1
1 2 1
v F F
B B
+
=
= + + +
J J
J J J J

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

Transitionsinthemicrowaveregion:
1100cm
1
( =1cm 100m)
Linesspaced by
2B

SpectralProfilegovernedbypopulationoflower p g y p p
levelsandJ dependenceofthetransitionstrength.
3.8GeneralClassificationofMolecules 3.8GeneralClassificationofMolecules
RecallDefinition:ThemomentofinertiaI ofasystemaboutanaxispassing
Backtothemomentofinertia
throughthecentreofmassisgivenby;

=
i
i i
r m I
2
Weclassifypolyatomicmolecules onthebasisoftheirmomentsofinertiaabout
threemutuallyperpendicularaxesthroughthecentreofmass(principalaxes).
Calltheseaxesa,b,c and(andthusI
a
, I
b
, I
c
) suchthatI
c
=I
max
and
c b a
I I I
3.9GeneralClassificationofMolecules 3.9GeneralClassificationofMolecules
T
d
O
h
I
h
I. Sphericaltops:
c b a
I I I = =
Zerodipolemoment
nopurerotationalabsorptionspectrum
II.Symmetrictops: (twoidenticalI
i
)
a)Prolate tops:
c b a
I I I = <
c b a
I I I < =
b)Oblatetops:
III. Asymmetrictops:
c b a
I I I < <
d d f d l
1 1
B

3.10Rotationalterms 3.10Rotationalterms
Fordiatomics wedefinedarotationalconstant
2
B
I R
=
Ingeneralwerequirethreesuchrotationalconstants:
h
B
~ h
A
~ h
C
~
b
b
cI
h
B
2
8
=
a
cI
h
A
2
8
=
c
cI
C
2
8
=
aswavenumbers:



H
2
O molecule
1
1
27.9cm
14.5 cm
A
B
=
=

1
14.5cm
9.3cm
B
C =

But,wecannolongerrelate
theseconstantsexplicitlyto p y
individualbondlengths
withinthemolecule.
K B A J J B F
K J
+ + = )
~ ~
( ) 1 (
~
2
,
3.11Prolate tops 3.11Prolate tops
J K
J
=
=

, 2 , 1 , 0
, 3 , 2 , 1 , 0
LevelslabelledJ
Ka
J isthetotalangularmomentum
orrotationalquantumnumber and
K
a
theprojectionquantumnumber
a
p j q
(forprojectionontheunique,a axis).

) J ( J J 1
K J
J
K
J
K
) J ( J J 1 + =
K J
a
=
J = 2
J
J
K=0
K
K=-1 K=-2
6
6
6
6
J
J
K=0
K
K=-1 K=-2
66
66
66
66
J =2
2
K +2
K=+1
J
K
6
6
K +2
K=+1
J
K
66
66
2
0
2
2
2
1
K=+2
K=+1
J
K
K=+2
K=+1
J
K
n.b., Eachlevelhas2J+1 degeneracy(arisingfromM
J
)
Inaddition,eachlevelK >0hasextratwofolddegeneracy(K)
3.12Oblatetops 3.12Oblatetops
K B C J J B F
K J
+ + = )
~ ~
( ) 1 (
~
2
,
J K
J
=
=

, 2 , 1 , 0
, 3 , 2 , 1 , 0
,
J i th t t l l t
LevelslabelledJ
Kc
J isthetotalangularmomentum
orrotationalquantumnumber and
K
c
theprojectionquantumnumber
(forprojectionontheunique,c axis).
Oblatetopsaretypicallyflat
discus likemolecules(e.g.,benzene)
n.b., Eachlevelhas2J+1 degeneracy(arisingfromM
J
)
In addition each level K > 0 has extra twofold degeneracy (K) Inaddition,eachlevelK >0hasextratwo folddegeneracy(K)
3.13Dontconfusevariousprojections 3.13Dontconfusevariousprojections
( )
= + J J J
K referstoaprojectionon
abodyfixedaxis
(inthiscase,foraprolate top,thea axis) ( , p p, )
M
J
referstoaprojectionon
aspacefixedaxis
3.14EnergylevelsforSymmetrictops 3.14EnergylevelsforSymmetrictops
2
1 K ) B
~
C
~
( ) J ( J B
~
F
Oblate topterms
2
1 K ) B
~
A
~
( ) J ( J B
~
F + +
Prolate topterms
2
1 K ) B C ( ) J ( J B F
K , J
+ + =
<0
1 K ) B A ( ) J ( J B F
K , J
+ + =
>0
2
3
4
3
4
J
K=0 K=1
K=2
2
3
2
1
1
0
2
K=0 K=1 K=2
0
1
K 0 K 0 K 1 K 2
K stacks
K stacks
ForagivenJ,energyincreaseswithK
ForagivenJ,energydecreases withK
b
3.15LinearMolecules (C
v
,D
h
) 3.15LinearMolecules (C
v
,D
h
)
= = A
~
I hence 0
a
Special,limitingcaseofprolate top:
A , I
a
hence 0
c
OnlyK =0exists,so
( )

( )
1 0 1 2 3 F B , , , .... = =

J
J J + J
b
3.16LinearMolecules (C
v
,D
h
) 3.16LinearMolecules (C
v
,D
h
)
= = A
~
I hence 0
a
Special,limitingcaseofprolate top:
A , I
a
hence 0
c
OnlyK =0exists,so
( )

( )
1 0 1 2 3 F B , , , .... = =

J
J J + J
3.17 Spherical Tops (T
d
, O
h
, I
h
) 3.17 Spherical Tops (T
d
, O
h
, I
h
) 3.17SphericalTops(T
d
,O
h
,I
h
) 3.17SphericalTops(T
d
,O
h
,I
h
)
C
~
B
~
A
~
= =
( )
1 0 1 2 3 F B , , , .... = =

J
J J + J
Degeneracy=(2J+1)
2
3.17Asymmetrictops 3.17Asymmetrictops
Alas,forthevastmajorityofmoleculesthereisnosimplegeneralanalyticalform
fortherotationallevels.Somemoleculesaredescribedasnearprolateandnear
oblate tops. In general, terms can be derived by matrix diagonalisation. oblate tops.Ingeneral,termscanbederivedbymatrixdiagonalisation.
H
2
O
A=27.88cm
1
m

1
B=14.52cm
1
C=9.28cm
1
m
b
e
r

c
m
W
a
v
e
n
u
m
2 e g J
21
2 e.g., , J
Kc , Ka
I G S l i l T hibi i l l l
3.18RotationalSpectroscopy 3.18RotationalSpectroscopy
I. GrossSelectionrule: Toexhibitapurerotationalspectrumamoleculemust
possessa permanentdipolemoment.
TDM=
el el el el el

, , M , , M , M , M , M , M

= =
J J J J J J
J J J J J J
l f |
II Specific Selection Rule: During a transition the allowed changes in the J K
Dipolemomentofstate|
el

0 1 K J
II. SpecificSelectionRule: DuringatransitiontheallowedchangesintheJ, K
quantumnumbersare:
0 1 = = K J
(arisesfromtheTDMbutwecanthinkofthisasacombinationof (
conservationofangularmomentumandneedtochangeparity)
3.19SpectraofSymmetrictops 3.19SpectraofSymmetrictops
Terms:
2
,
)
~ ~
( ) 1 (
~
K B A J J B F
K J
+ + =
2
,
)
~ ~
( ) 1 (
~
K B C J J B F
K J
+ + =
prolate
oblate
K J K J
F F v
~
=
1
Allowed
K , J K , J
F F v
+1
transitions:
) 1 (
~
2
~
., . + = J B v e i
Withintherigidrotorapproximation spectraofprolate &oblatetopsarethesame g pp p p p
asforlinearmolecules(andindeedsphericaltops):
i.e., Equally spaced lines with separation = 2B

i.e.,Equallyspacedlineswithseparation
Wethusobtainnoinformationontheuniqueaxis(a forprolate,c foroblate)i.e.,
nothingabouttheotherrotationalconstants.
2B
3.20BeyondtheRigidRotor:Centrifugal Distortion 3.20BeyondtheRigidRotor:Centrifugal Distortion
Therigidrotormodelholdsfor,well,rigidrotors.
Molecules,unfortunately,arenot rigidrotors theirbondsstretchduringrotation.
Asaresult,thevariousI (andthus
rotationalconstants)change withJ.
Itismoreconvenient(i.e.,easier)to
treatcentrifugaldistortionasa
perturbationtotherigidrotorterms.
2 2
) 1 (
~
) 1 (
~
) ( J J D J J B J F
3.21Centrifugal Distortionindiatomicmolecules 3.21Centrifugal Distortionindiatomicmolecules
R t ti l t b
2 2
) 1 ( ) 1 ( ) ( + + = J J D J J B J F
whereD isthecentrifugaldistortionconstant(incm
1
)
Rotationaltermsbecome
3
2
4B
D =

g ( )
30B
J
5
J
Typicalvaluesof
RigidRotor
Centrifugal
distortion
2
e

m
b
e
r
20B
4
D
~
B
~
H
35
Cl 10.44 0.0005282
incm
1
w
a
v
e
n
u
m
0
4
12B
3
12
C
16
O 1.923 0.0000061
HCN 1.478 0.0000029
2B
6B
0
1
2
3
0 0 0
( )
( )
1

J
J
2B

4D

= = J
Transitionsoccurat
3
) 1 (
~
4 ) 1 (
~
2
) ( ) 1 ( ) (
~
+ + =
+ =
J D J B
J F J F J
( )
2
1 + J
Prolate tops:
3.22Centrifugal Distortioninsymmetrictops 3.22Centrifugal Distortioninsymmetrictops
Prolate tops:
, K D
~
K ) J ( J D
~
) J ( J D
~
K ) B
~
A
~
( ) J ( J B
~
) K , J ( F
K JK J
4 2 2 2 2
1 1 1 + + + + =
Obl t t
, K D
~
K ) J ( J D
~
) J ( J D
~
K ) B
~
C
~
( ) J ( J B
~
) K , J ( F
K JK J
4 2 2 2 2
1 1 1 + + + + =
Oblatetops:
Rigidrotorterms Centrifugaldistortionterms
i.e.,threedistortionconstants!
J
Transitionsoccurat:
3 2
1 4 1 2
1
) J ( D
~
) J )( K D
~
B
~
(
) K , J ( F ) K , J ( F
~
+ =
= = J
3 2
1 4 1 2 ) J ( D ) J )( K D B (
J JK
+ + =
J =12
J =23
Effecton
Spectrum:
cm
1
3.23EffectsofExternalFields 3.23EffectsofExternalFields
Weknowthateveryrotationallevel,J, comprises 2J+1 statesduetospace
quantization:
M
J
e.g., J = 2
M
J
= -2, -1, 0, 1, 2
1
2
1
2
M
J
2, 1, 0, 1, 2
M
J
0
1
0
1 1
2
1
2
Intheabsenceofexternalfieldsthesestatesarealldegenerate.However,externalE
(or B) fields can lift this degeneracy: (orB)fieldscanliftthisdegeneracy:
E
3.23ElectricFields:The LinearStarkEffect 3.23ElectricFields:The LinearStarkEffect
Anelectricdipole interactswithanappliedfieldresultingin
aninteractionenergy
=

E
cos
=

cos
Effectonenergylevels:Symmetrictops Effectonenergylevels:Symmetrictops
ConsiderJ levelofCH
3
F:
3
pointsalongtheC
3
axiswithJ atsomeangletoit:
Butweknowthisanglefrom
the ratio of J
A
and J (and hence J, K): cos =
K
theratioofJ
A
andJ (andhenceJ, K):
) 1 (
cos
+ J J

AsJ precesses,thecomponentof
perpendicular to J cancels leaving only
J
: perpendiculartoJ cancelsleavingonly
J
:
cos = =
K

) 1 (
cos
+
= =
J J
J

So,anexternalfieldmakinganangle to J yieldsan
i i interactionenergy
cos E
J

) 1 (
cos
+
=
J J
M
J
and
) (
cos ) , , ( = E M K J E
J J Stark

.
) 1 (
) 1 ( ) 1 (
+

=
+ +
=
J J
EKM
J J
M
E
J J
K
J J

n.b.,E
stark
,E, K, M
J
butE
stark
|J|
2
EKM
J

3.24ElectricFields:SymmetricTops 3.24ElectricFields:SymmetricTops
Example:
.
) 1 (
) , , (
+
=
J J
EKM
M K J E
J
J Stark

Consider the transition 2
1
1
1
in a symmetric top:
ForJ =2,K = 1, M
J
=2,1,0
Considerthetransition2
1
1
1
inasymmetrictop:
0 , ,
2 E E
E
Stark

= ,
6
,
6
Stark
In J 1 K 1 M 1 0
0
E
E
S k

=
InJ =1,K = 1, M
J
=1,0
0 ,
2
E
Stark
=
Eff t th t f t i t
3.25ElectricFields:The EffectsontheSpectrum 3.25ElectricFields:The EffectsontheSpectrum
Effectonthespectrumofasymmetricrotor:
RemembertheselectionruleM
J
=0.
Nofield
Usefulfordeterminingabsolutevaluesof J incomplexspectra.
N l ( t t ) F i d lt l i i l
3.26Effectsofnuclearspinsonrotational energylevels 3.26Effectsofnuclearspinsonrotational energylevels
Nucleons(protons,neutrons)areFermionsandasaresultnucleipossessspinangular
momentumI withcorrespondingquantumnumberI.
If the mass number is even: I is integral such nuclei are Bosons Ifthemassnumberiseven: I isintegral suchnucleiareBosons
odd:I ishalfintegralsuchnucleiare Fermions
ThiscanaffectrotationalenergyLevelsintwoways:
1) The nuclear spin gives rise to a magnetic moment which can interact 1) Thenuclearspingivesrisetoamagneticmomentwhichcaninteract
withexternalmagneticfields(thebasisofNMR)andinternalmagnetic
fieldstogivenuclearhyperfinestructure:smallsplittings inthespectrum
2) Theycandeterminewhetherornotrotationallevelsinsymmetric
moleculesactuallyexistasaresultofnuclearspinstatistics
RecallthePauliPrinciple:
Anyacceptablewavefunction mustbeantisymmetricwithrespectto
theexchangeoftwoidenticalfermionsandtotallysymmetricwith
respecttotheexchangeofidenticalbosons
3.27NuclearSpinstatisticsinH
2
:ortho andpara hydrogen 3.27NuclearSpinstatisticsinH
2
:ortho andpara hydrogen
W h f h l i i h l f i hi h b

tot
=
el

vib

rot

ns
Wehavetoaccountforthenuclearspininthetotalwavefunction whichbecomes:
Consider
ns
[c.f.electron spins in Section 2.16]
In H each nucleus is a fermion with s = and therefore m = (or ) InH
2
eachnucleusisafermion withs=andthereforem
s
=(or, )
Fourcombinationsarepossible:(1)(2), (1)(2), (1)(2), (1)(2)
Butweareinterestedinsymmetrywithrespecttoexchangesotakelinear
combinationsoflattertwoandweachieve:
( ) ( )
( ) ( )
1 2
1 2


Symmetric to exchange
( ) ( )
( ) ( ) ( ) ( )
( ) ( ) ( ) ( )
1
1 2 2 1
2
1
1 2 2 1



+


Symmetrictoexchange
[3of]
( ) ( ) ( ) ( )
1 2 2 1
2

Antisymmetrictoexchange
[1of]
3.27NuclearSpinstatisticsinH
2
: ortho andpara hydrogen 3.27NuclearSpinstatisticsinH
2
: ortho andpara hydrogen

tot
=
el

vib

rot

ns

tot
mustbeantisymmetricwithrespecttothepermutationofHnuclei:
12

P =

tot
InthegroundstateofH
2
:

el
(
1

g
+
)issymmetric withrespectnuclearinterchangeand
12

el
(
g
) y p g
Allv =0vibrational levelsaresymmetric
So, for acceptable
tot
we need antisymmetric
rot

ns
products So,foracceptable
tot
weneedanti symmetric
rot

ns
products

rot
:permutationequivalenttoac
2
rotation
evenJ levelsaresymmetric
oddJ levelsareantisymmetric
( )
2
1
rot rot

c =
J
All even J levels correspond with AntiSymm of which there is one AllevenJ levelscorrespondwithAnti Symm
ns
ofwhichthereisone
AlloddJ levelscorrespondwithSymm
ns
ofwhichtherearethree
3.27NuclearSpinstatisticsinH
2
: ortho andpara hydrogen 3.27NuclearSpinstatisticsinH
2
: ortho andpara hydrogen
TheextrastatisticalweightingoforthoH
2
(oddJ
levels)overparaH
2
(even J)meansintensity
alternationsof3:1 inrotationallyresolvedspectra
ofH
2
.
OfcourseH
2
doesntexhibitapurerotational
absorptionspectrumbutthiseffectisclearinthe
(idealised) rotational Raman spectrum: (idealised)rotationalRamanspectrum:
oH
2
andpH
2
areessentiallydifferentformsofH
2
:Theydonotinterconvertexcept
inthepresenceofahighspincatalyst.
oH
2
hasaJ =1groundstateandthusexhibitszeropointrotationalmotion=2B
3.28NuclearSpinStatistics:General 3.28NuclearSpinStatistics:General
Consider symmetry of
el

ib
individually.
el
is usually symmetric but beware O
2
Considersymmetryof
el

vib
individually.
el
isusuallysymmetric butbewareO
2
groundstate(
3

)whichisantisymmetric.
Ingeneral,thestatisticalweightingof
. of SYM
1
no
I

+
nuclearspinfunctionsisgivenby:
.ofSYM
1
.ofANTISYM
ns
ns
no
I
no I

+
=

Example1:
14
N
2
14
NisaBoson(I =1),
tot
SYM

el
isSYM (
1

g
+
),hence:

tot
=
el

vib

rot

ns
SYM
AS
S S S S
AS
Weight:
2
1
2:1
intensity
alternation

el
(
g
),
AS AS 1
Example2:
16
O
2
tot
=
el

vib

rot

ns
Weight:
evenJ
alternation
16
OisaBoson(I =0),
tot
SYM

el
is AS(
3

),hence:

tot

el

vib

rot

ns
SYM
AS
AS S S AS
S
Weight:
1
0
levels
missing!
Example3:C
16
O
2
16
OisaBoson(I =0),
tot
SYM

tot
=
el

vib

rot

ns
SYM
S S S S
Weight:
1
oddJ ( ),
tot

el
isSYM(
1

g
+
),hence:
SYM
AS
S S S S
AS
1
0
levels
missing!