Professional Documents
Culture Documents
ThematerialinthislecturecoversthefollowinginAtkins.
15MolecularSymmetry
CharacterTables
15.4Charactertablesandsymmetrylabels
(a)Thestructureofcharactertables
(b)Charactertablesandorbitaldegeneracy
(c)Charactersandoperators
(d)Theclassificationoflinearcombinationsoforbitals
15.5Vanishingintegralsandorbitaloverlaps
(a)Thecriteriaforvanishingintegrals
(b)Orbitalswithnonzerooverlaps
(c)Symmetryadaptedlinearcombinations
Lectureonline
SymmetryOrbitals(PowerPoint)
SymmetryOrbitals(PowerPoint)
Handoutsforthislecture
C2v
Onedimensionalirreducible
representationshavethe
character1forE.
C2
TheyaretermedAorB.
Aisusedifthecharacterofthe
principlerotationis1.
Bisusedifthecharacterofthe
principlerotationis1
A1hasthecharacter1forall
operations
C3
C3
C2
C3
Irreduciblerepresentationswith
dimension2aredenotedE
Irreduciblerepresentationswith
dimension3aredenotedT
C3
Numberofsymmetryspecies
(irreduciblerepresentations)=
Numberofclasses
Character Table
Apxorbitalonthecentralatom
ofaC2vmoleculeandthe
symmetryelementsofthegroup.
Epx=1px;C2px=1px
vpx=1px;vpx=1px
Theirrep.isB1and
Thesymmetryb1
Character Table
C2 v
++
Apyorbitalonthecentralatom
v' ofaC2vmoleculeandthe
symmetryelementsofthegroup.
Epy=1py;C2py=1py
vpy=1py;vpy=1py
Theirrep.isB2and
Thesymmetryb2
Character Table
C2
Apzorbitalonthecentralatom
v' ofaC2vmoleculeandthe
symmetryelementsofthegroup.
Epz=1pz;C2pz=1pz
vpz=1pz;vpz=1pz
Theirrep.isA1and
Thesymmetrya1
Character Table
Adxyorbitalonthecentralatom
ofaC2vmoleculeandthe
symmetryelementsofthegroup.
Edxy=1dxy;C2dxy=1dxy
vdxy=1dxy;vdxy=1dxy
Theirrep.isA2and
Thesymmetrya2
Character Table
C2
A1s orbitalonthetwo
+
terminalatoms
ofaC moleculeandthe
2v
symmetryelementsofthegroup.
E1s+=11s+;C21s+=11s+
v1s+=11s+;v1s+=11s+
Theirrep.isA1and
Thesymmetrya1
Character Table
C2
orbitalonthetwo
A1s
terminalatoms
ofaC2vmoleculeandthe
symmetryelementsofthegroup.
E1s=11s;C21s=11s
v1s=11s;v1s=11s
Theirrep.isB2and
Thesymmetryb2
Character Table
A2porbitalonthetwo
terminalatoms
ofaC2vmoleculeandthe
symmetryelementsofthegroup.
E2p=12p;C22p=12p
v2p=12p;v2p=12p
Theirrep.isA2and
Thesymmetrya
2
Character Table
Structure
Structure
ofof
character
character
table
table
I = s1s2dv
ThevalueofanintegralI(forexample,anarea)isindependent
ofthecoordinatesystemusedtoevaluateit.
Thatis,Iisabasisofarepresentation
ofsymmetryspeciesA1(oritsequivalent).
Character Table
I = 1s+(1)[2py (1)][dv] =
2py
Y
2py
Y
Character Table
I =C21s(1)2pz(1)dv =
I = 1s(1)2pz(1)dv =
I = [C21s(1)][C22pz(1)][C2dv] =
I = [1s(1)]2pz(1)dv =
2pz
Y
z
2pz
Character Table
(Of1)(Of2)dv=
I= 0
writetheircharactersintworowsin
cf1f2dv
thesamesameorderasinthetable
with c = 1
Generalprocedure
for determining the
symmetry of product
f1f2
Character Table
I = 1s+(1)2py (1)dv
1.Decideonthesymmetryspeciesofthe
individualfunctionsf1andf2by
referencetothecharactertable,and
writetheircharactersintworowsin
thesamesameorderasinthetable
2pz
Y
2.Multiplythenumbewrsineachcolumn,
Writingtheresultsinthesameorder
2py1111
1s+1111 3.ThenewcharactermustbeA1
2py1s+1111 Fortheintegraltobenonzero
ThesymmetryspeciesisB
2
Character Table
I = 1s(1)2py (1)dv
I = f1f2dv
2pz
2py1111
1s1111
2py1s1111
ThesymmetryspeciesisA
Character Table
py
pz
px
B1
B2
A1
1s
1s+
A1
B2
C2v
C2
Thecharactertableofagroup
isthelistofcharactersofallits
irreduciblerepresentations.
Namesofirreducible
representations:A1,A2,B1,B2.
Charactersofirreducible
representations
Character Table
I = xyf(x,y)dxdy
f(x,y) = 1 inside triangle;
f(x,y) =0 outside triangle
Theintegralofthefunctionf=xy
overthetintedregioniszero.
Inthiscase,theresultisobvious
byinspection,butgroup
theorycanbeusedtoestablish
similarresultsinlessobvious
cases.
Appendix
1
Character TableStructure of character table
C3v
I = xyf(x,y)dxdy
f(x,y) = 1 inside pentagon;
f(x,y) =0 outside pentagon
Theintegrationofafunction
overapentagonalregion.
ex
a2
a2
Typicalsymmetryadapted
linearcombinations
oforbitalsina
C3vmolecule.
ey
Twosymmetryadaptedlinear
combinationsofthepbasis
orbitals.
Thetwocombinationseachspana
onedimensionalirreducible
representation,andtheirsymmetry
speciesaredifferent.
2v
1s1 +
1s
2
E
C2
v
v'
Original basis
11S 1S
2
1S 1S
1
2
1S
2 1S
1
1S
2 1S
1
1S
1 1S
2
For A1 :
Constructatableshowingtheeffect
ofeachoperationoneachorbital
oftheoriginalbasis
Togeneratethecombinationofa
Specificsymmetryspecies,take
Eachcolumninturnand
(I)Multiplyeachmemberofthe
Columnbythecharacterofthe
Correspondingoperator
2v
1s1 +
1s
2
E
C2
v
v'
Original basis
11S 1S
2
1S 1S
1
2
1S
2 1S
1
1S
2 1S
1
1S
1 1S
2
For A1 :
(I)Multiplyeachmemberofthe
Columnbythecharacterofthe
Correspondingoperator
(2)Addanddividebygrouporder
1
1
1 = (1s1 +1s2 +1s2 +1s1)= (1s1 +1s2)
4
2
1
1
'1 = (1s2 +1s1 +1s1 +1s2) = (1s1 +1s2)
4
2v
1s1 +
1s
2
E
C2
v
v'
Original basis
11S 1S
2
1S 1S
1
2
1S
2 1S
1
1S
2 1S
1
1S
1 1S
2
For A2 :
(I)Multiplyeachmemberofthe
Columnbythecharacterofthe
Correspondingoperator
(2)Addanddividebygrouporder
1
1 = (1s1 +1s2 1s2 1s1)=0
4
1
'1 = (1s2 +1s1 1s1 1s2)=0
4
2v
1s1 +
1s
2
E
C2
v
v'
Original basis
11S 1S
2
1S 1S
1
2
1S
2 1S
1
1S
2 1S
1
1S
1 1S
2
For B1 :
(I)Multiplyeachmemberofthe
Columnbythecharacterofthe
Correspondingoperator
(2)Addanddividebygrouporder
1
1 = (1s1 1s2 +1s2 1s1)=0
4
1
'1 = (1s2 1s1 +1s1 1s2)=0
4
2v
1s1 +
1s
2
E
C2
v
v'
Original basis
11S 1S
2
1S 1S
1
2
1S
2 1S
1
1S
2 1S
1
1S
1 1S
2
For B2 :
(I)Multiplyeachmemberofthe
Columnbythecharacterofthe
Correspondingoperator
(2)Addanddividebygrouporder
1
1
1 = (1s1 1s2 1s2 +1s1)= (1s1 1s2)
4
2
1
1
'1 = (1s2 1s1 1s1 +1s2)= (1s2 1s1)
4
C2v
2pA
x
2pB
x
Original basis
E
C2
v
v'
A2p 2p
B
x
x
A
B
2p
2p
x
x
A
- 2pB
-2p
x
x
B
A
2p
2p
x
x
B
-2pA
-2p
x
x
(I)Multiplyeachmemberofthe
Columnbythecharacterofthe
Correspondingoperator
(2)Addanddividebygrouporder
1
1 A
B
B
A
B)
For A2 : 1 = (2pA
2p
2p
+
2p
)
=
(2p
2p
x
x
x
x
4 x
2 x
1 B
1 B
'
A
A
B
1 = (2px 2px 2px +2px ) = (2px 2pA
x)
4
2
C2v
2pA
x
2pB
x
Original basis
E
C2
v
v'
A2p 2p
B
x
x
A
B
2p
2p
x
x
A
- 2pB
-2p
x
x
B
A
2p
2p
x
x
B
-2pA
-2p
x
x
(I)Multiplyeachmemberofthe
Columnbythecharacterofthe
Correspondingoperator
(2)Addanddividebygrouporder
1
1 A
B
B
A
B)
For B1 : 1 = (2pA
+2p
+2p
+
2p
)=
(2p
+2p
x
x
x
x
4 x
2 x
1 B
1 B
'
A
A
B
1 = (2px +2px +2px +2px ) = (2px +2pA
x)
4
2
Whatyoushouldlearnfromthiscourse
1.Beabletoassignsymmetriestoorbitalsfromcharacter
tables.
2.Beabletousecharactertablestodeterminewhether
theoverlapbetweentwofunctionsmightbedifferent
fromzero.
3.Beabletousecharactertabletoconstructsymmetry
orbitalsaslinearcombinationofsymmetryequivalent
atomicorbitals