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# Lecture37:SymmetryOrbitals

ThematerialinthislecturecoversthefollowinginAtkins.
15MolecularSymmetry
CharacterTables
15.4Charactertablesandsymmetrylabels
(a)Thestructureofcharactertables
(b)Charactertablesandorbitaldegeneracy
(c)Charactersandoperators
(d)Theclassificationoflinearcombinationsoforbitals
15.5Vanishingintegralsandorbitaloverlaps
(a)Thecriteriaforvanishingintegrals
(b)Orbitalswithnonzerooverlaps
Lectureonline
SymmetryOrbitals(PowerPoint)
SymmetryOrbitals(PowerPoint)
Handoutsforthislecture

## Character Table Structure of character table

C2v

Onedimensionalirreducible
representationshavethe
character1forE.

C2

TheyaretermedAorB.
Aisusedifthecharacterofthe
principlerotationis1.

Bisusedifthecharacterofthe
principlerotationis1
A1hasthecharacter1forall

operations

## Character Table Structure of character tableTd

C3

C3

C2

C3

Irreduciblerepresentationswith
dimension2aredenotedE
Irreduciblerepresentationswith
dimension3aredenotedT

C3

Numberofsymmetryspecies
(irreduciblerepresentations)=
Numberofclasses

Character Table

## Structure of character tableC2v

Apxorbitalonthecentralatom
ofaC2vmoleculeandthe
symmetryelementsofthegroup.
Epx=1px;C2px=1px
vpx=1px;vpx=1px

Theirrep.isB1and
Thesymmetryb1

Character Table

C2 v

++

## Structure of character tableC2v

Apyorbitalonthecentralatom
v' ofaC2vmoleculeandthe
symmetryelementsofthegroup.
Epy=1py;C2py=1py
vpy=1py;vpy=1py

Theirrep.isB2and
Thesymmetryb2

Character Table

C2

## Structure of character tableC2v

Apzorbitalonthecentralatom
v' ofaC2vmoleculeandthe
symmetryelementsofthegroup.
Epz=1pz;C2pz=1pz
vpz=1pz;vpz=1pz

Theirrep.isA1and
Thesymmetrya1

Character Table

## Structure of character tableC2v

ofaC2vmoleculeandthe
symmetryelementsofthegroup.

Edxy=1dxy;C2dxy=1dxy
vdxy=1dxy;vdxy=1dxy
Theirrep.isA2and
Thesymmetrya2

Character Table

C2

## Structure of character tableC2v

A1s orbitalonthetwo
+

terminalatoms
ofaC moleculeandthe
2v
symmetryelementsofthegroup.
E1s+=11s+;C21s+=11s+

v1s+=11s+;v1s+=11s+
Theirrep.isA1and
Thesymmetrya1

Character Table

C2

## Structure of character tableC2v

orbitalonthetwo
A1s
terminalatoms
ofaC2vmoleculeandthe
symmetryelementsofthegroup.
E1s=11s;C21s=11s

v1s=11s;v1s=11s
Theirrep.isB2and
Thesymmetryb2

Character Table

## Structure of character tableC2v

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).

## Structure of character table

I =C2 1s+(1)2py (1)dv =
I = 1s+(1)2py (1)dv =
I = [C 21s+(1)][C 22py (1)][C 2dv] =

Character Table

I = 1s+(1)[2py (1)][dv] =

2py
Y

z

2py
Y

Character Table

## Structure of 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

## We must have in general1.Decideonthesymetryspeciesofthe

Individualfunctionsf1andf2by
f1f2dv=
I =O
If c 1 referencetothecharactertable,and

(Of1)(Of2)dv=
I= 0
writetheircharactersintworowsin
cf1f2dv
thesamesameorderasinthetable
with c = 1
Generalprocedure
for determining the
symmetry of product
f1f2

Character Table

## Structure of character table

I = 1s+(1)2py (1)dv

1.Decideonthesymmetryspeciesofthe
individualfunctionsf1andf2by
referencetothecharactertable,and
writetheircharactersintworowsin
thesamesameorderasinthetable

2pz
Y

## 1s+= 1s1 +1s2

2.Multiplythenumbewrsineachcolumn,
Writingtheresultsinthesameorder

2py1111
1s+1111 3.ThenewcharactermustbeA1
2py1s+1111 Fortheintegraltobenonzero

ThesymmetryspeciesisB
2

Character Table

I = 1s(1)2py (1)dv

I = f1f2dv

2pz

## It should be clear that

the above procedure
only provide a1 A
character if
f
1 and
2f

## 1s= 1s1 1s2

2py1111
1s1111
2py1s1111

ThesymmetryspeciesisA

representation
1

Character Table

py

pz

px
B1

B2

A1

1s

1s+

A1

B2

with 1s
+

with 1s

## Character Table Structure of character table

C2v

C2

Thecharactertableofagroup
isthelistofcharactersofallits
irreduciblerepresentations.
Namesofirreducible
representations:A1,A2,B1,B2.
Charactersofirreducible
representations

Character Table

## Structure of character table

Appendix
1 C3v

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.

## Howare they constructed

Character Table
ConstructingLinearcombinations
b1
a1

ex
a2

a2

linearcombinations
oforbitalsina
C3vmolecule.

ey
combinationsofthepbasis
orbitals.
Thetwocombinationseachspana
onedimensionalirreducible
representation,andtheirsymmetry
speciesaredifferent.

## Character Table ConstructingLinearcombinations

C2
C

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

## Character Table ConstructingLinearcombinations

C2
C

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

1
1
1 = (1s1 +1s2 +1s2 +1s1)= (1s1 +1s2)
4
2
1
1
'1 = (1s2 +1s1 +1s1 +1s2) = (1s1 +1s2)
4

## Character Table ConstructingLinearcombinations

C2
C

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

1
1 = (1s1 +1s2 1s2 1s1)=0
4
1
'1 = (1s2 +1s1 1s1 1s2)=0
4

## Character Table ConstructingLinearcombinations

C2
C

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

1
1 = (1s1 1s2 +1s2 1s1)=0
4
1
'1 = (1s2 1s1 +1s1 1s2)=0
4

## Character Table ConstructingLinearcombinations

C2
C

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

1
1
1 = (1s1 1s2 1s2 +1s1)= (1s1 1s2)
4
2
1
1
'1 = (1s2 1s1 1s1 +1s2)= (1s2 1s1)
4

## Character Table ConstructingLinearcombinations

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

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

## Character Table ConstructingLinearcombinations

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

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