Lecture37:SymmetryOrbitals

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

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

Adxyorbitalonthecentralatom
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

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

z

1s+= 1s1 +1s2

2py
Y

1s+= 1s1 +1s2

This is only possible if=0I

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 =

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

2pz
Y

z
2pz

1s= 1s1 1s2

1s= 1s1 1s2

This is only possible if=0I

Character Table

Structure of 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

Structure of character table

For the integral

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

belongsto the same sym.

representation
1

Character Table

Structure of character table

py

pz

px
B1

B2

A1

1s

1s+

A1

B2

2pz overlaps (interacts)

with 1s
+

2py overlaps (interacts)

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

Typicalsymmetryadapted
linearcombinations
oforbitalsina
C3vmolecule.

ey
Twosymmetryadaptedlinear
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
(2)Addanddividebygrouporder

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
(2)Addanddividebygrouporder

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
(2)Addanddividebygrouporder

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
(2)Addanddividebygrouporder

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
(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

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
(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