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Symmetry

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Reflection
Translation

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Rotation

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Sliderotation(Sn)

Lecture36:CharacterTables
ThematerialinthislecturecoversthefollowinginAtkins.
15MolecularSymmetry
Charactertables
15.4Charactertablesandsymmetrylabels
(a)Thestructureofcharactertables
(b)Charactertablesandorbitaldegeneracy
(c)Charactersandoperators
Lectureonline
CharacterTables(PowerPoint)
Charactertables(PDF)
Handoutforthislecture

Audiovisualsonline
Symmetry(GreatsiteonsymmetryinartandsciencebyMargret
J.Geselbracht,ReedCollege,PortlandOregon)
TheWorldofEscher:
WallpaperGroups:The17planesymmetrygroups
3DExercisesinPointGroupSymmetry

Character Table

Usage

We shall now turn our attention away from


the symmetries of molecules themselves

and direct it towards the symmetry characteristics of :


1. Molecular orbitals

2. Normal modes of vibrations

This discussion will enable us to:

I. Symmetry label molecular orbitals


II. Discuss selection rules in spectroscopy

Character Table

Simple case

Arotationthrough180abouttheinternuclearaxisleaves
the
signofaorbitalunchanged
butthesignofaorbitalischanged.
Inthelanguageintroducedinthislectture:
ThecharactersoftheC2rotationare+1and1fortheand
orbitals,respectively.

Character Table
A

Simple case

B
180
C2

Symmetry label

C2

(i.e. rotation by 180)


1

-1

180
C2

Character Table

Symmetry group

Structure of character table

C3v

Symmetry Operations
C

C
E

A
B

Character Table

Structure of character table

Symmetry group

Symmetry Operations

C31

C3 C3 C31

C3

C3v

C3 C3 C3 E

A
B

C31C3 E

Structure of character table

Character Table

Symmetry Operations

Symmetry group

v'

A
C
C

C
B

"

C
C

C3v

Character Table

Classes of elements

C3v

InagroupG={E,A,B,C,...},
wesaythattwoelementsBandC
areconjugatetoeachotherif:
ABA1=C,
forsomeelementAinG.
Anelementandallitsconjugates
formaclass.
A

C C

B A

1
v

C3 1
v

v C3 1
v

C31

Character Table

Classes of elements

Wehaveingeneral:

C3v

EC3E 1 C3

C3 C3 C1
3 C3
C31C3C3 C3

1
vC3 1

C
v
3

1 C 1
v''C3 v''
3
1 C 1
v'C3 v'
3

ThusC3andC31form
aclassofdimension2

The two elements C 3 and C-1


3
can be related to each other by
v , v' , and v' '
C3 v C1
3

Character Table

Classes of elements

C3v

Elementsconjugatedtov?
A

Ingeneral
EvE 1 v
C3 vC31 v"
C31 v C3 v'
v v 1
v v
v' v 1
v' v"
1
v" v v"
v'

C31

C B

v C 1 C3 v C 1
3
3

Thus v , v'
and v"
form a class
of dimension
3. The elements
are related by
C3 and C-1
3

v"

Character Table

Structure of character table

C3v

Symmetry Operations

Symmetry group

The symmetry operations are


grouped by classes with
the dimension of each class
indicated

C3

Also indicated is the dimension


of the group h
v

' v

'' v

h total number of symmetry


elements

Character Table

C2

Structure of character table

C 2v

Name of point group


Number of symmetry
elements
Symmetry elements
E : identity
C2 : Rotation
(xz) mirror plane
' (yz) mirror plane

Character Table

C2

Structure of character table

C 2v

Name of irreducible
representations
A1 A2 B1 B2

Characters of irreducible
representations

of character table
Character Table C Structure
2 v
v'

++

C2

v
v'

+
-

Thepx,py,andpzorbitals
onthecentralatomof
aC2vmoleculeandthe
symmetryelementsofthe
group.

Character Table

Structure of character table

C 2v

Irrep is A1
Symmetry is a1

C2

C2

v (xz )
v' (yz )

pz

pz

pz

pz

pz
pz

pz

pz

Character Table

Structure of character table

C 2v

Irrep. is B2
Symmetry is b2

C2

C2

v (xz )
v' (yz )

py

py

py

py

py

py

py

py

Character Table

Structure of character table

C 2v

Irrep. is B1
Symmetry is b1
C2

C2

v (xz )
v' (yz )

px
px
px
px

px

px
px

px

Character Table

Structure of character table

C 2v

Symmetry is ?

C2

C2

v (xz )
v' (yz )

1s2
1s2
1s2
1s2

1s2
1s1
1s1

1s2

Character Table

Structure of character table

C 2v

Symmetry is ?

C2

C2

1s1
1s1

1s1

1s2

v (xz )

1s1

1s2

v' (yz )

1s1

1s1

Character Table

Structure of character table

1 0
E(1s1 1s2 ) (1s1 1s2 )

0 1
0 1
C2 (1s1 1s2 ) (1s1 1s2 )

1 0

1s1

C 2v
1s2

0 1
v (1s1 1s 2 ) (1s1 1s2 )

1 0
0 1
v' (1s1 1s2 ) (1s1 1s2 )

1 0

This representation is not reduced

Character Table

Structure of character table

C2v

Irrep is A1
Symmetry is a1

C2

C2

1s+
1s+

1s+

1s+

v (xz )

1s+

v' (yz )

1s+

1s+
1s+

Character Table

Structure of character table

C2v

Irrep. is B1

Symmetry is b1

C2

C2

1s
1s

v (xz ) 1s

v' (yz )

1s

1s

1s

1s

1s

Character Table

C2

Structure of character table

C2v

1s+

A1

A1

pz
py

1s
B1

B2

B1

px

Only orbitals with same


symmetry label interact

A1
B1

Character Table

Structure of character table

C2v

Vibrations and
normal modes
O

C2

O
H

H
O
H

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Character Table

Structure of character table

C2v

Symmetry

C2

C2

O
H

v (xz )H

H
O

O
H

O
H

v' (yz )

is a1

O
H

Character Table

Structure of character table

C 2v

Symmetry is b1
O

C2

C2

O
H

v (xz )

v' (yz )

O
H

C2v
Vibrations and
normal modes

A1
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A1

B1

Character Table

C3v

We have three classes of


symmetry elements :
E

the identity

Two three fold rotations

C3 and C-1
3

Three mirror planes


v , ' v , ' ' v

Character Table

C3v

Molecular orbitals of NH3

a1

ex
Normal modes of NH3

ey

Whatyoumustlearnfromthislecture
1.Youarenotexpectedtoderiveanyofthetheoremofgroup
theory.However,youareexpectedtouseitasatool
2..Youmustunderstandthedifferentpartsofacharacter
tableforasymmetrygroup:(a)Nameofsymmetrygroup;
(b)Classesofsymmetryoperators;(c)Namesofirreducible
symmetryrepresentations.(d)Theirreduciblecharacters
3.Forsimplecasesyoumustbeabletodeducewhatirreducible
representationafunctionoranormalmodebelongstobythe
helpofacharactertable.

Character Table

Appendix on C3v

Symmetryoperationsin
thesameclassarerelatedtoone
anotherbythesymmetryoperations
ofthegroup.Thus,the
threemirrorplanesshownhere
arerelatedbythreefold
rotations,andthetworotations
shownherearerelatedby
reflectioninv.

Character Table

Appendix on C3v

The dimension is 6 since we


have 6 elements.
We have three different symmetry
representations as we have three
different classes of symmetry elements

Character Table

Appendix on C3v

px
py
does not change

The pz orbital
does not change
with E, C3 , C-1
3
v , 'v , "v
The symmetry
rep. is A1

with E, C3 , C-1
3
v , 'v , "v
Y

Appendix on C3v

Character Table

px

p'x

p' ' x

Epx = px ; C3px p'x ; C-1


3 px = p"x
Y

Character Table

Appendix on C3v

1 0
px py D(E) px py

0 1
The trace is 2
which is also the
1
3


dimension of
1
2
2

px py D(C3 ) p x p y
the representation
3 1
2
2

px

py D(C3 ) px

1
3

py 2 2
3 1
2
2

The trace is - 1 for


both matrices

Character Table

px

Appendix on C3v

1 0
py D( v ) px p y

0
1

1
3

'
2
px py D( v ) px p y 2
3 1
2
2
1
3

"
2
px py D( v ) px p y 2
3 1
2
2

The trace is - 1 for


both matrices

Character Table

Appendix on C3v

Typicalsymmetry
adapted
linearcombinations
of
orbitalsina
C3vmolecule.