Symmetry

Reflection Translation

Rotation

Slide rotation (Sn)

Lecture 36: Character Tables The material in this lecture covers the following in Atkins. 15 Molecular Symmetry Character tables 15.4 Character tables and symmetry labels (a) The structure of character tables (b) Character tables and orbital degeneracy (c) Characters and operators Lecture on-line Character Tables (PowerPoint) Character tables (PDF) Handout for this lecture

Audio-visuals on-line Symmetry (Great site on symmetry in art and science by Margret J. Geselbracht, Reed College , Portland Oregon) The World of Escher: Wallpaper Groups: The 17 plane symmetry groups 3D Exercises in Point Group Symmetry

Character Table

sage

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

A rotation through 180 about the internuclear axis leaves the sign of a orbital unchanged but the sign of a orbital is changed. In the language introduced in this lectture: The characters of the C2 rotation are +1 and -1 for the and orbitals, respectively.

Character Table
A B

Simple case

180 C2

C2 1 -1 (i.e. rotation by 180)

Symmetry label

180 C2

Character Table

Structure of character table

C3 v

Symmetry group

Symmetry Operations
C E A B A B C

Character Table

Structure of character table

C3 v

Symmetry group

Symmetry Operations

A B B C

B C B A

C 31

C3

C 3C 3 = C 3 1

C 3C 3C 3 = E

C31C3 = E

Character Table

Structure of character table

C3 v

Symmetry group
C A

Symmetry Operations
B

v
B
C

' v
A

C C B

A C
C B

"

Character Table

Classes of elements

C3 v

In a group G={E,A,B,C,...}, we say that two elements B and C are conjugate to each other if : ABA-1 = C, for some element A in G. An element and all its conjugates form a class.
A
A

=
B A

C C

1 v

1 C3 v

1 v C3 v

C 31

Character Table
We have in general:

Classes of elements

C3 v

C 3C 3C 3 1 = C 3
vC3 v1 = C31

EC3E 1 = C3

C31C3C3 = C3

v''C3 v1 = C31 ''

v'C3 v1 = C31 '

Thus C3 and C3-1 form a class of dimension 2

-1 The two elements C3 and C3 can be related to each other by v , v' , and v' '
C 3 = v C 31

Character Table Classes of elements Elements conjugated to v ?

A
B
B

C3 v

=
C B

In general

C 31

v C 1 C3 v C 1 3 3

v"

E vE 1 = v C 3 v C 31 = v " C31 vC3 = v' v v v1 = v v' v v1 = v" ' v" v 1 =

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

Character Table

Structure of character table

C3 v

Symmetry group
C3

Symmetry Operations

The symmetry operations are grouped by classes with the dimension of each class indicated
Also indicated is the dimension of the group h

' v

' ' v

h = total number of symmetry elements

Character Table

Structure of character table

2v

Name of point group

Number of symmetry elements Symmetry elements

E : identity
C2 : Rotation

(xz) mirror plane ' (yz) mirror plane

Character Table

Structure of character table

2v

Name of irreducible representations A1 A 2 B1 B2

Characters of irreducible representations

Character Table C Structure of character table 2 v

v'

+ +

C2

v v'

+ -

The px,py, and pz orbitals on the central atom of a C2v molecule and the symmetry elements of the group.

Character Table

Structure of character table

2v
Irrep is A1 Symmetry is a1
2

pz
2

pz pz

pz
v ( xz )

pz
' v (yz )

pz
=

pz

pz

Character Table

Structure of character table

2v
Irrep. is B2 Symmetry is b2
2

py

= = =

py

py
py

-py
-py
py

v ( xz )
' v (yz )

py

Character Table

Structure of character table

2v
Irrep. is B1 Symmetry is b1
2

px px

= = =

px

-px
px

v ( xz )
' v (yz )

px px

-px

Character Table

Structure of character table

2v
Symmetry is ?

1s2 1s2

= = =

1s2
1s1 1s1

v ( xz )
' v (yz )

1s2
1s2

1s2

Character Table

Structure of character table

2v
Symmetry is ?

1s1 1s1

= =

1s1

1s2

v ( xz )
' v (yz )

1s1 = 1s1 =

1s2
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

2v

1s1

1s2

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

This representation is not reduced

Character Table

Structure of character table

C2 v

Irrep is A1

Symmetry is a1
2

1s+ 1s+ 1s+

= = =

1s+ 1s+

v ( xz )
' v (yz )

1s+ 1s+

1s+ =

Character Table

Structure of character table

C2 v

Irrep. is B1

Symmetry is b1
2

1s
1s

= = =

1s

-1s-1s1s

v ( xz ) 1s
' v (yz )

1s

Character Table

Structure of character table

C2 v

1s+
A1 A1

pz

A1

1s
B1 B2

py

B1

B1

px

Only orbitals with same symmetry label interact

Character Table

Structure of character table

C2 v

Vibrations and normal modes

O

O H H

O H H

Character Table

Structure of character table

C2 v
is a1
O

Symmetry
O

= =

O
O

O O

v ( xz )H
O

O
H

' v (yz )

Character Table

Structure of character table

2v
Symmetry is b1
O O

= = =

O
H

H
O

H
O

v ( xz )
' v (yz )

O H H =

O H H

2v
Vibrations and normal modes

A1

A1

B1

Character Table

3v

We have three classes of symmetry elements :

the identity

Two three fold rotations

-1 C3 and C3

Three mirror planes v , ' v , ' ' v

Character Table

3v

Molecular orbitals of NH3

a1

ex

ey

Normal modes of NH3

What you must learn from this lecture 1. You are not expected to derive any of the theorem of group theory. However, you are expected to use it as a tool 2.. You must understand the different parts of a character table for a symmetry group: (a) Name of symmetry group; (b)Classes of symmetry operators; (c) Names of irreducible symmetry representations. (d) The irreducible characters 3. For simple cases you must be able to deduce what irreducible representation a function or a normal mode belongs to by the help of a character table.

Character Table

Appendix on C3 v

Symmetry operations in the same class are related to one another by the symmetry operations of the group. Thus, the three mirror planes shown here are related by threefold rotations, and the two rotations shown here are related by reflection in v.

Character Table

Appendix on C3 v

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 C3 v

The pz orbital does not change

-1 with E, C3 , C3 v , 'v , "v The symmetry rep. is A1
Y

py px does not change

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

Character Table

Appendix on C3 v

px

p' x

p' ' x
Y

-1 Ep x = p x ; C3p x = p' x ; C3 p x = p"x

Y Y

Character Table

Appendix on C3 v

1 0 p x p y D(E) = p x p y 0 1 The trace is 2 which is also the 3 1 dimension of 2 1 ) = p p 2 px p y D(C3 the representation x y 3 1 2 2

(px

p y D(C3 ) = p x

3 1 py 2 2 3 1 2 2

The trace is - 1 for both matrices

Character Table

Appendix on C3 v

(px
(
)

p y D( v ) = p x

1 0 py 0 1

3 1 2 p x p y D('v ) = p x p y 2 3 1 2 2 3 1 2 p x p y D(" ) = p x p y 2 v 3 1 2 2

The trace is - 1 for both matrices

Character Table

Appendix on C3 v

Typical symmetry -adapted linear combinations of orbitals in a C 3v molecule.