Character Tables

1
 Review
• Character table structure
– Mulliken symbols
– Order
– Basis functions
• Properties of Char. Tables
• Driving the table
– From the rules
– From matrix math

2
 Character Table
Group Symbol
Schönflies symbols

Hermann-Mauguin Symbol
For the 32 crystallographic point groups.
There must be a lecture on different notations of point group/space group 3
 Character Table

Group Symbol Symmetry Elements

Irreducible Characters Basis Functions

Representations

4
 Properties of the Character Table
1. The characters of all matrices belonging to the operations in the same
class are identical in a given irreducible representation.

2. The number of irreducible representations in a group is equal to the

number of classes of that group.

3. There is always a totally symmetric representation for any group.

4. The sum of the squares of the dimensionality of all the irreducible

representations is equal to the order of the group.

5. The sum of the squares of the characters multiplied by the number of

operations in the class equals the order of the group.

6. The sum of the products of the corresponding characters of any two

different irreducible representations of the same group is zero.

5
 Properties of the Character Table
1. The characters of all matrices belonging to the operations in the same
class are identical in a given irreducible representation.

No similar
operations.
Each operation in
its own class.

Rotational Class Reflection Class Rotational Class Reflection Class

6
 Properties of the Character Table
2. The number of irreducible representations in a group is equal to the
number of classes of that group.
4 x 4 table

10 x 10 table
3 x 3 table

7
 Properties of the Character Table
3. There is always a totally symmetric representation for any group.

A, A1, A1g, Ag, A’, A’1, (Σ+, Σg+ for infinity groups) 8
 Properties of the Character Table
4. The sum of the squares of the dimensionality of all the irreducible
representations is equal to the order of the group.
order (h)
h=1+1+1+1=4

dimensionality = character under E

12 + 1 2 + 1 2 + 1 2 = 4

h=1+2+3=6

12 + 1 2 + 2 2 = 6
9
c(E) = characters under E
 Properties of the Character Table
5. The sum of the squares of the characters multiplied by the number of
operations in the class equals the order of the group.

Order = 1 + 1 + 1 + 1 = 4

(1)2(1) + (-1)2(1) + (-1)2(1) + (1)2(1) = 4

Order = 1 + 2 + 3 = 6

(1)2(1) + (1)2(2) + (1)2(3)= 6

(2)2(1) + (-1)2(2) + (0)2(3)= 6

c(R)= characters under an operation

10
gc = the number of operations in a class
 Properties of the Character Table
6. The sum of the products of the corresponding characters of any two
different irreducible representations of the same group is zero.

(1)(1)(1) + (-1)(-1)(1) + (-1)(1)(1) + (1)(-1)(1) = 0

(1)(1)(1) + (1)(1)(2) + (-1)(1)(3) = 0

(2)(1)(1) + (-1)(1)(2) + (0)(-1)(3) = 0

ci(R)= characters for irreducible representation i Irreducible representations

are orthoganal to each other. 11
gc = the number of operations in a class
 Properties of the Character Table
1. The characters of all matrices belonging to the operations in the same
class are identical in a given irreducible representation.

2. The number of irreducible representations in a group is equal to the

number of classes of that group.

3. There is always a totally symmetric representation for any group.

4. The sum of the squares of the dimensionality of all the irreducible

representations is equal to the order of the group.

5. The sum of the squares of the characters multiplied by the number of

operations in the class equals the order of the group.

6. The sum of the products of the corresponding characters of any two

different irreducible representations of the same group is zero.

12
 Example Table
1. Classes are grouped.

2. The table is square.

3. There is always a G = 1 representation.

D4h
4. The sum of the squares under E =
order of the group.

5. The sum of the squares x # of

operations = order of the group.

6. Irreducible reps are orthoganal

S(G1 x G2 x opperation) = 0

13
 Derive the character table

• Open an book or google

– Easy Mode

• From the rules/inspection

– Heroic Mode

• From matrix math

– Legendary Mode

14
 From the Rules: C2v
1. Classes are grouped. Operations: E, C2, σ, σ'
-no groups for C2v

15
 From the Rules: C2v
1. Classes are grouped. Operations: E, C2, σ, σ'
-no groups for C2v
h=1+1+1+1=4
2. The table is square.
-4 x 4 table
G 1
3. There is always a G = 1 representation.
-Easiest step
G 2 d2
G 3 d3
4. The sum of the squares under E =
order of the group. G 4 d4
- Algebra
(1)2 + d22 + d32 + d42 = h = 4
d2 = d3 = d4 = 1 or -1
Under E always positive.

16
 From the Rules: C2v
1. Classes are grouped. Operations: E, C2, σ, σ'
-no groups for C2v
h=1+1+1+1=4
2. The table is square.
-4 x 4 table
G 1
3. There is always a G = 1 representation.
-Easiest step
G 2 e2 e3 e4
G 3
4. The sum of the squares under E =
order of the group. G 4

- Algebra
1(1)2 + 1(e2)2 + 1(e3)2 + 1(e4)2 = h = 4
5. The sum of the squares times # of
operations = order of the group. e2 = e3 = e4 = 1 or -1
- Algebra

17
 From the Rules: C2v
1. Classes are grouped. Operations: E, C2, σ, σ'
-no groups for C2v

2. The table is square.

-4 x 4 table
G 1
3. There is always a G = 1 representation.
-Easiest step
G 2 e2 e3 e4
G 3
4. The sum of the squares under E =
order of the group. G 4

- Algebra e2 = e3 = e4 = 1 or -1

5. The sum of the squares times # of 1(1)(1) + 1(1)(e2) + 1(1)(e3) + 1(1)(e4) = 0

operations = order of the group.
- Algebra (1) + (e2) + (e3) + (e4) = 0
e2 = e3 = e4 = two -1 and one 1
6. Irreducible reps are orthoganal
S(G1 x G2 x opperation) = 0 18
 From the Rules: C2v
1. Classes are grouped. Operations: E, C2, σ, σ'
-no groups for C2v

2. The table is square.

-4 x 4 table
G 1
3. There is always a G = 1 representation.
G 2
-Easiest step
G 3
4. The sum of the squares under E =
order of the group. G 4

- Algebra e2 = e3 = e4 = 1 or -1

5. The sum of the squares times # of 1(1)(1) + 1(1)(e2) + 1(1)(e3) + 1(1)(e4) = 0

operations = order of the group.
- Algebra (1) + (e2) + (e3) + (e4) = 0
e2 = e3 = e4 = two -1 and one 1
6. Irreducible reps are orthoganal
S(G1 x G2 x opperation) = 0 19
 From the Rules: C2v
1. Classes are grouped. Operations: E, C2, σ, σ'
-no groups for C2v

2. The table is square.

-4 x 4 table
G 1
3. There is always a G = 1 representation.
G 2
-Easiest step
G 3
4. The sum of the squares under E =
order of the group. G 4

- Algebra e2 = e3 = e4 = 1 or -1

5. The sum of the squares times # of 1(1)(1) + 1(1)(e2) + 1(-1)(e3) + 1(-1)(e4) = 0

operations = order of the group.
- Algebra (1) + (e2) + -(e3) + -(e4) = 0
e2 = -1 e3 = 1, e4 = -1
6. Irreducible reps are orthoganal or
S(G1 x G2 x opperation) = 0 e3 = -1, e4 = 1 20
 From the Rules: C2v
1. Classes are grouped. Operations: E, C2, σ, σ'
-no groups for C2v

2. The table is square.

-4 x 4 table
G 1
3. There is always a G = 1 representation.
G 2
-Easiest step
G 3
4. The sum of the squares under E =
order of the group. G 4

- Algebra e2 = e3 = e4 = 1 or -1

5. The sum of the squares times # of 1(1)(1) + 1(1)(e2) + 1(-1)(e3) + 1(-1)(e4) = 0

operations = order of the group.
- Algebra (1) + (e2) + -(e3) + -(e4) = 0
e2 = -1 e3 = 1, e4 = -1
6. Irreducible reps are orthoganal or
S(G1 x G2 x opperation) = 0 e3 = -1, e4 = 121
 From the Rules: C2v
1. Classes are grouped. Operations: E, C2, σ, σ'
-no groups for C2v

2. The table is square.

-4 x 4 table
G 1
3. There is always a G = 1 representation.
G 2
-Easiest step
G 3
4. The sum of the squares under E =
order of the group. G 4

- Algebra

5. The sum of the squares times # of

operations = order of the group.
- Algebra
6. Irreducible reps are orthoganal
S(G1 x G2 x opperation) = 0 22
 Character Table
Two-dimensional table compose of elements and irreducible
representations of a point group.

23
 Character Table

Group Symbol Symmetry Elements

Irreducible Characters Basis Functions

Representations
Area II Area I Area III

24
 Mulliken Symbols
A or B: singly degenerate
E: doubly degenerate
T: triply degenerate

A: symmetric (+) with respect to Cn

B: anti-symmetric (-) with respect to Cn

subscript g: symmetric (+) with respect to i

subscript u: anti-symmetric (-) with respect to i

subscript 1: symmetric (+) with respect to ⊥C2 or sv

subscript 2: anti-symmetric (-) with respect to ⊥C 2 or sv

superscript ‘ : symmetric (+) under sh (if no i)

superscript “: anti-symmetric (-) under sh (if no i)

25
Don’t mistake the operation E for the Mulliken symbol E!
 Mulliken Symbols

26
Don’t mistake the operation E for the Mulliken symbol E!
 Mulliken Symbols

⊥C2
D4h

C2h

27
Mulliken Symbols

28
 Infinity Character Tables
Infinity tables us Greek rather than Latin letters.

C∞v D∞h

29
Infinity Character Tables

30
 Order (h)
Order of a group (h) = the number of elements in the group
Symmetry Elements order (h)
h=1+1+1+1=4

D3

h = 1 + 2 + 2 + 2 + 1 + 4 + 4 = 16
h=1+2+3 =6

Infinite groups (C∞v , D∞h ) have a infinite order. 31

 Basis Functions
Basis Functions

linear quadratic
functions, functions
rotations

In the C2v point group

px has B1 symmetry
px transforms as B1
px has the same symmetry as B1
B1 B2 A1 px forms a basis for the B1 irrep
32
 Basis Functions
Basis Functions

linear quadratic
functions, functions
rotations

A1 A1 dxz:
B: Anti symmetric with respect to Cn
sub 1: symmetric with respect to sv
B2 A2 B1

33
 Basis Functions
C4v E 2C4 C2 2 v 2 d
A1 1 1 1 1 1 z x2  y2 , z 2 z2
A2 1 1 1 1 1 Rz
B1 1 1 1 1 1 x2  y2 z( x 2  y 2 )
B2 1 1 1 1 1 xy xyz
E 2 0 2 0 0 ( x, y ), ( Rx , R y ) ( xz , yz ) ( xz 2 , yz 2 ), [ x( x 2  3 y 2 ), y (3 x 2  y 2 )]

linear quadratic cubic

functions functions functions

34
Lanthanide and Actinide coordination chemistry.
 From the Rules: C2v
1. Classes are grouped. Operations: E, C2, σ, σ'
-no groups for C2v

2. The table is square.

-4 x 4 table
G 1
3. There is always a G = 1 representation.
G 2
-Easiest step
G 3
4. The sum of the squares under E =
order of the group. G 4

- Algebra

5. The sum of the squares times # of

operations = order of the group.
- Algebra
6. Irreducible reps are orthoganal
S(G1 x G2 x opperation) = 0 35
From the Rules: C2v
?
G2

G3

G4

36
From the Rules: C2v
A1
G1 = A1
G2

G3

G4

37
From the Rules: C2v
A1
?

G3

G4

38
From the Rules: C2v
A1
A2

39
From the Rules: C2v
A1
A2

B1

B2

40
 From the Rules: C3v
1. Classes are grouped.

A1
2. The table is square.
A2

B1
3. There is always a G = 1 representation.
B2

4. The sum of the squares under E =

order of the group.

5. The sum of the squares times # of

operations = order of the group.

6. Irreducible reps are orthoganal

S(G1 x G2 x opperation) = 0 41
 From Matrix Math
1. Assign/pick a point group
2. Choose basis function
3. Apply operations
4. Generate a representation matrix
5. Apply similarity transformations
6. Generate an irreducible block diagonal matrix
7. Character of the irreducible blocks
8. Fill in the character table
9. Complete the table
10. Assign symmetry labels
11. Assign basis functions 42
 Example 1: H2O (C2v)
1. Assign a point group

Steps 2-11

C2v
Character Table

43
 Example 1: H2O (C2v)
2. Choose a basis function

Cartesian Coordinates of O

44
 Example 1: H2O (C2v)
3. Apply operations
E, C2, sxz, syz
4. Generate a representation matrix

E= C2 = sxz = syz =
45
 Example 1: H2O (C2v)
5. Apply similarity transformations
6. Generate an irreducible block diagonal matrix

E= C2 = sxz = syz =

Block diagonal and single number.

These representations cannot be reduced any further.

46
 Example 1: H2O (C2v)
7. Character of the irreducible blocks

E= C2 = sxz = syz =

8. Fill in the character table

47
 Example 1: H2O (C2v)
9. Complete the table

G1

G2

G3

G4 x
Rule 2) The number of irreducible representations is equal to the number of
classes in the group.
4 classes = 4 irreducible representations. Table must be 4 x 4!
Rule 4) The sum of the squares of the dimensions under E is equal to the
order of the group.
Order = 4, Therefore 12 + 12 + 12 + x2 = 4
48
 Example 1: H2O (C2v)
9. Complete the table

G1

G2

G3

G4 1 e2 e3 e4

Rule 5) The sum of the squares times # of operations = order of the group.

1(1)2 + 1(e2)2 + 1(e3)2 + 1(e4)2 = h = 4

e2 = e3 = e4 = 1 or -1

49
 Example 1: H2O (C2v)
9. Complete the table

G1

G2

G3

G4 1 e2 e3 e4

Rule 6) Irreducible reps are orthoganal S(G1 x G2 x opperation) = 0.

1(1)(1) + 1(-1)(e2) + 1(1)(e3) + 1(-1)(e4) = 0
(1) - (e2) + (e3) - (e4) = 0

e2 = 1, e3 = 1, e4 = 1 or e2 = 1, e3 = -1, e4 = -1 or e2 = -1, e3 = -1, e4 = 1

50
Bonus rule: no two G can be the same.
 Example 1: H2O (C2v)
9. Complete the table

G1

G2

G3

G4 1 1 -1 -1
Rule 6) Irreducible reps are orthoganal S(G1 x G2 x opperation) = 0.
1(1)(1) + 1(-1)(e2) + 1(1)(e3) + 1(-1)(e4) = 0
(1) - (e2) + (e3) - (e4) = 0

e2 = 1, e3 = 1, e4 = 1 or e2 = 1, e3 = -1, e4 = -1 or e2 = -1, e3 = -1, e4 = 1

51
Bonus rule: no two G can be the same.
 Example 1: H2O (C2v)
10.Assign symmetry labels

Symmetry Labels

1 1 -1 -1

52
 Example 1: H2O (C2v)
10.Assign symmetry labels

Rearrange

1 1 -1 -1

53
 Example 1: H2O (C2v)
11.Assign Basis Function x, y, z, Rx, Ry, Rz

xy, xz, yz, x2, y2, z2

54
 Example 1: H2O (C2v)
11.Assign Basis Function x, y, z, Rx, Ry, Rz
z

z 1 1 1 1

Start with z or pz:

E
C2
sxz
syz
If the orbital/vector stays the same = 1
If the sign/arrow direction flips = -1 55
 Example 1: H2O (C2v)
11.Assign Basis Function x, y, Rx, Ry, Rz
z

x 1 -1 1 -1

x or px:

E, sxz

C2, syz

56
 Example 1: H2O (C2v)
11.Assign Basis Function y, Rx, Ry, Rz
z

x
y
y 1 -1 -1 1

y or py:

E, syz

C2, sxz

57
 Example 1: H2O (C2v)
11.Assign Basis Function Rx, Ry, Rz
z
Rz
x
y
Rz 1 1 -1 -1 z
z
R z:
y

z E, C2 x

y z
syz, sxz
x
y

Rotation direction unchanged = 1 x

Rotation direction flips = -1 58
 Example 1: H2O (C2v)
11.Assign Basis Function Rx, Ry
z
Rz
x
y, Rx
Rx 1 -1 -1 1 z

Rx:
y

z E, syz x

x y z
C2, sxz
x
y
Rotation direction unchanged = 1 x
Rotation direction flips = -1 59
 Example 1: H2O (C2v)
11.Assign Basis Function Ry
z
Rz
x, Ry
y, Rx
Ry 1 -1 1 -1 z

Ry :
y
z
y E, sxz x

y z
C2, syz
x
y
Rotation direction unchanged = 1 x
Rotation direction flips = -1 60
 Example 1: H2O (C2v)
11.Assign Basis Function
z
Rz
xy, xz, yz, x2, y2, z2
x, Ry
y, Rx yz
yz 1 -1 -1 1 z

yz or dyz:
y
z
z
E, syz x
y
y z
x C2, sxz
x
y

If the orbital is unchanged = 1 x

61
If the orbital sign flips = -1
 Example 1: H2O (C2v)
11.Assign Basis Function
z x2, y2, z2
Rz xy
x, Ry xz
y, Rx yz

xz or dxz: xy or dxy: s orbital (x2, y2, z2):

z

B1 A2 A1 62
 C2v Char. Table from Matrix Math
1. Assign/pick a point group
2. Choose basis function
3. Apply operations
4. Generate a representation matrix
5. Apply similarity transformations
6. Generate an irreducible block diagonal matrix
7. Character of the irreducible blocks
8.
9.
Fill in the character table
Complete the table
C2v
10. Assign symmetry labels
11. Assign basis functions

z x2, y2, z2
Rz xy
x, Ry xz
y, Rx yz 63
 Example 2: NH3 (C3v)
1. Assign a point group

Steps 2-11

C3v
Character Table

64
 Example 2: NH3 (C3v)
2. Choose a basis function

C A
B
Hydrogen Atoms (A, B, C)

65
 Example 2: NH3 (C3v)
3. Apply operations
E, C3, C32, sv, sv’, sv”
4. Generate a representation matrix
Starting Position
A B C
A’
Ending
C3 Position B’
C’

C3 Representation Matrix 66
 Example 2: NH3 (C3v)
3. Apply operations
E, C3, C32, sv, sv’, sv”
4. Generate a representation matrix

E sv

C3 s v’

C32 sv’’
67
 Example 2: NH3 (C3v)
5. Apply similarity transformations
6. Generate an irreducible block diagonal matrix

Irreducible Matrix Reducible Matrices

sv
E
C3
s v’
C32
Matrix must be reduced down to either
blocks of 1x1 matrices or a matrix that sv’’
68
cannot be reduced further.
 Example 2: NH3 (C3v)
5. Apply similarity transformations
n-1 • A • n = A’
A is a matrix representation for some type of symmetry operation
n is a similarity transform operator
n-1 is the transpose of the similarity transform operator
A’ is the product matrix

A A’

n-1 • •n =

non-block block
diagonal diagonal
69
 Example 2: NH3 (C3v)
5. Apply similarity transformations
n-1 • A • n = A’

AC =
3

70
 Example 2: NH3 (C3v)
5. Apply similarity transformations
n-1 • A • n = A’
A’
A1

A2
Irreducible Matrix!

n2-1 • A2 • n2 = A2

71
 A1

Transformation

A2
Irreducible Matrix!
Trace =0 Trace =0
3x3 matrxi 3x3 matrxi

72
 Example 2: NH3 (C3v)
5. Apply similarity transformations
n-1 • A • n = A’

73
 Example 2: NH3 (C3v)
5. Apply similarity transformations
6. Generate an irreducible block diagonal matrix

E sv

Irreducible Matrices
C3 s v’
Block Diagonal Matrices

C32 sv’’
74
 Example 2: NH3 (C3v)
7. Character of the irreducible blocks
1
1 1
E 2
C32 sv 0
-1

1 1 1
C3 -1 sv’’ s v’ 0
0

8. Fill in the character table

Group Similar
Classes
(C3, C32)
75
gamma = general label for a rep. (sv, sv’, sv”)
 Example 2: NH3 (C3v)
9. Complete the table

G1 1 1 1
G2 2 -1 0
G3 x

Rule 2) The number of irreducible representations is equal to the number of

classes in the group.
3 classes = 3 irreducible representations. Table must be 3 x 3!
Rule 4) The sum of the squares of the dimensions under E is equal to the
order of the group.
Order = 6, Therefore 12 + 22 + x2 = 6

76
 Example 2: NH3 (C3v)
9. Complete the table

G1 1 1 1
G2 2 -1 0
G3 1 e2 e3

Rule 5) The sum of the squares times # of operations = order of the group.

1(1)2 + 2(e2)2 + 3(e3)2 = h = 6

e2 = e3 = 1 or -1

77
 Example 2: NH3 (C3v)
9. Complete the table

G1 1 1 1
G2 2 -1 0
G3 1 e2 e3

Rule 6) Irreducible reps are orthoganal S(G1 x G2 x opperation) = 0.

1(1)(1) + 2(1)(e2) + 3(1)(e3) = 0
1 + 2e2 + 3e3 = 0
e2 = 1, e3 = -1

78
 Example 2: NH3 (C3v)
9. Complete the table

G1 1 1 1
G2 2 -1 0
G3 1 e2 e3

Rule 6) Irreducible reps are orthoganal S(G1 x G2 x opperation) = 0.

1(1)(1) + 2(1)(e2) + 3(1)(e3) = 0
1 + 2e2 + 3e3 = 0
e2 = 1, e3 = -1

79
 Example 2: NH3 (C3v)
10.Assign symmetry labels

G1 1 1 1
G2 2 -1 0
G3 1 1 -1

Symmetry Labels

80
 Example 2: NH3 (C3v)
10.Assign symmetry labels

A1 1 1 1
E 2 -1 0
A2 1 1 -1

Rearrange

81
 Example 2: NH3 (C3v)
11.Assign Basis Function

xy, xz, yz,

x, y, z, Rx, Ry, Rz z2, x2-y2

82
 Example 2: NH3 (C3v)
11.Assign Basis Function

z, Rz
z

83
 Example 2: NH3 (C3v)
11.Assign Basis Function

x, y, Rx, Ry

py px
px and py are neither symmetric nor antisymmetric with
respect to the C3 operations, but rather go into linear
combinations of one another and must therefore be
considered together as components of a 2 dimensional 84
representation.
 Example 2: NH3 (C3v)
11.Assign Basis Function

xy, xz, yz,

z2, x2-y2

85
 Example 2: NH3 (C3v)
11.Assign Basis Function

86