Transformation Matrices

z z
(1,1,1)
y y
i
x x

(-1,-1-,1)

x -1 0 0 x' -1 0 0 x
y 0 -1 0 y' = 0 -1 0 y
z 0 0 -1 z' 0 0 -1 z

transformation
original coord new coord
matrix
 Matrix Math
Number of columns x' x
-1 0 0
in first matrix must y' y
= 0 -1 0
equal number of
z' 0 0 -1 z
rows in the second
Row1 x Column1 x' -1(x) + 0(y) + 0(z)

Row1 x Column2 y' = 0(x) + -1(y) + 0(z)

Row1 x Column3 z' 0(x) + 0(y) + -1(z)

x' -x
y' = -y
z' -z
 E
z z
y y

x do nothing x
O O
H1 H2 H1 H2

x 1 0 0 x' 1 0 0 x
y 0 1 0 y' = 0 1 0 y
z 0 0 1 z' 0 0 1 z

transformation
original coord new coord
matrix
 σ(yz)
z z z
y y y
reflect
x on x x
O yz plane O
H1 H2 H2 H1

x -1 0 0 x' -1 0 0 x
y 0 1 0 y' = 0 1 0 y
z 0 0 1 z' 0 0 1 z

transformation
original coord new coord
matrix
 σ(xz)
z z z
y y y
reflect
x on x x
O xz plane O
H1 H2 H1 H2

x 1 0 0 x' 1 0 0 x
y 0 -1 0 y' = 0 -1 0 y
z 0 0 1 z' 0 0 1 z

transformation
original coord new coord
matrix
 C2
z z
y y
rotate
x x
O 180° O
H1 H2 on z axis H2 H1

x -1 0 0 x' -1 0 0 x
y 0 -1 0 y' = 0 -1 0 y
z 0 0 1 z' 0 0 1 z

transformation
original coord new coord
matrix
 The Set of Operations
E C2 σv(xz) σv(yz)

1 0 0 -1 0 0 1 0 0 -1 0 0
0 1 0 0 -1 0 0 -1 0 0 1 0
0 0 1 0 0 1 0 0 1 0 0 1

traces
3 -1 1 1
Create Irreducible Representations
E C2 σv(xz) σv(yz)

1 0 0 -1 0 0 1 0 0 -1 0 0
0 1 0 0 -1 0 0 -1 0 0 1 0
0 0 1 0 0 1 0 0 1 0 0 1

3 -1 1 1
what happens on x, y, and z... separately
x 1 -1 1 -1
y 1 -1 -1 1
z 1 1 1 1
 Traits of a Character Table

1. order, h is the total number of symmetry operations in the point group

2. classes are the operations that have different characters for their transformation
matrix. If the operations have the same characters they are in the same class(column)

3. The number of irreducible representations equals the number of classes (character

tables are square).

4. the sum of the squares of the dimensions (the characters under E) equals the order of
the group

5. the sum of the squares of the of the characters of an irreducible representation times
the number of operations in the class equals the order of the group (sum after multiplying
the number of operations in the class by the square of the character of the class).

6. irreducible representations are orthogonal: the sum of the products of the characters
(multiplied together for each class) for any two irreducible representations is 0. Take two
irreducible representations, for each class in the irreducible representations multiply the
characters of the class together, sum all of those numbers. The result must be 0.

7. all groups contain an irreducible representation that has all 1’s for each class.
 Traits of a Character Table

1. order, h is the total number of symmetry operations in the point group

C4v E 2 C4 C2 2 σv 2 σd

A1 1 1 1 1 1 z x 2 + y 2 , z2

A2 1 1 1 -1 -1 Rz

B1 1 -1 1 1 -1 x2 – y 2

B2 1 -1 1 -1 1 xy

E 2 0 -2 0 0 (x, y), (Rx, Ry) (xz, yz)

 Traits of a Character Table

2. classes are the operations that have different characters for their transformation
matrix. If the operations have the same characters they are in the same class(column)

C4v E 2 C4 C2 2 σv 2 σd

A1 1 1 1 1 1 z x 2 + y 2 , z2

A2 1 1 1 -1 -1 Rz

B1 1 -1 1 1 -1 x2 – y 2

B2 1 -1 1 -1 1 xy

E 2 0 -2 0 0 (x, y), (Rx, Ry) (xz, yz)

 Traits of a Character Table

3. The number of irreducible representations equals the number of classes (character

tables are square).

C4v E 2 C4 C2 2 σv 2 σd

A1 1 1 1 1 1 z x 2 + y 2 , z2

A2 1 1 1 -1 -1 Rz

B1 1 -1 1 1 -1 x2 – y 2

B2 1 -1 1 -1 1 xy

E 2 0 -2 0 0 (x, y), (Rx, Ry) (xz, yz)

 Traits of a Character Table

4. the sum of the squares of the dimensions (the characters under E) equals the order of
the group

C4v E 2 C4 C2 2 σv 2 σd

A1 1 1 1 1 1 z x 2 + y 2 , z2

A2 1 1 1 -1 -1 Rz

B1 1 -1 1 1 -1 x2 – y 2

B2 1 -1 1 -1 1 xy

E 2 0 -2 0 0 (x, y), (Rx, Ry) (xz, yz)

E.g. 12 + 1 2 + 1 2 + 1 2 + 2 2 = 1 + 2 + 1 + 2 + 2
 Traits of a Character Table

5. the sum of the squares of the of the characters of the irreducible representations times
the number of operations in a class equals the order of the group (sum after multiplying
the number of operations in the class by the square of the character of the class).

C4v E 2 C4 C2 2 σv 2 σd

A1 1 1 1 1 1 z x 2 + y 2 , z2

A2 1 1 1 -1 -1 Rz

B1 1 -1 1 1 -1 x2 – y 2

B2 1 -1 1 -1 1 xy

E 2 0 -2 0 0 (x, y), (Rx, Ry) (xz, yz)

For A2 1•12 + 2•12 + 1•12 + 2•(-1)2 + 2•(-1)2 = 1 + 2 + 1 + 2 + 2

 Traits of a Character Table

6. irreducible representations are orthogonal: the sum of the products of the characters
(multiplied together for each class) for any two irreducible representations is 0. Take two
irreducible representations, for each class in the irreducible representations multiply the
characters of the class together, sum all of those numbers. The result must be 0.

C4v E 2 C4 C2 2 σv 2 σd

A1 1 1 1 1 1 z x 2 + y 2 , z2

A2 1 1 1 -1 -1 Rz

B1 1 -1 1 1 -1 x2 – y 2

B2 1 -1 1 -1 1 xy

E 2 0 -2 0 0 (x, y), (Rx, Ry) (xz, yz)

A1 and A2 1(1•1) + 2 (1•1) + 1 (1•1) + 2 (–1•1) + 2 (-1•1) = 0

 Traits of a Character Table

7. all groups contain an irreducible representation that has all 1’s for each class.

C4v E 2 C4 C2 2 σv 2 σd

A1 1 1 1 1 1 z x 2 + y 2 , z2

A2 1 1 1 -1 -1 Rz

B1 1 -1 1 1 -1 x2 – y 2

B2 1 -1 1 -1 1 xy

E 2 0 -2 0 0 (x, y), (Rx, Ry) (xz, yz)

 We almost have a character table
based on group theory

E C2 σv(xz) σv(yz)
x 1 -1 1 -1
y 1 -1 -1 1
z 1 1 1 1
Since character tables must be square…
We are missing an irreducible representation, and…

The missing irreducible representation must satisfy

the properties of a character table….
 We almost have a character table
based on group theory

For the missing irreducible representation, the following

must be true:
Orthogonality
1 (χE) + -1 (χC2) + 1 (χσ(xz)) + -1 (χσ(yz)) = 0
1 (χE) + -1 (χC2) + -1 (χσ(xz)) + 1 (χσ(yz)) = 0
1 (χE) + 1 (χC2) + 1 (χσ(xz)) + 1 (χσ(yz)) = 0
If only there was a fourth equation…
(χE)2 + (1)2 + (1)2 + (1)2 = 4
1 (χE)2 + 1 (χC2)2 + 1 (χσ(xz))2 + 1(χσ(yz))2 = 4
 We almost have a character table
based on group theory

the missing irreducible representation must be

1 1 -1 -1
E C2 σv(xz) σv(yz)
1 (1) + -1 (1) + 1 (-1) + -1 (-1) = 0
1 (1) + -1 (1) + -1 (-1) + 1 (-1) = 0
1 (1) + 1 (1) + 1 (-1) + 1 (-1) = 0

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

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

 The Character Table for the C2v Point Group

E C2 σv(xz) σv(yz)
A1 1 1 1 1 z x2, y2, z2
A2 1 1 -1 -1 Rz xy
B1 1 -1 1 -1 x, Ry xz
B2 1 -1 -1 1 y, Rx yz