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Example 1 of Matrix Multiplication

In the first example we multiply two 2x2 matrices, meaning that they both have two rows and two columns (Fig. 2.3.2). First,
we need to check if the two matrices can be multiplied. We can see that the number columns of the first matrix is 2, and the
number of rows of the second matrix is also 2. Therefore, we can multiply the two matrices.

Figure 2.3.2 Example 1 of matrix multiplication

The product matrix is expected to be also a 2x2 matrix. Now we need to multiply the first row of the first matrix with the first
column of the second matrix, and that means that we to multiply 1x7 and 5x4. The sum of 1x7+5x4=27 gives us the first
character of the first row of the product matrix. Next, we multiply the first row of the first matrix with the second column of the
second matrix. So we have to multiply 1x3 and 5x8. The sum of the two products gives the second character of the first row of
the product matrix. Because the second matrix has no additional column, there is no further column with which the first row of
the first matrix could be multiplied. Therefore, we now go to the second row of the first matrix, and multiply it with the first
column of the second matrix. This gives the products 2x7 and 6x4. When added together, then this gives 38, and this is now the
first character of the second row of the product matrix. Lastly, we multiply the second row of the first matrix with the second
row of the second matrix. This gives 2x3 and 6x8 which gives 54 when added together. This is the second character in the
second row of the product matrix.

Example 2 of Matrix Multiplication

In the next example, we multiply a 1x3 matrix with a 3x3 matrix (Fig. 2.3.3). This is possible because the number of the columns
of the second matrix is 3, and the number of rows of the second matrix is also 3.

Figure 2.3.3 Example 2 of matrix multiplication

The product matrix would be expected to have one row and three columns. The first matrix has only one row, so we multiply it
with the three columns of the second matrix. Multiplying the first row of the first matrix with the first column of the second
matrix gives (1)(1) + (2)(0) + (3)(0) = 1. This is the first character in the first, and only row in the product matrix. The
multiplication of the first row of the first matrix with the second column of the second matrix is (1)(0) + (2)(-1) + (3)(0) = -2
which is the second character of the first row of the product matrix. The multiplication of the first row of the first matrix with
the third column of the second matrix gives (1)(0) + (2)(0) + (3)(1) = 3. This is the third character of the first row of the product
matrix. Overall, the product matrix is [1 -2 3].

Example 3 of Matrix Multiplication

In the last example let us multiply a 3x3 matrix with a 3x1 matrix (Fig. 2.3.4). Again, the number of the columns of the first
matrix is the same as the number of the rows of the second matrix, they are both 3. Thus, we can multiply the two matrices.

Figure 2.3.4 Example 3 of matrix multiplication

Multiplying the first row of the first matrix with the first, and in this case only column of the second matrix gives 1x1 + 0x2 +
0x3 = 1. This is the first and only character of the first row of the product matrix. The second matrix has only one column,

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therefore we multiply the second row of the first matrix with the only column of the second matrix in the next step. This gives
0x1 + (-1)x2 + 0x3 = -2. This the character of the second row of the product matrix. Lastly, we multiply the third row of the first
matrix with the column of the second matrix. This gives 0x1 + 0x2 + 1x3 = 3. This is the character of the third row of the product
matrix.

Applying Matrix Multiplications to Symmetry Operations

So what do symmetry operations have to do with the multiplication of matrices? The answer is that a symmetry operation can
be described as a matrix, and the multiplication of this matrix with the matrix that represents the coordinates of the position of
the points in an object, will give the new coordinates of the object after the symmetry operation has been carried out (Fig. 2.3.5).

Figure 2.3.5 Relationships between symmetry operations and matrices

Example H2O
A matrix that represents a symmetry operation is a 3x3 matrix and the matrix that describes coordinates is a 3x1 matrix. When
two are multiplied then this gives a 3x1 matrix that describes the new coordinates of the object. For example, let us look at the
water molecule H2O.

Figure 2.3.6 Transformation of coordinates in H2O upon application of the C2 symmetry operation
We can define a coordinate system in the water molecule so that the molecule is within the xz plane, whereby the z-axis is
chosen so that it bisects the H-O-H bond angle. The y-axis would stand perpendicular and point into the board plane (Fig.
2.3.6). Any point within the water molecule, would have coordinates x,y,z that are defined by vectors  ,  ,   that point to these
coordinates. For example, the center of a particular hydrogen atoms would have specific coordinates that would be described
by three vectors that when added up, would point to the center of the hydrogen atom. Now let us think how the coordinates
will change as we carry out a specific symmetry operations. For instance, take the C2 symmetry operation that is carried out
around the z-axis. How will the rotation change, the x,y, and z coordinates, respectively?
The x-coordinate is defined by a vector pointing into x-direction. As we rotate this vector 180° around the z-axis, it will retain its
length but will point into the opposite direction (Fig. 2.3.6). Hence, we can say that the coordinate x has changed its algebraic
sign, and is now –x. Now what about the y-coordinate? A vector pointing into y-direction will also be rotated around 180°, and
point into the opposite direction. That means it is –y after the execution of the symmetry operation. Finally, how will the z-
coordinate change? Because we rotate around z, there will not be any change to the z-vector, and thus the new coordinate z will
be identical to the old coordinate z. If we represent the three vectors of the old coordinates by a 3x1 matrix  ,  ,    , the new
coordinates of the matrix  ',  ',  ' are represented by the matrix - ,-  ,   . The matrix that when multiplied with the matrix for the
old coordinates gives the matrix for the new coordinates, would be the matrix that would represent the symmetry operation C2.
In the case of the C2 symmetry operation the matrix has the form below (Fig. 2.3.7).

Figure 2.3.7 C2 symmetry operation for H2O in matrix form

We can show that this matrix correctly represents the symmetry operation C2 by applying the multiplication rules for matrices.
Multiplying the first row of the matrix for C2 with the only column of the matrix for the old coordinates would give (-1 x  ) + (0
x  ) + (0 x  ) = -   for the first character of the product matrix. Multiplying the second row of the matrix representation of C2with
the only column of the matrix for the old coordinates gives (0 x  ) + (-1 x  ) + (0 x  ) = -   for the second character of the product
matrix. Multiplication of the third row of the matrix for C2 with the column of the matrix for the old coordinates gives (0 x  ) +(0
x  ) + (1 x  ) =   This proves that the matrix correctly represents the symmetry operation C2.

Figure 2.3.8 The symmetry operation C2 in matrix form transforming the coordinates in H2O

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We can develop the matrix representation for the σ(xz) reflection operation along the same line we did for the C2 operation. Let
us first think about how the vectors representing the coordinate changes as the reflection operation is carried out. The vectors 
and   do not change because they are within the xz mirror plane. However, the  vector changes its direction as it is reflected to
the other side of the mirror plane. Thus, the y-coordinate changes its algebraic sign.

Figure 2.3.9 Transformation of coordinates of H2O upon the application of the σxz symmetry operation
The matrix representing the new coordinates therefore has the form  , -  ,   . The matrix that when multiplied with the matrix of
the old coordinates, gives the matrix of the new coordinates must be the matrix representing the symmetry operation σxz. It has
the form below (Fig. 2.3.10).

Figure 2.3.10 σxz symmetry operation in H2O in matrix form

We could again show using the multiplication rules for matrices that multiplication of this matrix with the matrix for the old
coordinates gives the matrix for the new coordinates (Fig. 2.3.11).

Figure 2.3.11 the symmetry operation for σxz in matrix form transforming the coordinates of H2O.
We can apply the same process for the σ(yz) symmetry operation. The σ(yz) mirror plane contains the coordinates y and z, and
thus their vectors do not change upon the application of the symmetry operation. However, the vector   changes its direction
upon reflection at the yz plane, and thus the algebraic sign of the x-coordinate changes (Fig. 2.3.12).

Figure 2.3.12 Transformation of the coordinates in H2O upon the application of the σyz symmetry operation
The matrix for the new coordinates is thus - ,  ,   . In this case the matrix that when multiplied with the matrix of the old
coordinates  ,  ,   gives the matrix with the new coordinates - ,  ,   has the form below (Fig. 2.3.13).

Figure 2.3.13 σyz symmetry operation in H2O in matrix form

We could again use the multiplication rules for matrices to show that the above matrix is the correct matrix representation of
the symmetry operation σ(yz), Fig. 2.3.14.

Figure 2.3.14 The multiplication of the σyz operation in matrix form with the coordinates of H2O produces the new coordinates
for H2O

Figure 2.3.15 Transformation of the coordinates of H2O by the E symmetry operation

Lastly, we can also determine the matrix representation of the identity operation (Fig. 2.3.15). It has the form below (Fig. 2.3.16).
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Figure 2.3.16 E symmetry operation in H2O in matrix form

Like previously, we could use the multiplication rules to show that this matrix produces the correct matrix for the new
coordinates. Since the identity does nothing to an object (Fig. 2.3.15), the new coordinates are the same as the old coordinates
(Fig. 2.3.17).

Figure 2.3.17 Multiplication of the symmetry operation E  for H2O with the coordinates of H2O produces the correct, new
coordinates for H2O

Reducible and Irreducible Representations

Let us look closer at the four matrices that we just derived (Fig. 2.3.18).

Figure 2.3.18 The four matrices for the symmetry operations in the point group C2v
It is noteworthy that all characters are zero, except those on a diagonal that goes from the top left corner in the matrix to the
bottom right corner. This diagonal is called the trace of the matrix. With good justification we can say that the characters on the
trace of the matrix tell us what the symmetry operation does with a coordinate. If it is a -1 the algebraic sign of the coordinate
changes, if it is +1, it does not. If we write the characters of the trace of the matrices that belong to a specific coordinate on a line
underneath the symmetry operations, we get what is called an irreducible representation for the specific coordinate (Fig. 2.3.19).

Figure 2.3.19 The irreducible and reducible representations associates with the coordinates in H2O
For example, for the x-coordinate the characters of the traces of the matrices for the symmetry operations E, C2, σyz, σxz, are 1,
-1, -1, and 1, respectively. For the y-coordinate the characters would be 1, -1, 1, and -1, and for the z- coordinate they are 1, 1, 1,
and 1. The use of an irreducible representation is that it tells us directly in a concise form what the symmetry operations do to a
specific coordinate. The sum of two or more irreducible representations is a so-called reducible representation. If we sum up the
three irreducible representations of Fig. 2.3.19, then this gives a reducible representation with the characters 1+1+1=3, (-1)+
(-1)+1=-1, (-1)+1+1=1, and 1+(-1)+1=1. We will see about the use of reducible representations in a little bit.

Symmetry Types of Irreducible Representations

The specific characters in an irreducible representation determine the symmetry type of the irreducible representation. It is
denoted by a capital letter with subscripts and/or superscripts. For example the irreducible representation for the x-coordinate
is of the type B1 (Fig. 2.3.20)

Figure 2.3.20 Symmetry types of of the irreducible representations associated with the coordinates of H2O
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B means that the symmetry is anti-symmetric with regard to the principal axis (Fig. 2.3.21).

Figure 2.3.21 The definition of the B irreducible representation

Anti-symmetric means that the algebraic sign of the coordinate changes as we rotate. In this case the principal axis is the C2axis.
We can see that the algebraic sign changes because the character of the irreducible representation for the x-coordinate
underneath C2 is -1. The subscript 1 means that the representation is symmetric to a C2 perpendicular to the principal axis, or if
lacking to a vertical σv (Figure 2.3.22)

Figure 2.3.22 The definition of the subscript 1 in an irreducible representation

In this case, we do not have a C2 perpendicular to the C2 which is our principal axis, but we have two vertical mirror planes.
Symmetric means that the coordinate does not change its algebraic sign as the symmetry operation is carried out. We can see
that this is true for the reflection with the lower number of primes which comes first in our considerations. It is indicated by the
character +1 underneath the symmetry operation.
The irreducible representation of the y-coordinate has the symmetry type B2 (Fig.2.3.20) The symmetry type is again B, because
the character underneath C2 is -1. The subscript is 2 in this case, and this means that the representation is antisymmetric to a
C2perpendicular to the principal axis or, if lacking to a vertical plane σv (Fig. 2.3.23)

Figure 2.3.23 The definition of the subscript 2 in the irreducible representation

We can see that the σv(xz) is anti-symmetric as indicated by the character -1 in the irreducible representation. Lastly, let us look
at the symmetry type of the irreducible representation for the z-coordinate which is A1 (Fig. 2.3.20) A means symmetric with
regard to rotation around the principle axis (Fig. 2.3.24).

Figure 2.3.24 The definition of the A irreducible representation

We can confirm the symmetric situation for the rotation around z by verifying that the character underneath the principal axis
C2 is +1.

Symmetry Types of Orbitals

Irreducible representations are more powerful than only telling you the symmetry type of a specific coordinate in a point
group. More generally, they can tell the symmetry type of a mathematical function in a specific point group. Remember, that
orbitals are mathematically wave functions. Thus, it should be possible to assign orbitals to a symmetry type within a given
point group. Let us look for example, at the 2s and the 2p orbitals of the oxygen atom in the water molecule. Let us consider the
2s orbital first, and determine what the symmetry operations do with it. We can see that no symmetry operation changes the 2s
orbital in any way, thus all characters of the irreducible representation that belongs to the orbital should be +1. We can see that
this is only the case for the irreducible representation with the symmetry type A1. Therefore we can say that the 2s orbital of the
O-atom in the water molecule has the symmetry type A1 (Fig. 2.3.25).

Figure 2.3.25 The 2s orbital of the O-atom in the water molecule has the symmetry type A1
Next, let us determine the symmetry type of the 2pz orbital. The 2pz orbital is oriented along the z-axis around which we rotate.
When carrying a C2 operation we can see that this operation does not make any changes to the orbital. The same is true for the
two reflection operations. Again, we can see that the symmetry operations do not change the 2pz  orbital in any way, and
therefore it also must belong to the symmetry type A1 (Fig. 2.3.26)

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Figure 2.3.26 The 2pz orbital of the O-atom in the water molecule has the symmetry type A1
For the 2px  orbital the situation is different though (Fig. 2.3.27). We can see that rotating around the C2  axis changes the
algebraic sign of the orbital. This means that the 2px orbital should belong to a symmetry type which has a character of -1 for
the C2 operation. We can see that this can be the B1 or the B2 symmetry type, but not A1. This rules out the A1 symmetry type.
We still need to decide if the symmetry type is B1 or B2. For B1 reflection at the σv(xz) mirror plane would need to be symmetric,
and for B2 it would need to be anti-symmetric. We can see that the orbital does not change when we carry out the σv (xz)
reflection, and thus the symmetry type must be B1.

Figure 2.3.27 The 2px orbital of the O-atom in the water molecule having the symmetry type B1
Lastly let us determine the symmetry type of the 2py orbital (Fig. 2.3.28). The 2py orbital is oriented perpendicular to the paper
plane, the blue lobe points to the front, and the orange one, hardly visible points to the back. We can see that when we rotate
around 180° the orange lobe points to the front, and the blue one points to the back. That means that the wave function of the
orbital has changed its algebraic sign. Therefore, it must be of B symmetry type. Which one is it? B1 or B2? We can see that in
this case the σv(xz) does change the algebraic sign of the wave function because the front lobe of the orbital gets reflected to the
back, and the lobe in the back gets reflected to the front. Thus, it is antisymmetric with respect to σv(xz) and thus it must belong
to the symmetry type B2.

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