CHE2107: Inorganic Chemistry

Chapter 4. Symmetry and Group Theory

박계현 (Jesse Park)

Yonsei University
 Announcement
• No class on 4/16 (대한화학회)

• Midterm exam
• Date: 4/21 Tuesday
• Time: 11 am – 1 pm
• Location: 과학관 B133
• Chapters 1~4
 4.1 Symmetry Elements and Operations
• Symmetry is a phenomenon of the
natural world, as well as the world
of human invention.
• In nature, many flowers and plants,
snowflakes, insects, certain fruits
and vegetables, and a wide variety
of microscopic plants and animals
exhibit characteristic symmetry.
• Many engineering achievements
have a degree of symmetry that
contributes to their esthetic appeal.
• Examples include cloverleaf
intersections, the pyramids of
ancient Egypt, and the Eiffel Tower.
 4.1 Symmetry Elements and Operations
• All molecules can be described in terms of their symmetry, even if it has
none.
• Molecules or any other objects may contain symmetry elements such as mirror
planes, axes of rotation, and inversion centers.
• The actual reflection, rotation, or inversion is called a symmetry operation.
• To contain a symmetry element, a molecule must look identical before and
after the operation.
• If a symmetry operation yields a molecule that can be distinguished from the
original in any way, that operation is not a symmetry operation of the molecule.
 4.1 Symmetry Elements and Operations
• The identity operation (E) causes no change in the molecule.
• An identity operation is characteristic of every molecule, even if it has no other
symmetry.
 4.1 Symmetry Elements and Operations
• The rotation operation (Cn), also called proper rotation, is 360º/n rotation about
a rotation axis.
• We use counterclockwise rotation as a positive rotation.
• An example of a molecule having a threefold (C3) axis is CHCl3.
 4.1 Symmetry Elements and Operations
• The rotation axis is coincident with the C-H bond axis, and the rotation angle is
360º/3 = 120º.
• Two C3 operations (C32) may be performed consecutively to give a new rotation
of 240º, and is also a symmetry operation of the molecule.
• Three successive C3 operations are the same as the identity operation (C33 ≡ E).
• The identity operation (E) causes no change in the molecule.
• An identity operation is characteristic of every molecule.
 4.1 Symmetry Elements and Operations
• Many molecules and other objects
have multiple rotation axes.
• For example, snowflakes exhibit
complex shapes that are hexagonal
and approximately planar.
• The rotation axis perpendicular to the
plane of the flake contains a twofold
(C2) axis, a threefold (C3) axis, and a
sixfold (C6) axis.
• Rotations by 240º (C32) and 300º
(C65) are also symmetry operations of
the snowflake.
• An identity operation is characteristic
of every molecule, even if it has no
other symmetry.
 4.1 Symmetry Elements and Operations
• There are also two sets of three C2
axes in the plane of the snowflake,
one set through opposite points and
one through the cut-in regions
between the points.
• With more than one rotation axis,
the largest Cn axis is the highest
order rotation axis or principal axis.
• The highest order rotation axis for a
snowflake is the C6 axis. (Chosen as
the z axis.)
 4.1 Symmetry Elements and Operations
• When necessary, the C2 axes
perpendicular to the principal axis
are designated with primes.
• A single prime (C2’) indicates that the
axis passes through several atoms
of the molecule, whereas a double
prime (C2”) indicates that it passes
between the outer atoms.
 4.1 Symmetry Elements and Operations
• Finding rotation axes for some three-dimensional figures can be more difficult but
the same in principle.
• Nature can be extraordinary when it comes to symmetry—the lowest energy
isomer of gas phase TaB10− has a ten-fold rotation axis!
 4.1 Symmetry Elements and Operations
• In the reflection operation () the molecule
contains a mirror plane.
• The human body has a left–right mirror
plane.
• Many molecules have mirror planes, too.
• The reflection operation exchanges left and
right.
• Linear objects, such as a round wood
pencil, or molecules, such as acetylene and
carbon dioxide, have an infinite number of
mirror planes that include the center line of
the object.
 4.1 Symmetry Elements and Operations
• When the plane is perpendicular to the principal axis of rotation, it is called h
(horizontal).
• Planes that contain the principal axis of rotation, are labeled v or d.
 4.1 Symmetry Elements and Operations
• Some molecules have an inversion center.
• Methane and other tetrahedral molecules lack inversion symmetry (i).
• The orientation of the molecule following the i operation differs from the original
orientation.
• On the other hand, inversion is a symmetry operation of ethane.
 4.1 Symmetry Elements and Operations
• Squares, rectangles, parallelograms, rectangular solids, octahedra, and
snowflakes have inversion centers.
• Tetrahedra, triangles, and pentagons do not have inversion centers.
 4.1 Symmetry Elements and Operations
• Rotation-reflection operation (Sn), or improper rotation, requires 360º/n rotation
followed by reflection through a horizontal mirror plane (h).
• For example, methane had a S4 axis bisecting H-C-H or two tetrahedron edges.
• The operation requires a 90° rotation, followed by reflection through h.
• There are three S4 axes bisecting a pair of opposite edges (total of 6 edges).
• In methane, two S4 operations are equivalent to a C2
• In methane, two Sn operations is equivalent to a Cn/2 operation.
 4.1 Symmetry Elements and Operations
• Molecules sometimes have an Sn axis that is coincident with a Cn axis.
• For example, in addition to the rotation axes, snowflakes have S2 (≡ C2/2 or i), S3,
and S6 axes coincident with the C6 axis.
 4.1 Symmetry Elements and Operations
• Note that an S1 operation is equivalent to a h reflection, and an S2 operation
is equivalent to inversion.
• The i and  notations are preferred in these cases!
 4.1 Symmetry Elements and Operations
• Symmetry elements and operations
are summarized in Table 4.1.
 4.2 Point Groups
• Each molecule has a set of symmetry operations that describes the
molecule's overall symmetry.
• This set of symmetry operations is called the point group of the molecule.
 4.2 Point Groups
• A sequence of steps allows systematic
deduction of point groups.
• 1. Determine whether the molecule
exhibits low symmetry (C1, Cs, Ci) or
high symmetry (Td, Oh, Cꝏv, Dꝏh or Ih).
• 2. If not, find the principle rotation axis,
the highest order Cn axis, for the
molecule.
• 3. Does the molecule have any C2 axes
perpendicular to the principal Cn axis?
• If yes, the molecule is in the D set of
groups.
• If no, it is in the C or S set.
 4.2 Point Groups
• 4. Does the molecule have a h, mirror
plane perpendicular to the principal axis?
• If yes, it is classified as Cnh or Dnh.
• If no, continue with Step 5.
• 5. Does the molecule have v or d, any
mirror planes that contain the principal Cn
axis?
• If yes, it is classified as Cnv or Dnd.
• If no and in the D set, it is classified
as Dn.
• If no and in the C or S set, continue
with Step 6.
• 6. Is there an S2n axis collinear with the
principal Cn axis?
• If yes, it is classified as S2n.
• If no, the molecule is classified as Cn.
 4.2 Point Groups
• Let’s try assigning point groups to the molecules below.
 4.2.1 Groups of Low and High Symmetry
• 1. Determine whether the molecule belongs to one of the special cases of
low or high symmetry.
• Inspection of the molecule will determine if it fits one of the low-symmetry cases.
• These groups have few or no symmetry operations and are described in Table 4.2
 4.2.1 High Symmetry
• Molecules with many
symmetry operations may fit
one of the high-symmetry
cases of linear, tetrahedral,
octahedral, or icosahedral
symmetry with the
characteristics described in
Table 4.3.

• Linear molecules with a

center of inversion have
Dꝏh symmetry.
• Those without an inversion
center have Cꝏv symmetry.
 4.2.1 High Symmetry
• For high symmetry point
groups Td, Oh, and Ih, it is
helpful to note the Cn axes.
• Molecules with Td symmetry
have only C3 and C2 axes.
 4.2.1 High Symmetry
• For high symmetry point
groups Td, Oh, and Ih, it is
helpful to note the Cn axes.
• Those with Oh symmetry
have C4 axes in addition to
C3 and C2
 4.2.1 High Symmetry
• For high symmetry point
groups Td, Oh, and Ih, it is
helpful to note the Cn axes.
• Ih molecules have C5, C3,
and C2 axes.
 4.2.2 Other Groups
• 2. Find the rotation axis with the highest n, the highest order Cn (or
principal) axis for the molecule.
• The rotation axes for the examples are shown below.
• With many equivalent rotation axes, choose any one of them as the principal axis.
 4.2.2 Other Groups
• 3. Does the molecule have any C2 axes perpendicular to the principal Cn
axis?

• If, Yes: D groups

• Molecules with C2 axes perpendicular to the principal axis are in one of the
groups designated by the letter D.

D group
 4.2.2 Other Groups
• 3. Does the molecule have any C2 axes perpendicular to the principal Cn
axis?

• If No: C or S groups
• Molecules with no perpendicular C2 axes are in one of the groups designated by
the letters C or S .

C or S
group

D group
 4.2.2 Other Groups
• 4. Does the molecule have a mirror plane (h horizontal plane) perpendicular
to the principal Cn axis?
• D Groups

• If Yes: Dnh

• If No: Dn or Dnd

Dn or Dnd group
 4.2.2 Other Groups
• 4. Does the molecule have a mirror plane (h horizontal plane) perpendicular
to the principal Cn axis?
• C and S Groups

• If Yes: Cnh

• If No: Cn or Cnv or S2n

Cn or Cnv or S2ngroup
 4.2.2 Other Groups
• 5. Does the molecule have any mirror planes that contain the principal C n
axis?
• D Groups

• If Yes: Dnd

• If No: Dn
 4.2.2 Other Groups
• 5. Does the molecule have any mirror planes that contain the principal C n
axis?
• C and S Groups

• If Yes: Cnv

• If No: Cn or S2n
Cn or S2ngroup
 4.2.2 Other Groups
• 6. Is there an S2n axis collinear with the principal Cn axis?
• C and S Groups

• If Yes: S2n

• If No: Cn
 4.2.2 Other Groups
• As practice, try finding the point groups for the examples in Table 4.4 .
 4.2.2 C Versus D Point Group Classifications
• All molecules having either C or D classifications must have a Cn axis.
• If more than one Cn axis is found, the principal axis (largest value of n) is used
as the reference axis and oriented vertically along z axis.
 4.2.2 Groups Related to Ih, Oh, and Td Groups
• The high-symmetry point groups Ih, Oh, and Td are ubiquitous in chemistry and
are represented by the classic molecules C60, SF6, and CH4.
• These point groups can be further classified into I, O, and T rotational
subgroups that only have identity operation and proper axes of rotation.
 4.2.2 Groups Related to Ih, Oh, and Td Groups
• One more high-symmetry Th point group is derived by adding a center of
inversion to the T point group.
• Adding i generates the symmetry operations S6, S65, and h.

• Th symmetry is known for only a few molecules.

• I, O, and T symmetry are rarely encountered in chemistry.

 4.3 Properties and Representations of Groups
• All mathematical groups, including point groups, must have certain properties.
• These properties are listed and illustrated in Table 4.6, using the symmetry
operations of NH3 as an example.
 4.3.1 Matrices
• Important information about the symmetry aspects of point groups is
summarized in character tables. (described later)
• To understand the character tables, we must consider the properties of matrices.
• A matrix is an ordered array of numbers, such as
 4.3.1 Matrices
• While the properties of the symmetry operations that comprise a group can be
examined by using a molecule or use of matrices that define the operations.
• To multiply matrices, the number of vertical columns of the first matrix must
be equal to the number of horizontal rows of the second matrix.
 4.3.1 Matrices
• To find the product, multiply each row of the first matrix by each column of the
second and add them together.
• Place the resulting sum in the product matrix with the row determined by the row
of the first matrix and the column determined by the column of the second matrix.
4.3.1 Matrices
 4.3.2 Symmetry Operations: Matrix Representations
• We will now consider how the C2v point group symmetry operations transform
a set of x, y, and z coordinates.
• The water molecule possesses C2v symmetry.
• It has a C2 axis through the oxygen and in the plane of the molecule, no
perpendicular C2 axes, and no horizontal mirror plane.
• But it does have two vertical mirror planes.
 4.3.2 Symmetry Operations: Matrix Representations
• The z axis is usually chosen as the principle axis.
• For H2O, this is the only rotational axis.
• The other axes are arbitrary.
• We will use the xz plane as the plane of the molecule.
 4.3.2 Symmetry Operations: Matrix Representations
• Each symmetry operation can be expressed as a transformation matrix as
follows:
[New coordinates] = [transformation matrix] [old coordinates]
 4.3.2 Symmetry Operations: Matrix Representations
• As examples, consider how transformation matrices can be used to represent the
symmetry operations of the C2v point group:
• C2: Rotate coordinates (x, y, z) about the C2(z) axis.
• New coordinates (x’, y’, z’) are given by

• In matrix notation,

• To generate these new coordinates, we use a transformation matrix.

 4.3.2 Symmetry Operations: Matrix Representations
• As examples, consider how transformation matrices can be used to represent the
symmetry operations of the C2v point group:
• C2:
• In full matrix notation,
 4.3.2 Symmetry Operations: Matrix Representations
• As examples, consider how transformation matrices can be used to represent the
symmetry operations of the C2v point group:
• v(xz): Reflect a point with coordinates (x, y, z) through the xz plane.

• In matrix notation,
 4.3.2 Symmetry Operations: Matrix Representations
• As examples, consider how transformation matrices can be used to represent the
symmetry operations of the C2v point group:
• The transformation matrices for the four symmetry operations of the group
are

• We call this a matrix representation of the C2v point group.

• This representation is a set of matrices corresponding to an symmetry
operation in the group.
 4.3.2 Symmetry Operations: Matrix Representations
• These matrices can combine in the same way as the operations themselves.
• For example, multiplying two of the matrices is equivalent to performing two
operations and results in a different transformation matrix (the operations are
carried out right to left, so C2  v means v followed by C2):

v(xz) C2 v’(yz)
=
 4.3.2 Characters
• The character is the trace of the matrix, or the sum of the numbers on the
diagonal from upper left to lower right.
• For the C2v point group, the following characters are obtained from the preceding
matrices:
 4.3.2 Characters
• This set of characters also forms a representation, a shorthand version of the
matrix representation.
• This representation is called a reducible representation, which can be further
broken down into irreducible representations (described later).
• Reducible representations are frequently designated with a capital gamma ().
 4.3.2 Reducible and Irreducible Representations
• Each transformation matrix in the C2v set can be “block diagonalized”.
• That is, it can be broken down into smaller matrices along the diagonal, with
all other matrix elements equal to zero:

• All the nonzero elements become 1  1 matrices along the principal diagonal.
 4.3.2 Reducible and Irreducible Representations
• When matrices are block diagonalized in this way, the x, y, and z coordinates
are also block diagonalized and become independent of each other.
• The matrix elements in the 1,1 positions describe the results of the symmetry
operations on the x coordinate, those in the 2,2 positions describe the results of
the operations on the y coordinate, and those in the 3,3 positions describe the
results of the operations on the z coordinate.
 4.3.2 Reducible and Irreducible Representations
• In other words, the four matrix elements for x form the first representation of
the group, those for y form a second representation, and those for z form a
third representation, all shown in the following table:

Irreducible

Reducible

• These irreducible representations of the C2v point group add to make up the
reducible representation .
 4.3.2 Reducible and Irreducible Representations
• Each row is an irreducible representation: it cannot be simplified further.
• The characters of irreducible representations added together under each
operation (column) make up the characters of the reducible representation ,
just as the combination of all the matrices for the x, y, and z coordinates
makes up the matrices of the reducible representation.
• For example, the sum of the three characters for x, y, and z under the C2
operation is −1 , the character for  under this same operation.
 4.3.2 Reducible and Irreducible Representations
• So, the set of 3  3 matrices obtained for H2O is called a reducible matrix
representation because it is the sum of irreducible matrix representations
(the block-diagonalized 1  1 matrices), which cannot be reduced to smaller
component parts.

Reducible matrix representation

Irreducible matrix representation

 4.3.3 Character Tables
• Three representations for C2v (A1, B1, and B2) have now been determined.
• Actually, there is the fourth representation, A2, which can be found using the
group properties described in Table 4.7.

B1
B2
A1
A2 = ?
 4.3.3 Character Tables
• A complete set of irreducible representations for a point group is called the
character table for that group.
• The character table for each point group is unique.
 4.3.3 Character Tables
• The complete character table for C2v, with the irreducible representations in the
order commonly used, is:

• The labels used with character tables are:

• The labels in the left column that designate the irreducible representations will be
described later.
 4.3.3 Character Tables
• The A2 representation of the C2v group can now be explained.

=?

• The character table has four columns.

• It has four classes of symmetry operations (Property 2 in Table 4.7).
• It must therefore have four irreducible representations (Property 3).
• The sum of the products of the characters of any two representations must
equal zero (orthogonality, Property 6).
• Therefore, a product of A1 and the unknown A2 representation must have two
characters of 1 and two characters of −1.
 4.3.3 Character Tables
• The A2 representation of the C2v group can now be explained.

=?

• The character for the identity operation of this new representation must be 1
[χ(E) = 1] (required by Property 4).
• Because no two representations can be the same, A2 must then have χ(E) =
χ(C2) = 1, and χ(xz) = χ(yz) = −1.
• This representation is also orthogonal to B1 and B2, as required.
 4.3.3 Character Tables
• The relationships among
symmetry operations, matrix
representations, reducible and
irreducible representations, and
character tables are conveniently
illustrated in a flowchart, as shown
for C2v symmetry in Table 4.8 .
 4.3.3 Another Example: C3v (NH3)
• Full descriptions of the matrices for the
operations in this group will not be given, but the
characters can be found by using the properties
of a group.
• First, consider the C3 rotation.
• Counterclockwise rotation of 120° results in a
new x and y as shown, which can be described
in terms of the vector sums of x and y by
using trigonometric functions:

Substitute
 = 2/3 = 120º
 4.3.3 Another Example: C3v (NH3)
• The transformation matrices for the symmetry operations are
 4.3.3 Another Example: C3v (NH3)
• In contrast to previous examples, the transformation matrix for C3 cannot be
block diagonalized into 11 matrices, because the C3 matrix has off-diagonal
entries.

• However, the matrices can be block diagonalized into 22 and 11 matrices,
with all other matrix elements equal to zero:
 4.3.3 Another Example: C3v (NH3)
• C3 matrix must be blocked this way because the (x,
y) combination is needed for the new x’ and y’.
• In other words, determination of each of the
transformed coordinates x’ and y’ requires both
original x and y coordinates.
• This is the case with most rotations, as defined
by the general transformation matrix.
• The other C3v matrices must follow the same
pattern for consistency across the representation.
 4.3.3 Another Example: C3v (NH3)
• Then, we may find the characters for two representations by summing the
diagonals for E, C3, and v(xz) transformation matrices.
 4.3.3 Another Example: C3v (NH3)
• In fact, C3v NH3 has other symmetry elements (C32 and two other reflections)
and corresponding transformation matrices. (try find the matrices on your own!)
• But, χ(C32) = χ(C3) in the C3v point group, meaning that characters from C32
and C3 transformation matrices are identical.
• So, they are may be classified into a same class and simply listed as 2C3 in
the character table.
• In addition, the three reflections have identical characters and are in the same
class, listed as 3v.
 4.3.3 Another Example: C3v (NH3)
• Below is the complete character table for C3v.
• The set of 2  2 matrices has generate the E representation.
• The set of 1  1 matrices matches the A1 representation.
• The third irreducible representation, A2, can be found using the defining
properties of a mathematical group, as in the C2v previously shown.
 4.3.3 Another Example: C3v (NH3)
• Table 4.9 gives the properties of the characters for the C3v point group.
 4.3.3 Additional Features of Character Tables
• 1. As shown already, when operations such as C3 and C32 are in the same
class, the listing in a character table is 2C3, indicating that the characters are the
same (or, alternately, that C3 and C32 give the same characters).
 4.3.3 Additional Features of Character Tables
• 2. When necessary, the C2 axes perpendicular to the principal axis (in a D
group) are designated with primes.
• A single prime (C2’) indicates that the axis passes through several atoms of
the molecule, while a double prime (C2’’) indicates that it passes between the
atoms.
 4.3.3 Additional Features of Character Tables
• 3. When the mirror plane is perpendicular to the principal axis, the horizontal
reflection is called h.
• Other planes are labeled v or d.
 4.3.3 Additional Features of Character Tables
• 4. The expressions listed to the right of the characters are used to find atomic
orbitals with symmetries that match the representation.
• For example, A1 representation derives from z component of transformation
matrices, and it remains unchanged after any symmetry operation.
• So does the pz orbital!
• Similarly, E irreducible representation drives from x and y coordinates.
• Notation (x, y) in the table means that x and y together have the same
symmetry properties as the E irreducible representation.
• So, the px and py orbitals together have the same symmetry as the E
irreducible representation in this point group.
 4.3.3 Additional Features of Character Tables
• 4. The function xy, with alternating signs in the four quadrants within the xy plane
matches the lobes of the dxy orbital.
• The totally symmetric s orbital always matches the A1 representation.
• The irreducible representations that describe rotations about the axes (Rx,
Ry, Rz) describe the rotational motions of molecules relative to these axes.
 4.3.3 Additional Features of Character Tables
• 5. Have trouble finding all the symmetry elements in a molecule?
• Simply determine the point group and look up the character table!
• The expected number and types of all symmetry elements will be there for you.
 4.3.3 Additional Features of Character Tables
• 6. Irreducible representations are assigned labels according to the following rules,
where symmetric means a character of 1 and antisymmetric for −1.
• a. Letters are assigned according to the dimension of the irreducible
representation.
 4.3.3 Additional Features of Character Tables
• 6. Irreducible representations are assigned labels according to the following rules,
where symmetric means a character of 1 and antisymmetric for −1.
• b. Subscript 1 is for a representation symmetric to a C2’ rotation
perpendicular to the principal axis, and subscript 2 designates a
representation antisymmetric to the C2’.
• Without C2’, 1 is for a representation symmetric to a vertical plane, and 2
is for a representation antisymmetric to a vertical plane.
 4.3.3 Additional Features of Character Tables
• 6. Irreducible representations are assigned labels according to the following rules,
where symmetric means a character of 1 and antisymmetric for −1.
• c. Subscript g (gerade) designates representations symmetric to
inversion, and subscript u (ungerade) designates representations
antisymmetric to inversion.
 4.3.3 Additional Features of Character Tables
• 6. Irreducible representations are assigned labels according to the following rules,
where symmetric means a character of 1 and antisymmetric for −1.
• d. When distinctions are further needed in some cases (C3h, C5h, D3h, D5h),
single primes are used when symmetric to h and double primes are used
when antisymmetric to h.
 4.4 Examples and Applications of Symmetry
• Now, we will consider two applications of symmetry and group theory, in the
realms of chirality and molecular vibrations.
 4.4.1 Chirality
• Chiral molecules are not superimposable on their
mirror image and may have distinct properties as a
consequence of this nonsuperimposability.
• One chiral molecule is CBrClFI, and many examples of
chiral objects can be found on the macroscopic scale.
• Chiral objects are termed dissymmetric.
• This term doesn’t mean that these objects have no
symmetry.
• For example, the propellers have a C3 axis, yet they are
nonsuperimposable.
• In general, a molecule or object is chiral if it has no
symmetry operations (other than E), or if it has only
proper rotation axes.
 4.4.1 Chirality
• Air blowing past the stationary propellers will be rotated in either a clockwise or
counterclockwise direction.
• By analogy, plane-polarized light will be rotated on passing through chiral
molecules.
• Clockwise rotation is designated dextrorotatory, and counterclockwise
rotation is levorotatory.
• The ability of chiral molecules to rotate plane-polarized light is termed
optical activity, which may be measured experimentally.
 4.4.1 Chirality
• Chiral coordination compounds exhibit optical activity if they can be resolved
into the two isomers.
• One of these is [Ru(NH2CH2CH2NH2)3]2+, with D3 symmetry.
• Mirror images of this molecule look much like left- and righthanded three-
bladed propellers.
 4.4.2 Molecular Vibrations
• Symmetry is helpful to determine the modes of vibration of molecules.
• The vibrational modes of water and the stretching modes of CO in carbonyl
complexes can be treated quite simply.
 4.4.2 Water (C2v Symmetry)
• Because the study of vibrations is the study of motion of the atoms in a
molecule, we must first attach a set of x, y, and z coordinates to each atom.
• For convenience, assign the z axes parallel to the C2 axis, the x axes in the
plane of the molecule, and the y axes perpendicular to the plane.
• Each atom can move in all three directions, so a total of 9 transformations must
be considered.
• For N atoms in a molecule, there are 3N total motions, known as degrees of
freedom.
 4.4.2 Water (C2v Symmetry)
• Degrees of freedom for different geometries are summarized in Table 4.10.
• Because water has three atoms, there must be nine different motions.
 4.4.2 Water (C2v Symmetry)
• We will use transformation matrices to determine the symmetry of all nine
motions within the C2v point group and then assign them to translation,
rotation, and vibration.
 4.4.2 Water (C2v Symmetry)
• In the C2v water example, each transformation matrix is 99 with the full 99
matrix for C2 is shown below.
 4.4.2 Water (C2v Symmetry)
• Looking at the principle diagonal for C2 transformation matrix,
• If the atom changes position during the symmetry operation, a zero is entered.
• If the atom remains in its original location and the vector direction is
unchanged, a 1 is entered.
• If the atom remains, but the vector direction is reversed, a −1 is entered.
(vector directions change by 0º or 180º in the C2v point group)
 4.4.2 Water (C2v Symmetry)
• The Ha and Hb entries are not on the principal diagonal, because Ha and Hb
exchange with each other in a C2 rotation, and x’(Ha) = −x(Hb), y’(Ha) = −y(Hb),
and z’(Ha) = z(Hb).
• Character of the reducible representation  is obtained by summing of the
principal diagonal, so all the hydrogen vectors have zero contribution to the
character.

Ha becomes
Hb with x and
y coordinates
reversed

Same
for Hb
 4.4.2 Water (C2v Symmetry)
• Oxygen atom vectors in the x and y directions are reversed, each contributing
−1.
• The vector in the z direction remains the same, contributing 1.
• Thus, character of the reducible representation  = χ(C2) = (−1) + (−1) + (1) = −1.
 4.4.2 Water (C2v Symmetry)
• The other characters for  can also be found without writing out the matrices:
• E: All nine vectors are unchanged in the identity operation, so the character is
9.

• v(xz): Reflection in the plane of the molecule leaves all the y vectors changed
and the x and z vectors unchanged, resulting in the character of 3 − 3 + 3 = 3.

• v(yz): Reflection perpendicular to the plane of the molecule changes the

position of the hydrogens so their contribution is zero.
• For oxygen, the x vector changes direction, and the y and z vectors are
unchanged, resulting in the character of 1 + 1 − 1 = 1.

v(xz) v(yz)
 4.4.2 Water (C2v Symmetry)
• The characters of the reducible representation  are shown as the last row
below the irreducible representations in the C2v character table.

• Notably, because all nine direction vectors were included in this representation,
it represents all the motions of the molecule: three translations, three
rotations, and three vibrations.
 4.4.2 Reducing Representations to Irreducible Representations
• Next, determine how the irreducible representations add to give the reducible
representation.
How many of each irreducible representation (A1, A2, B1, and B2) contribute to Γ?

• The number of each irreducible representation contributing to a reducible

representation can be found by the adding the product of characters of the
reducible and irreducible representations and the number of operations in
the class, divided by the order of the group.
• Taken over all symmetry operations, we get the final number.
 4.4.2 Reducing Representations to Irreducible Representations
• In the water example, the order of C2v is 4, with one operation in each class.

• The results are as follows:

1 1 1 1

• The reducible representation for all motions of the water molecule is

therefore reduced to 3A1 + A2 + 3B1 + 2B2.
 4.4.2 Reducing Representations to Irreducible Representations
• Among 9 types of motions with symmetries of 3A1 + A2 + 3B1 + 2B2,

• A1 + B1 + B2 correspond to translation along the x, y, and z directions.

• A2 + B1 + B2 correspond to rotation in the three directions (Rx, Ry, Rz).
• Then, we are left with remaining vibrational modes 2A1 + B1.
 4.4.2 Reducing Representations to Irreducible Representations
• As described earlier, the number of vibrational modes equals 3N − 6 (or 3 in H2O)
• Among vibrational modes 2A1 + B1,
• Two of the A1 modes are totally symmetric and do not change the symmetry of
the molecule.
• One B1 mode is antisymmetric to C2 rotation and to v(yz) reflection.
 4.4.2 Infrared Spectra
• A molecular vibration is infrared active (i.e., excitation of the vibrational mode
can be measured via an IR spectrum absorption) only if it results in a change in
the dipole moment of the molecule.
• The three vibrations of water (Table 4.12) can be analyzed in this way to
determine their infrared behavior.
 4.4.2 Selected Vibrational Modes
• IR spectra are useful for characterizing inorganic compounds.
• For example, useful information often can be obtained from the C-O stretching
bands in infrared spectra of metal carbonyl complexes ligands.
• Let’s consider cis- and trans-dicarbonyl square planar complexes.
• A routine IR spectrum can distinguish cis- or trans-ML2(CO)2.
• The number of C-O stretching bands is determined by the geometry of the
complex.
 4.4.2 cis-ML2(CO)2, point group C2v
• The principal axis (C2) is the z x
axis, and the xz plane assigned as
the plane of the molecule.
• Possible C-O stretching motions z
are shown by arrows/vectors.
• If a symmetry operation
belonging to C2v point group
changes the C-O bond location,
a character of 0 is assigned. 1 0
• If unchanged, character of 1 is
1 0
assigned.
• These vectors are used to create
the reducible representation.
 4.4.2 cis-ML2(CO)2, point group C2v
• The reducible representation  reduces to A1 + B1:

• A1 is an appropriate irreducible representation for an IR-active band, because it

transforms as (has the symmetry of) the Cartesian coordinate z.
• Furthermore, the vibrational mode corresponding to B1 should be IR active,
because it transforms as the Cartesian coordinate x.
 4.4.2 cis-ML2(CO)2, point group C2v
• In summary, there are two vibrational modes for C-O stretching (one A1
symmetry and one B1 symmetry).
• Both modes are IR active, and we therefore expect to see two C-O stretches in
the IR.
 4.4.2 trans-ML2(CO)2, point group D2h
• The principal axis, C2, is again chosen as the z axis, which renders the plane of
the molecule the xy plane.

• Using the symmetry operation of the D2h point group, we obtain a reducible
representation for C-O stretches that reduces to Ag + B3u:
 4.4.2 trans-ML2(CO)2, point group D2h
• The vibrational mode of Ag symmetry is not IR active, because it does not
have the same symmetry as a Cartesian coordinate x, y, or z (this is the IR-
inactive symmetric stretch).
• The mode of symmetry B3u, on the other hand, is IR active, because it has the
same symmetry as x.
 4.4.2 trans-ML2(CO)2, point group D2h
• In summary, there are two vibrational modes for C-O stretching.
• But!
• The Ag mode is IR inactive (it does not have the symmetry of x, y, or z)
• The B3u mode is IR active (it has the symmetry of x).
• We therefore expect to see one C-O stretch in the IR.
 4.4.2 trans-ML2(CO)2, point group D2h
• So, it’s possible to distinguish cis- and trans-ML2(CO)2 using IR spectra.
• If one C-O band appears, the molecule is trans.
• If two bands appear, the molecule is cis.
• A significant distinction can be made by a very simple measurement.
 4.4.2 Raman spectroscopy
• Raman spectroscopic method uses a different approach to observe molecular
vibrations.
• Rather than directly observing absorption of infrared radiation as in IR
spectroscopy, high energy laser irradiation excites molecules to higher
electronic “virtual” states.
• Scattered radiation from decay of these excited states to a vibrational state
provides information about vibrational energy levels that is complementary to
information gained from IR spectroscopy.
 4.4.2 Raman spectroscopy
• A vibration can yield a Raman signal if it causes a change in polarizability.
• From a symmetry standpoint, vibrational modes are Raman active if they match
the symmetries of the functions xy, xz, yz, x2, y2, or z2 or a linear
combination of any of these.
• If vibrations match these functions, they also occur with a change in polarizability.
• These functions are among those commonly listed in character tables.

• When molecular vibrations match both these functions and x, y, or z, they are
both IR and Raman active.