Character Tables

The symmetry properties of each point group are

summarized on a character table. The character table lists
all of the symmetry elements of the group, along with a
complete set of irreducible representations.
Character Table (C2v)
Character Table (C2v)

The functions to the right are called basis functions.

They represent mathematical functions such as
orbitals, rotations, etc.
The px orbital
If a px orbital on the
central atom of a
molecule with C2v
symmetry is rotated
about the C2 axis, the
orbital is reversed, so
the character will be -1.
The px orbital
If a px orbital on the central atom of a molecule with
C2v symmetry is rotated about the C2 axis, the orbital
is reversed, so the character will be -1.
The px orbital
If a px orbital on the
central atom of a
molecule with C2v
symmetry is reflected in
the yz plane, the orbital is
also reversed, and the
character will be -1.
The px orbital
If a px orbital on the central atom of a molecule with
C2v symmetry is reflected in the yz plane, the orbital
is also reversed, and the character will be -1.
The px orbital
If a px orbital on the central atom of a molecule with
C2v symmetry is reflected in the xz plane, the orbital
is unchanged, so the character is +1.
Character Table Representations
1. Characters of +1 indicate that the basis function is
unchanged by the symmetry operation.
2. Characters of -1 indicate that the basis function is
reversed by the symmetry operation.
3. Characters of 0 indicate that the basis function
undergoes a more complicated change.
Character Table Representations
1. An A representation indicates that the functions are
symmetric with respect to rotation about the principal
axis of rotation.
2. B representations are asymmetric with respect to
rotation about the principal axis.
3. E representations are doubly degenerate.
4. T representations are triply degenerate.
5. Subscrips u and g indicate asymmetric (ungerade) or
symmetric (gerade) with respect to a center of inversion.
Applications of Group Theory
1. Predicting polarity of molecules. A molecule cannot have
a permanent dipole moment if it
a) has a center of inversion
b) belongs to any of the D point groups
c) belongs to the cubic groups T or O
Applications of Group Theory
2. Predicting chirality of molecules. Chiral molecules lack
an improper axis of rotation (Sn), a center of symmetry (i)
or a mirror plane (σ).  
Applications of Group Theory
3. Predicting the orbitals used in σ bonds. Group theory
can be used to predict which orbitals on a central atom
can be mixed to create hybrid orbitals.  
Applications of Group Theory
4. Predicting the orbitals used in molecular orbitals.
Molecular orbitals result from the combining or overlap
of atomic orbitals, and they encompass the entire
molecule.  
Applications of Group Theory
5. Determining the symmetry properties of all molecular
motion (rotations, translations and vibrations). Group
theory can be used to predict which molecular vibrations
will be seen in the infrared or Raman spectra.  
Determining Hybridization
1. Determine the point group of the molecule.
2. Consider the σ bonds as vectors, and determine
how they are transformed by the symmetry
operations of the group.
3. Obtain the characters for the bonds. For each
symmetry operation, a bond which remains in place
contributes a value of +1. If the bond is moved to
another position, it contributes a value of 0.
4. Reduce the set of characters to a linear combination
of the character sets of the point group.
Hybridization
! Determine the hybridization of boron in BF3. The
molecule is trigonal planar, and belongs to point group
D3h.

1. Consider the σ bonds as vectors.

Fa
B Fc
Fb  
Hybridization
! Determine the hybridization of boron in BF3. The
molecule is trigonal planar, and belongs to point group
D3h.

1. Consider the σ bonds as vectors.

Fa
B Fc
Fb  
Hybridization
Determine how each vector (σ bond) is
transformed by the symmetry operations of the
group.  
Determining Hybridization
E 2C3 3C2 σh 2S3 3σv
Гred  
Determining Hybridization
E 2C3 3C2 σh 2S3 3σv
Гred 3  
Determining Hybridization
E 2C3 3C2 σh 2S3 3σv
Гred 3 0  
Determining Hybridization
E 2C3 3C2 σh 2S3 3σv
Гred 3 0 1  
Determining Hybridization
E 2C3 3C2 σh 2S3 3σv
Гred 3 0 1  
Determining Hybridization
E 2C3 3C2 σh 2S3 3σv
Гred 3 0 1 3  
Determining Hybridization
E 2C3 3C2 σh 2S3 3σv
Гred 3 0 1 3 0  
Determining Hybridization
E 2C3 3C2 σh 2S3 3σv
Гred 3 0 1 3 0 1  
Reducing a Representation

ni = the number of times an irreducible

representation i occurs in the reducible
representation
h = the order of the group (the total number of
operations in the point group)
c = the class (type) of operation
gc= the number of operations in the class
χi = the character of the irreducible representation
χr = the character of the reducible representation  
Reducing a Representation

The order of the group, h, is the total number of

operations.
h = 1+2+3+1+2+3=12
Hybridization of BF3
Гred reduces to A1′ + E ′. The orbitals used in
hybridization must have this symmetry.
Hybridization of BF3
Гred reduces to A1′ + E ′. The orbitals used in
hybridization must have this symmetry.
Hybridization of BF3
Гred reduces to A1′ + E ′. The orbitals used in
hybridization must have this symmetry.
Hybridization of BF3
Гred reduces to A1′ + E ′. The orbitals used in
hybridization must have this symmetry.
Molecular Vibrations
Molecular motion includes translations, rotations and
vibrations. The total number of degrees of freedom
(types of molecular motion) is equal to 3N, where N is
the number of atoms in the molecule.
Molecular Vibrations
Of the 3N types of motion, three represent molecular
translations in the x, y or z directions. Linear molecules
have two rotational degrees of freedom, and non-linear
molecules have three rotational degrees of freedom.
Molecular Vibrations
For linear molecules, the number of molecular vibrations
= 3N-3-2 = 3N-5.

For non-linear molecules, the number of molecular

vibrations = 3N-3-3= 3N-6.
Molecular Vibrations
To obtain Гred for all molecular motion, we must
consider the symmetry properties of the three cartesian
coordinates on all atoms of the molecule.  
Molecular Vibrations
z y
x

The molecule lies in the xz plane. The x axis is drawn in

blue, and the y axis is drawn in black. The red arrows
indicate the z axis.  
Molecular Vibrations
y
x

The molecule lies in the xz plane. The x axis is drawn in

blue, and the y axis is drawn in black. The red arrows
indicate the z axis.  
Molecular Vibrations
z y
x

If a symmetry operation changes the position of an

atom, all three cartesian coordinates contribute a value of
0.  
Molecular Vibrations
z y
x

For operations that leave an atom in place, the character

is +1 for an axis that remains in position, -1 for an axis
that is reversed, and 0 for an axis that has been moved.  
Molecular Vibrations

Identity leaves all 3 atoms

in position, so the
character will be 9.
Molecular Vibrations

Identity leaves all 3 atoms

in position, so the
character will be 9.
Molecular Vibrations

The C2 axis goes through

the oxygen atom, and
exchanges the hydrogen
atoms.  
Molecular Vibrations

The z axis (red) on

oxygen stays in position.
This axis contributes +1
towards the character
for C2.  
Molecular Vibrations

The y axis (black) on

oxygen is rotated by
180o. This reverses the
axis, and contributes -1
to the character for C2.  
Molecular Vibrations

The x axis (blue) on oxygen

is also rotated by 180o. This
reverses the axis, and
contributes -1 to the
character for C2.  
Molecular Vibrations

The character for the C2 operation will

be +1 (z axis on oxygen) -1 (y axis on
oxygen) -1 (x axis on oxygen) = -1  
Molecular Vibrations

The character for the C2 operation will

be +1 (z axis on oxygen) -1 (y axis on
oxygen) -1 (x axis on oxygen) = -1  
Molecular Vibrations

The xz mirror plane is the

x molecular plane, and all
three atoms remain in
position.
Molecular Vibrations

The z axis and the x axis

x both lie within the xz plane,
and remain unchanged.
Molecular Vibrations

Each unchanged axis

x contributes +1 to the
character for the symmetry
operation.
Molecular Vibrations

For 3 atoms, the

x contribution to the
character will be:
3(1+1) =6
Molecular Vibrations

y The y axis will be reversed

x by the mirror plane,
contributing a value of -1
for each of the three atoms
on the plane.
Molecular Vibrations

y The character for the xz

x mirror plane will be:
6-3 = 3
Molecular Vibrations

y The yz mirror plane bisects

x the molecule. Only the
oxygen atom lies in the
plane.
Molecular Vibrations

y The y and z axis lie within

x the yz plane, and each
contributes +1 to the
character.
Molecular Vibrations

y The x axis on oxygen is

x reversed by the reflection,
and contributes a -1
towards the character.
Molecular Vibrations

y The character for reflection

x in the yz plane is:
1+1-1=1
Molecular Vibrations

The above reducible representation is sometimes called

Г3N, because it reduces to all (3N) modes of molecular
motion.
Г3N for water reduces to:
3A1 + A2 + 3B1 + 2B2
Molecular Vibrations
Г3N for water = 3A1 + A2 + 3B1 + 2B2

Note that there are 9 modes of motion.

These include vibrations, rotations and
translations.
Molecular Vibrations
Г3N for water = 3A1 + A2 + 3B1 + 2B2

Translations have the same symmetry properties as x, y

and z.
Molecular Vibrations
Г3N for water = 3A1 + A2 + 3B1 + 2B2

Translations have the same symmetry properties as x, y

and z.
Molecular Vibrations
2
Г3N for water = 3A1 + A2 + 3B1 + 2B2

Translations have the same symmetry properties as x, y

and z.
Molecular Vibrations
2 2
Г3N for water = 3A1 + A2 + 3B1 + 2B2

Translations have the same symmetry properties as x, y

and z.
Molecular Vibrations
2 2
Г3N for water = 3A1 + A2 + 3B1 + 2B2

Translations have the same symmetry properties as x, y

and z.
Molecular Vibrations
2 2 1
Г3N for water = 3A1 + A2 + 3B1 + 2B2

Translations have the same symmetry properties as x, y

and z.
Molecular Vibrations
Гrot & vib = 2A1 + A2 + 2B1 + 1B2

 
Molecular Vibrations
Гrot & vib = 2A1 + A2 + 2B1 + 1B2

Rotations have the same symmetry as

Rx, Ry and Rz.  
Molecular Vibrations
Гrot & vib = 2A1 + A2 + 2B1 + 1B2

Rotations have the same symmetry as

Rx, Ry and Rz.  
Molecular Vibrations
1
Гrot & vib = 2A1 + 2B1 + 1B2

Rotations have the same symmetry as

Rx, Ry and Rz.  
Molecular Vibrations
Гrot & vib = 2A1 + 1B1 + 1B2

Rotations have the same symmetry as

Rx, Ry and Rz.  
Rotations and Translations

Transz Rz

Transy
Rx

Transx Ry
Molecular Vibrations
Гvib = 2A1 + B1
The three vibrational modes remain.
Two have A1 symmetry, and one has B1
symmetry.  
Molecular Vibrations
Гvib = 2A1 + B1
Two vibrations are symmetric with
respect to all symmetry operations of the
group.  
Molecular Vibrations
Гvib = 2A1 + B1
One vibration is asymmetric with
respect to rotation and reflection
perpendicular to the molecular plane.  
Molecular Vibrations
Гvib = 2A1 + B1
 
A1 symmetric stretch

A1 bend

B1 asymmetric stretch
Molecular Vibrations
For a molecular vibration to be seen in the infrared
spectrum (IR active), it must change the dipole moment of
the molecule. The dipole moment vectors have the same
symmetry properties as the cartesian coordinates x, y and
z.
Molecular Vibrations
Raman spectroscopy measures the wavelengths of light
(in the IR range) scatted by a molecule. Certain
molecular vibrations will cause the frequency of the
scattered radiation to be less than the frequency of the
incident radiation.
Molecular Vibrations
For a molecular vibration to be seen in the Raman
spectrum (Raman active), it must change the polarizability
of the molecule. The polarizability has the same
symmetry properties as the quadratic functions:
xy, yz, xz, x2, y2 and z2
Molecular Vibrations of Water
Гvib = 2A1 + B1
 

The two vibrations with A1 symmetry

have z as a basis function, so they will be
seen in the infrared spectrum of water.
This will result in two peaks (at different
frequencies) in the IR spectrum of water.
Molecular Vibrations of Water
Гvib = 2A1 + B1
 

The two vibrations with A1 symmetry

also have quadratic basis functions, so they
will be seen in the Raman spectrum of
water as well.
Molecular Vibrations of Water
Гvib = 2A1 + B1
 

The two vibrations with A1 symmetry

will appear as two peaks in both the IR and
Raman spectra. The two frequencies
observed in the IR and Raman for these
vibrations will be the same in both spectra.
Molecular Vibrations of Water
Гvib = 2A1 + B1
 

The vibration with B1 symmetry has x

and xz as basis functions. This vibration
will be both IR active and Raman active.
This vibration will appear as a peak (at the
same frequency) in both spectra.
Molecular Vibrations of Water
Гvib = 2A1 + B1
 

Both the IR and Raman spectra

should show three different peaks.
Summary
1. Obtain the point group of the molecule.
2. Obtain Г3N by considering the three cartesian
coordinates on all atoms that aren’t moved by the
symmetry operation.
3. Reduce Г3N .
4. Eliminate translations and rotations.
5. Determine if remaining vibrations are IR and/or Raman
active.  
Application: Carbonyl Stretches
! Can IR and Raman spectroscopy determine the difference
between two square planar complexes: cis-ML2(CO)2 and
trans-ML2(CO)2?
 cis and trans ML2(CO)2

cis isomer – C2v trans isomer – D2h

 cis - ML2(CO)2

C2v: E C2 σxz σyz

ГCO: 2 0 2 0
cis - ML2(CO)2
ГCO reduces to A1 + B1.
A1 is a symmetric stretch,
and B1 is an asymmetric
stretch.
cis - ML2(CO)2
ГCO reduces to A1 + B1.
The symmetric stretch
(A1) is IR and Raman
active.
cis - ML2(CO)2
ГCO reduces to A1 + B1.
The asymmetric stretch
(B1) is both IR and Raman
active.
 trans ML2(CO)2
The trans isomer lies in
the xy plane. The x
point group D2h has y
the following
symmetry elements:
trans isomer – D2h
 trans ML2(CO)2
The trans isomer lies in
the xy plane. ГCO is x
obtained by looking y
only at the two C-O
bonds.
trans isomer – D2h

ГCO
 trans ML2(CO)2
ГCO reduces to Ag (a
symmetric stretch) and x
B3u(an asymmetric y
stretch).

trans isomer – D2h

 trans ML2(CO)2
ГCO reduces to Ag (a
symmetric stretch) and x
B3u(an asymmetric y
stretch).
Ag has x2, y2 and
z2 as basis functions, trans isomer – D2h
so this vibration is
Raman active.
 trans ML2(CO)2
Ag has x2, y2 and
z2 as basis functions, x
so this vibration is y
Raman active.
B3u has x as a
basis function, so this trans isomer – D2h
vibration is IR active.
 trans ML2(CO)2

Ag has x2, y2 and z2 as basis functions, so

this vibration is Raman active.
B3u has x as a basis function, so this
vibration is IR active.
The IR and Raman spectra will each show
one absorption at different frequencies.
Exclusion Rule

If a molecule has a center of symmetry, none of its modes of

vibration can be both infrared and Raman active.
Exclusion Rule

If a molecule has a center of symmetry, none of its modes of

vibration can be both infrared and Raman active.