KI2141-2011-Molecular Symmetry 2013 11 29

Molecular Symmetry
Achmad Rochliadi, MS., PhD.

and Dr. Veinardi suendo
Contents
What and Why?
The symmetry elements and operations
The symmetry classification
Consequences of symmetry
Linear algebra in symmetry
Group representation and character tables
Molecular Symmetry
What is symmetry ?
According to Webster Dictionary
Correspondence in size, shape and relative

position of parts that are on opposite sides of a
dividing line or median plane or that are
distributed about a center of axis.
Molecular symmetry
If a molecule has two or more orientation that

are indistinguishable then the molecule
possesses symmetry.
Molecular Symmetry
Why symmetry important in chemistry

The symmetry of the molecule tells us whether
the molecule is chiral, and whether it has a
dipole moment.
Symmetry will allow us to interpret
spectroscopic measurements on molecules. It is
particularly important when we come to
interpreting the infrared (vibrational) spectra of
molecules.
Molecular Symmetry
Symmetry is important in interpreting the crystal

structures of molecules. Modern X-ray diffraction
methods use symmetry in order to interpret the spectra
obtained and determine the absolute position of atoms
within a crystalline solid, and hence its structure.
Symmetry is crucial both in understanding the
electronic structure of molecules (Molecular orbital, or
MO theory). It is crucial in simplifying the otherwise
computationally intensive calculations that need to be
carried out in order to find the energies of molecules
and hence predict their structure and the chemical
reactions that can be carried out on them
Molecular Symmetry
Molecular Symmetry
Molecular Symmetry
Symmetry Elements and Operations
Symmetry Elements
A point, line or plane in the molecule about

which the symmetry operation take out. There is
only 5 symmetry elements related to molecule
symmetry.
Symmetry Operations
Some transformations of the molecule such as a

rotation or reflection which leaves the molecule
in a configuration in space that is
indistinguishable from its initial configuration.
Molecular Symmetry
Symmetry Elements
Elements
Symbol Operation
Identity
Leaves each particles in its

original position
N-fold proper
axis
Cn
Rotation about the axis by

3600/n (or by multiply)
Plane
Reflexion in plane
Inversion
center
Inversion through center
N-fold
improper axis
Rotation by 3600/n followed

by reflexion in a plane
perpendicular to the axis
Sn
Molecular Symmetry
1. The identity operators, E
The simplest symmetry operation is known as the

identity operator, given the symbol E (E from the
German word Einheit, meaning unity). The E operator
basically means do nothing to the molecule.
Evidently, if you do nothing to the molecule it will look
the same as when you started. The identity operation
will thus work on all molecules.
Many non-symmetrical molecules,
such as the amino acid alanine
shown here, contain only the
E operator.
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Molecular Symmetry
2. The n-fold rotation operators, Cn
Rotation axes have the nomenclature Cn which means

rotate the molecule around the specified axis through
an angle of 360/n. Thus, a C2 axis means rotate by
180, C3 by 120, C4 by 90 and so on.
An easy way to remember this is that n is the number of
times you would have to rotate the molecule before you
would get back to the beginning.
Note that some molecules can contain more than one
rotation axis. When this occurs we refer to the axis with
the highest degree of rotational symmetry as the
principle axis.
Operation C1 is a rotation through 360, and it is
equivalent to E Operator.
Operation Cnm, corresponding to m successive Cn
rotations.
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Molecular Symmetry
Some of the rotation symmetry elements of a cube. The twofold,

threefold and fourfold axes are labeled with the conventional
symbols.
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Molecular Symmetry
(a) An NH3 molecule has a threefold (C3) axis and (b) H2O molecule has a
twofold (C2) axis.
Symmetry modeling : http://www.ch.ic.ac.uk/local/symmetry/
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Molecular Symmetry
Successive rotations
14
Molecular Symmetry
Benzene have C6, C2, the principal axis is the sixfold

axis that perpendicular to the hexagonal ring.
15
Molecular Symmetry
3. The reflections operators,
A mirror plane (symbol ) is a symmetry

element that results in the reflections of
the molecule through a mirror plane.
If the plane is parallel to the principal
axis, it is called vertical and denoted v.
If the plane is perpendicular to the
principal axis, it is called horizontal and
denoted h
A vertical mirror plane that bisect
(divide) the angle between two C2 axes is
called a dihedral plane and denoted d.
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Molecular Symmetry
An H2O molecule has two mirror planes. They are both

vertical so denoted v and v.
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Molecular Symmetry
Dihedral mirror planes (d) bisect the C2 axes

perpendicular to the principal axis.
18
Molecular Symmetry
3. The inversion operators, i
Imagine taking each point in a molecule, moving it to the

centre of the molecule, and then moving it out the same
distance on the other side.
Move every atom at position (x,y,z) to position (-x,-y,-z).
If the molecule still looks the same, then it contains a
centre of inversion.
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Molecular Symmetry
A Regular octahedron has a centre of inversion

20
Molecular Symmetry
Inversion of benzene, notice that the three of the C-H

groups have been color coded. When the inversion is
performed, these groups move to the mirrored side.
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Molecular Symmetry
5. The n-fold improper rotation, Sn
An improper is the most complex symmetry element to

understand. An improper rotation consist of TWO steps
and neither operation alone needs to be a symmetry
operation:
The rotation like Cn, where the molecule is rotate around the
axis.
Reflection through a plane perpendicular to the axis of that
rotation,
22
Molecular Symmetry
(a) A CH4 molecule has a fourfold improper rotation axis (S4); the
molecule is indistinguishable after a 90 rotation followed by a
reflection across the horizontal plane, (b) The staggered form of
ethane has an S6 axis composed of a 60 rotation followed by a
reflections.
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Molecular Symmetry
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Molecular Symmetry
The symmetry classification (Group Theory)

To classify the molecules according to their
symmetries, the molecule symmetry elements is
listed and collect together the molecules with
the same list of elements.
The name of the group is determined by the
symmetry elements it possesses.
Two system of notation
The Schoenflies system, more common.

The Hermann-Mauguin system/International
system, exclusively used in crystal symmetry.
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Molecular Symmetry
What is point group
A point group is a collection of symmetry

operations that together are specific to a wide
number of different molecules. These
molecules are from a symmetry viewpoint,
equivalent. For example, both water and cisdichloroethene are members of the C2v point
group. Once you have learned about the various
symmetry operations, go to the link on point
groups to find out more about this concept.
27
Molecular Symmetry
Group Theory
In essence, group theory is a set of

mathematical relationships that allow us to
study symmetry. An in depth and rigorous
study of group theory requires an extensive
knowledge of matrix algebra. As chemists, we
can usually concern ourselves less with the
details of the math, and more on visualizing
how symmetry operations transform molecules
in three dimensional space.
28
Molecular Symmetry
The diagram for

determining the point
group of a molecule
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Molecular Symmetry
30
Molecular Symmetry
31
Molecular Symmetry
32
Summary of shapes corresponding to

different point groups.
Molecular Symmetry
Group C1 Ci Cs
Molecule belong to C1 if has no other element

than the identity (1). Ci if has identity and
inversion (3), and Cs if it has identity and a
mirror plane alone (4).
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Molecular Symmetry
Group Cn Cnv Cnh

Cn : possess n-fold axis (5)
Cnv : possess n-fold + v (H2O; NH3)
Cnh : possess n-fold + h (6) - (7)
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Molecular Symmetry
Group Dn Dnv Dnh

Dn : possess n-fold axis ntwofold axes
perpendicular to Cn
Dnh : possess n-fold axis n-twofold axes
perpendicular to Cn + h (8, 9, 10, 11)
Dnd : possess Dn + n dihedral mirror planes d
(12. 13)
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Molecular Symmetry
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Molecular Symmetry
Group S2n
Its the molecule that has not classified into one

of the group above but possess one S2n axis.
37
Molecular Symmetry
The cubic groups

Molecule that possess more than one principal
axis belong to the cubic groups.
Tetrahedral groups : Td (a), T (a), and Th (a)
Octahedral groups : Oh (b) and O (b)
Icosahedral group : Ih (c) and I (c)
38
Molecular Symmetry
(a) T
(b) O
(c) I
(a) Th
39
Molecular Symmetry
The full rotation group

The molecule rotational group, R3, consists of
infinite number of rotation axes with all
possible values of n.
Sphere and an atom belong to R3
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Molecular Symmetry
Cv and Dh point groups
Asymmetrical diatomics (e.g. HF, CO and [CN]-) and linear

polyatomics that do not possess a centre of symmetry (e.g. OCS and
HCN) possess an infinite number of sv planes but no sh plane or
inversion centre. These species belong to the Cv point group.
Symmetrical diatomics (e.g. H2, [O2]2-) and linear polyatomics that
contain a centre of symmetry (e.g. [N3]-, CO2, HCCH) possess a sh
plane in addition to a C axis and an infinite number of sv planes.
These species belong to the Dh point group.
41
Molecular Symmetry
Groups of high symmetry
42
Molecular Symmetry
Exercise 1
D5h
D5d
43
Molecular Symmetry
Polarity
If the molecule belongs to group Cn with n > 1,

it cannot possess a charge distribution with a
moment dipole perpedicular to the symmetry
axis but it may have one parallel to the axis.
Molecule belong to Cn, Cnv, Cs may be polar.
All other group such C3h, D, ets there are
symmetry operations that take one end ot
molecule into the other.
44
Molecular Symmetry
45
(a) A molecule with a Cn

axis cannot have a dipole
perpendicular to the axis,
but (b) it may have one
parallel to the axis.
Molecular Symmetry
Chirality
A chiral molecule is a molecule that cannot be

superimposed on its mirror image. A chiral
molecule is an optic active molecule.
A molecule may be chiral only if it does not
posses an axis of improper rotation, Sn.
Take notice that Sn operation could be present
under different symmetry element. Example:
molecules belonging to the groups Cnh posses
an Sn axis implicity because the possess both Cn
and h, which are the two components of an
improper rotation axis. So as the molecule have
i elements.
46
Molecular Symmetry
Some symmetry
elements are implied by
the other symmetry
elements in a group.
Any molecule
containing an inversion
also possesses at least
an S2 element because i
and S2 are equivalent
47
Molecular Symmetry
S4
48
Molecular Symmetry
Exercise 2
49
Molecular Symmetry
Linear algebra in symmetry: Dictionary
50
Molecular Symmetry
The effect on a matrix of a change in coordinate system
51
Molecular Symmetry
Traces and determinants
The trace of a matrix is defined as the sum of the

diagonal elements.
The determinant of a matrix is a value associated

with a square matrix that can be computed from
the entries of the matrix by a specific arithmetic
expression:
52
Molecular Symmetry
53
Molecular Symmetry
Group representation and character tables
54
Molecular Symmetry
Example: C2v point group
C2 operation
sv(xz) operation
55
Molecular Symmetry
Example 1: C2v point group (H2O)
C2 sv(xz) operation
Proof the following statements:
C2 C2 = E
sv(xz) sv(yz) = C2
sv(yz) sv(yz) = E
56
Molecular Symmetry
Characters
The character, defined only for a square matrix, 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, we can obtained the
following characters:
We can say that this set of characters also forms a representation,

which is an alternate shorthand version of the matrix
representation.
Whether in matrix or character format, this is called a reducible
representation, a combination of more fundamental irreducible
representations.
Reducible representations are designated with a capital gamma
(G).
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Molecular Symmetry
Reducible and irreducible representations
58
Molecular Symmetry
Character tables
59
Molecular Symmetry
Properties of characters of irreducible

representations in point groups
Also
h i (E)
i
60
Molecular Symmetry
Properties of characters of irreducible

representations in point groups
61
Molecular Symmetry
Example 2: C3v point group (NH3)
62
Molecular Symmetry
Transformation matrices
63
Molecular Symmetry
Transformation matrices
In the C3v point group (C32) = (C3), which means that

they are in the same class and described as 2C3 in
character table.
In addition, the three reflections have identical characters
and are in the same class, as described as 3sv.
The transformation matrices for C3 and C32cannot be
block diagonalized into 1 1 matrices because the C3
matrix has off-diagonal entries. However, they can be
block diagonalized into 2 2 and 1 1 matrices, with all
other matrix elements equal to zero.
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Molecular Symmetry
Character tables of C3v point group

The C3 matrix must be blocked this way
because the (x,y) combination is needed for the
new x and y, while the other matrices must
follow the same pattern for consistency across
the representation.
The set 2 2 matrices has the characters
corresponding to the E representation, while the
set of 1 1 matrices matches the A1
representation.
The A2 representation can be found using the
defining properties of a mathematical group as
in previous example.
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Molecular Symmetry
Character tables of C3v point group: A1
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Molecular Symmetry
Character tables of C3v point group: E
Symmetric
Antisymmetric
67
disymmetric
Molecular Symmetry
Properties of the characters for C3v point group
68
Molecular Symmetry
Addition feature of character tables
The expression listed to the right of the characters

indicate the symmetry of mathematical functions of the
coordinates x, y and z and of rotation about the axes (Rx,
Ry, Rz).
This can be used to find the orbitals that match the
representation. For example: x with (+) and (-) direction
matches the px orbital with (+) and (-) lobes in the
quadrants in the xy plane; the product xy with alternating
signs on the quadrants matches lobes of the dxy orbital.
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Molecular Symmetry
In all cases, the totally symmetric s orbital

matches the first representation of in the group,
one of the A set.
The rotational functions are used to describe the
rotational motion of the molecule.
In the C3v example, the x and y coordinates
appeared together in the E irreducible
representation with notation (x,y). This means
that x and y together have the same symmetry
properties as the E irreducible representation.
Consequently, the px and py orbitals together
have the same symmetry as the E irreducible
representation in this point group.
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Molecular Symmetry
Matching the symmetry operations of a molecule

with those listed in the top row of the character
table will confirm any point group assignment.
Irreducible representations are assigned labels
according to the following rules, in which
symmetric means a character of 1 and
antisymmetric a character of -1.
Letter are assigned according to the dimension of

the irreducible representation.
71
Molecular Symmetry

This might also give us information about degeneracies as
follows:
A and B (or a and b) indicate non-degenerate

E (or e) refers to doubly degenerate
T (or t) means triply degenerate
Subscript 1 designates a representation symmetric to a C2

rotation perpendicular to the principal axis, and subscript 2
designates a representation of antisymmetric to the C2. If
there are no perpendicular C2 axes, 1 designates a
representation symmetric to vertical plane, and 2
designates a representation antisymmetric to a vertical
plane.
Subscript g (gerade) designates symmetric to inversion,
and subscript u (ungerade) designates antisymmetric to
inversion.
Single prime () are symmetric to sh and double prime ()
are antisymmetric to sh when a distinction between
representations is needed (C3h, C5h, D3h, D5h).
72
Molecular Symmetry
Molecular vibration: H2O (C2v)
Degree of freedom
73
Molecular Symmetry
Full C2 operation of H2O
The Ha and Hb entries are not on the principal diagonal

because Ha and Hb exchange each other in a C2 rotation,
and x(Ha) = -x(Hb), y(Ha) = -y(Hb) and z(Ha) = z(Hb).
Only oxygen contribute to the character for this
operation, for total of -1.
74
Molecular Symmetry
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Molecular Symmetry
Reducing representations to irreducible representations
76
Molecular Symmetry
Symmetry molecular motion of water
77
Molecular Symmetry
Symmetry molecular motion of water
78
Molecular Symmetry
IR Spectra of H2O
Calculated IR spectrum of gaseous H2O
Experimental values are 3756, 3657 and 1595 cm1

79
Molecular Symmetry
A bent triatomic: H2O (C2v)
80
Molecular Symmetry
2s atomic orbital of the O (a1)
81
Molecular Symmetry
2px atomic orbital of the O (b1)
82
Molecular Symmetry
2py atomic orbital of the O (b2)
83
Molecular Symmetry
2pz atomic orbital of the O (a1)
84
Molecular Symmetry
1s atomic orbital of the H (a1 and b2)

and
a1
85
b2
Molecular Symmetry
summation
86
Molecular Symmetry
Normalization
87
Molecular Symmetry
88
Molecular Symmetry
89
Molecular Symmetry
The MO Diagram of Water with the 2a1 Showing Bonding

and Antibonding Character
90
Molecular Symmetry
The MO Diagram of Water with the 2a1 Labeled as

Non-bonding
91
Molecular Symmetry
The MO Diagram of Water with the 1a1 Labeled as Nonbonding
92
Molecular Symmetry
Further on character tables
93
Molecular Symmetry
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Molecular Symmetry
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Molecular Symmetry
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Molecular Symmetry
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Molecular Symmetry
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Molecular Symmetry
References and further readings
P. Atkins and J. de Paula, Atkins Physical Chemistry,

8th Edition, Oxford University Press, Oxford, 2006.
S.F.A. Kettle, Symmetry and Structure: Readable
Group Theory for Chemists, 3rd Edition, John Wiley &
Sons, Chichester, 2007.
A.M. Lesk, Introduction to Symmetry and Group
Theory for Chemists, Kluwer Academic Publishers,
Dordrecht, 2004.
C.E. Housecroft and A.G. Sharpe, Inorganic Chemistry,
3rd Edition, Pearson Education Limited, Harlow, 2008.
G.L. Miessler and D.A. Tarr, Inorganic Chemistry, 4th
Edition, Pearson Education Limited, Harlow, 2010.
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Molecular Symmetry

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Molecular Symmetry

Achmad Rochliadi, MS., PhD.

According to Webster Dictionary

Correspondence in size, shape and relative

If a molecule has two or more orientation that

Why symmetry important in chemistry

Symmetry is important in interpreting the crystal

Symmetry Elements and Operations

A point, line or plane in the molecule about

Some transformations of the molecule such as a

Leaves each particles in its

Rotation about the axis by

Inversion through center

Rotation by 3600/n followed

1. The identity operators, E

The simplest symmetry operation is known as the

2. The n-fold rotation operators, Cn

Rotation axes have the nomenclature Cn which means

Some of the rotation symmetry elements of a cube. The twofold,

Benzene have C6, C2, the principal axis is the sixfold

3. The reflections operators,

A mirror plane (symbol ) is a symmetry

An H2O molecule has two mirror planes. They are both

Dihedral mirror planes (d) bisect the C2 axes

3. The inversion operators, i

Imagine taking each point in a molecule, moving it to the

A Regular octahedron has a centre of inversion

Inversion of benzene, notice that the three of the C-H

5. The n-fold improper rotation, Sn

An improper is the most complex symmetry element to

The symmetry classification (Group Theory)

The Schoenflies system, more common.

What is point group

A point group is a collection of symmetry

In essence, group theory is a set of

The diagram for

Summary of shapes corresponding to

Molecule belong to C1 if has no other element

Group Cn Cnv Cnh

Group Dn Dnv Dnh

Its the molecule that has not classified into one

The cubic groups

The full rotation group

Cv and Dh point groups

Asymmetrical diatomics (e.g. HF, CO and [CN]-) and linear

Groups of high symmetry

If the molecule belongs to group Cn with n > 1,

(a) A molecule with a Cn

A chiral molecule is a molecule that cannot be

Linear algebra in symmetry: Dictionary

The effect on a matrix of a change in coordinate system

Traces and determinants

The trace of a matrix is defined as the sum of the

The determinant of a matrix is a value associated

Group representation and character tables

Example: C2v point group

Example 1: C2v point group (H2O)

Proof the following statements:

We can say that this set of characters also forms a representation,

Reducible and irreducible representations

Properties of characters of irreducible

Properties of characters of irreducible

Example 2: C3v point group (NH3)