Molecular symmetry

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Symmetry operations and symmetry elements

A symmetry operation is carried out with respect to points,

lines or planes, the latter being the symmetry elements.
A symmetry operation is an operation performed on an
object/molecule which leaves it in a configuration that is
indistinguishable from, and superimposable on, the original
configuration.

The rotations are performed about an axis perpendicular to

the plane of the paper and passing through the boron atom;
the axis is an example of a symmetry element.
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Molecular structures of planar BF3 and BF2H molecules

BF bond distances the BH bond is shorter (119 pm)

are all identical (131 pm) than the BF bonds (131 pm).
trigonal planar pseudo-trigonal planar
The molecular symmetry properties are not the same !!

Group theory is the mathematical treatment of symmetry

dealing with symmetry operator, symmetry element, point
group and character table.
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 A symmetry operation leaves the molecule unchanged even
though atoms and bonds may have been moved.

Symmetry Element Symmetry Operation Symbol

Identity E
n-fold axis Rotation by 2/n Cn
Mirror plane Reflection
Center of inversion Inversion I
n-fold axis of improper Rotation by 2/n followed by Sn
rotation reflection perpendicular to
the axis of rotation

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Identity, E
All molecules have Identity.
A highly asymmetric molecule (ex: tetrahedral carbon with 4
different groups attached) has only E symmetry element.
All the points in a molecule can be described with Cartesian
coordinates x, y and z. These points can be transformed by
the following matrix equation:

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 n-fold Rotation Cn H2O has a 2-fold axis of
rotation (C2)
The proper rotation (clockwise direction)
about the z axis can be described by the
following matrix equation.

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 Ammonia (NH3) has a C3 axis.

Rotation by 120o in a clockwise or a counterclockwise

direction provide two different orientations of the
molecule.

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If a molecule possesses more than one type of n-axis, the axis
of highest value of n is called the principal axis; it is the axis of
highest molecular symmetry. For example, in BF3, the C3 axis is
the principal axis.

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 Mirror Planes, s
H2O molecule
Subscript v indicates a vertical
plane of symmetry. This
indicates that the mirror
plane includes the principal
axis of rotation (C2).

If the plane lies perpendicular to

the vertical principal axis, it is
denoted by the symbol sh.

If the plane contains the principal Both are v planes. h-plane

axis, it is labeled sv. has to be perpendicular to
Cn axis (principal axis).
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Mirror planes coinciding with xy, xz or yz Cartesian
planes can be described by the following matrix
equations:

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 Benzene ring:
C6 axis as its principal axis of
rotation.
Mirror plane, h which is
perpendicular to the C6 axis
(principal axis).
Mirror planes, v go through the
carbon atoms, and include the
C6 axis.
Mirror plane, d (dihedral plane)
is perpendicular to the rotation
axis and bisects the bonds.

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XeF4 : a square planar molecule

One C2 axis
coincides with the
principal (C4) axis
the molecule lies in
a sh plane which
contains two C2
and two C2 axes.

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 Each of the two sv Each of the two sd planes
planes contains the contains the C4 axis and one
C4 axis and one C2 C2 axis.
axis.

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Inversion, i
If reflection of all parts of a molecule through the centre of
the molecule produces an indistinguishable configuration,
the centre is a center of symmetry, also called a center of
inversion; it is designated by the symbol i.

CO2 benzene SF6

Reflection through a center of symmetry (inversion center)

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 The inversion operation projects
each atom through the center of
inversion, and across to the
other side of the molecule
(changes sign of all the x,y,z
coordinates.

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 Improper rotation Sn
A rotation followed by reflection in the plane perpendicular to the axis
of rotation (hence changing the sign of the z coordinate only)

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Examples

No i

H2S
cis-N2F2
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The staggered conformation of ethane has an
S6 axis that goes through both carbon atoms.

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 Not an Improper rotation Sn

S1 axis doesnt exist; it is S2 axis is a center of

same as a mirror plane. inversion.

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Successive operations
For NH3

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For example, in planar BCl3, the S3 improper axis of rotation
corresponds to rotation about the C3 axis followed by
reflection through the sh plane.

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SF6

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 Point groups
Molecules are classified and grouped based on their symmetry.
Molecules with similar symmetry are placed into the same point group.
A point group contains all objects that have the same symmetry
elements.
The number and nature of the symmetry elements of a given molecule
are denoted by its point group
Each point group has a complete set of possible symmetry operations
that are conveniently listed as a matrix known as a Character Table.

C1 point group

C1 = E

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Groups with a single symmetry element

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Cnv Point groups
Water and ammonia both
belong to the Cnv class of
molecules. These have
vertical planes of reflection,
but no horizontal planes.

Water C2v point group

Ammonia C3v point group

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 Cv point group
-fold axis of rotation of a linear molecule
It must also possess an infinite number of sv planes
but no sh plane or inversion center.

Examples:
Asymmetrical diatomics such as HF, CO and [CN], and
linear polyatomics that do not possess a center of
symmetry, e.g. OCS and HCN.
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Dnh Point group
Y

The Dnh groups have X

X
a horizontal plane in
addition to vertical
planes. X
X

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Dh 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

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 Td, Oh or Ih Point groups
Molecular species that belong to the Td, Oh or Ih
point groups possess many symmetry elements

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Summary table of point groups

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Determining the point group of a molecule

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Example: trans-N2F2

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Example : PF5

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Character Tables for point groups
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.

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Total representation for C2v

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 Character Table (C2v)

Each row an irreducible rep of the point group

represented by symmetry species A, B, etc.

Representations are orthogonal to each other

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 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.

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 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.
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 Character Table (C2v)
The effect of symmetry elements on mathematical functions is useful because
orbitals are mathematical functions! Analysis of the symmetry of a molecule will
provide insight into the orbitals used in bonding.

The functions to the right are called basis

functions. They represent mathematical functions
such as orbitals, rotations, etc.
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Symmetry of orbitals and functions

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 Applications of Group Theory
1. Predicting polarity of molecules : A molecule cannot have a permanent
dipole moment if a) it has a center of inversion, b) it belongs to any of the D
point groups, c) it belongs to the cubic groups T or O
2. Predicting chirality of molecules : Chiral molecules lack an improper
axis of rotation (Sn), a center of symmetry (i) or a mirror plane ().
3. Predicting the orbitals used in bonds : Group theory can be used to
predict which orbitals on a central atom can be mixed to create hybrid
orbitals.
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.
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.

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 Symmetry considerations

Rule of mutual exclusion: For molecules with center of

symmetry, IR active vibrational modes are R inactive and
vice-versa. Examples: CO 2,room
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 behaves as linear function

behaves as quadratic
function

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Normal modes of vibrations

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cis-PdCl2(NH3)2

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trans-PdCl2(NH3)2

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