Symmetry and Group Theory

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 Symmetry
Symmetry is a phenomenon of the natural world, as well
as the world of human invention.

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 Symmetry
❖ Symmetry concepts are extremely useful in chemistry.
❖ By analyzing the symmetry of molecules, we can:
o predict infrared spectra,
o describe orbitals used in bonding,
o predict optical activity,
o interpret electronic spectra,
o study a number of additional molecular properties.

What do we study?
1. Define symmetry very specifically in terms of five fundamental symmetry
operations.
2. Describe how molecules can be classified on the basis of the types of
symmetry they possess.
3. Examples of how symmetry can be used to predict optical activity of
molecules and to determine the number and types of infrared- and Raman-
active molecular vibrations.

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 Symmetry Elements and Operations
Definitions
A symmetry elements is a geometrical entity such as mirror planes,
axes of rotation, and inversion centers, with respect to which one or
more symmetry operations may be carried out.

A symmetry operation, such as the actual reflection, rotation, or

inversion, is an operation, in which a molecule must have exactly the
same appearance after the operation as before.
a symmetry element
(a point in 2D, or
rotational axis in 3D)

A symmetry operation: rotation 90°

A paper windmill
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Five fundamental symmetry operations.

Symmetry operation Symmetry element Notation

Identity - E
Reflection in a plane Plane of symmetry σ
Proper rotation Rotation axis (line) Cn
Rotation followed by Improper rotation Sn
reflection in the plane axis (line)
perpendicular to the
rotation axis
Inversion Center of inversion i

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 Identity operation (E)
• 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.
• SiHClBrF: has only this symmetry

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A≠B
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 The rotation operation (Cn)
The rotation operation (Cn), also called proper rotation, is rotation
through 360°/n about a rotation axis.

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 The C2 rotation operation
C2 operation rotation by 360°/2 = 180°
H2O

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 The C3 rotation operation
C3 operation rotation by 360°/3 = 120°
BF3

NH3

Dr. Said M. El-Kurdi

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 The C32 rotation operation

C3

360°/3 = 120°

C3 2

2 x 120° = 240°
Dr. Said M. El-Kurdi
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 The C4 rotation operation
C4 operation rotation by 360°/4 = 90°

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The C5 & C6 rotation operation

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 Successive operations
A Cn axis generates n operations
For NH3

The three operations generated are:

C3, C32, C33 (=E)
Dr. Said M. El-Kurdi 13
The C2n rotation operation

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 Examples

CHCl3: having a threefold (C3). The C:H bond axis: 360/3 = 120; Two C3 operations: a new
rotation of 240 (C32). Three successive C3 operations (C33 ≡ E).

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 Examples

a ten-fold
rotation
axis

Snowflakes: a twofold (C2) axis, a threefold (C3) axis, and a sixfold (C6) axis, 240 (C32)
and 300 (C65). Two sets of three C2 axes in the plane of the snowflakes, one set through
opposite points and one through the cut-in regions between the points.

In molecules with more than one rotation axis, the Cn axis having the largest value of n is
the highest order rotation axis or principal axis. The highest order rotation axis for a
snowake is the C6 axis.
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 Practice
Indicate the Cn of:
- H2O2
- BrF5
- Triphenylphosphine

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 The reflection operation (σ)
• In the reflection operation (σ) the molecule contains a
mirror plane.

• The reflection operation exchanges left and right, as if each

point had moved perpendicularly through the plane to a
position exactly as far from the plane as when it started.

• 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.

• σv (vertical): the plane contains the principal axis of

rotation.
• σh (horizontal): the plane is perpendicular (vuông góc) to
the principal axis of rotation.
• σd (dihedral) vertical, parallel to principal axis, σ parallel
to Cn and bisecting (chia đôi) two C2' axes
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 The reflection operation (σ)

H2O contains 2 σV

contain the principal axis of rotation

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 The reflection operation (σ)
BF3 has 1 σh and 3 σv planes

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 The reflection operation (σ)

σh perpendicular (vuông
góc) to the principal axis
σv:contain the principal of rotation
axis of rotation

σd (dihedral) vertical,
parallel to principal
axis, σ parallel to Cn
and bisecting (chia đôi)
two C2' axes
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 Inversion (i) – đảo ngược
• Inversion (i) is a more complex operation.
• Each point moves through the center of the
molecule to a position opposite the original
position and as far from the central point as
where it started.

• Squares, rectangles, parallelograms, rectangular

solids, octahedra, and snowflakes have inversion
centers; tetrahedra, triangles, and pentagons do
not.

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 Inversion (i) – đảo ngược

SF6

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 A rotation-reflection operation (Sn)
A rotation-reflection operation (Sn), or improper rotation, requires
rotation of 360/n, followed by reflection through a plane perpendicular to the
axis of rotation.

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A rotation-reflection operation (Sn)

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 Summary

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180°

120°

90°

72°

60°

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The Cn rotation operation + the reflection operation (σ)

Subscript number: order of

the principal rotational axis
(example 3-fold or 4-fold.

Letter: rotational group

3 C2 ┴ C3 axis

C3v D3h
3-fold
rotational
axis

σh mirror plane
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C and D groups

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 The C point group
• Only a single rotational axis (high fold)
• Include Cn, Cnv, and Cnh

❑Cn: NO other symmetry elements

❑Cnv: have also n mirror planes containing

the Cn rotational axis

❑Cnh: also have a σh mirror plane

perpendicular to the principal rotational axis.

C2v

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The C point group
• Only a single rotational
axis (high fold)
• Include Cn, Cnv, and Cnh

❑Cn: NO other symmetry elements

❑Cnv: have also n mirror planes containing

the Cn rotational axis

❑Cnh: also have a σh mirror plane

perpendicular to the principal rotational axis.

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 Practice
NH3, [FeCl3Br3]–, SF4, COCl2

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C3v

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 The D point group
• n C2 axes perpendicular to the principal axis
• Include Dn, Dnd, and Dnh
❑Dn: NO other symmetry elements

❑Dnd: have also vertical mirror planes

containing the Cn axis

❑Dnh: also have a σh mirror plane

D3 3 C2 ┴ C3 axis bisecting the principal axis

Ruthenium triethylenediamine
Ru(en)32+ – D3

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 The D point group
• n C2 axes perpendicular to the principal axis
• Include Dn, Dnd, and Dnh

❑Dn: NO other symmetry elements

❑Dnd: have also vertical mirror planes

containing the Cn axis

❑Dnh: also have a σh mirror plane

bisecting the principal axis

C6H12
D3d
3 C2 ┴ C3 axis
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 The D point group
• n C2 axes perpendicular to the principal axis
• Include Dn, Dnd, and Dnh

❑Dn: NO other symmetry elements

❑Dnd: have also vertical mirror planes

containing the Cn axis

❑Dnh: also have a σh mirror plane

bisecting the principal axis
3 C2 ┴ C3 axis

D3h
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 Practice
PCl5, [FeCl4Br2]3-, C6H6, Mn2F6

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 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.

Group theory, the mathematical treatment of the properties of groups, can

be used to determine the molecular orbitals, vibrations, and other
molecular properties.

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Diagram of the Point Group Assignment Method

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 A Simpler Approach

Ref: The slide of Prof. Marcetta Darensbourg 46

 Diagram of the Point Group Assignment Method
1. Determine whether the molecule exhibits very low symmetry (C1, Cs, Ci) or
high symmetry (Td, Oh, Cv, Dh or Ih).
2. If not, find the rotation axis with the highest n , the highest order Cn (or
principal ) axis, for the molecule.
3. Does the molecule have any C2 axes perpendicular to the principal Cn axis?
If it does, there will be n of such C2 axes, and the molecule is in the D set of
groups. If not, it is in the C or S set.

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 Diagram of the Point Group Assignment Method
4. Does the molecule have a mirror plane (σh) perpendicular to the principal Cn axis? If so, it
is classified as Cnh or Dnh. If not, continue with Step 5.
5. Does the molecule have any mirror planes that contain the principal Cn axis (σv or σd)? If
so, it is classified as Cnv or Dnd. If not, but it is in the D set, it is classified as Dn. If the
molecule is in the C or S set, continue with Step 6.
6. Is there an S2n axis collinear with the principal Cn axis? If so, it is classified as S2n. If not,
the molecule is classified as Cn.

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 C1 group
• The molecule has no symmetry element.
• It has only the identity operation (E),
• or C1: 360°/1 = 360°

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 Cs group
• The molecule has only one plane of symmetry
(reflection plane), and no other symmetry operation.

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 Ci group
• The molecule has only one inversion center (inversion
operation), and no other symmetry.

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 C1, Cs and Ci group

C1 Cs Ci
No symmetry element Contain only one Contain only one
360°/1 = 360° plane of symmetry inversion center

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T = Tetrahedral
O = Octahedral
i = icosahedral

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 Tetrahedral (Td) group
❑ Most (but not all)
molecules in this point
group have the familiar
tetrahedral geometry.
❑ They have:
✓ four C3 axes,
✓ three C2 axes,
✓ three S4 axes,
✓ six σd planes.
✓ No C4 axes.

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 Octahedral (Oh) group
Oh point group contains 3 C4, 4 C3, 9 C2, 4 S6, 3 S4, 3 σh, 6 σd and a centre of
inversion

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 Octahedral (Oh) group
Oh point group contains 3 C4, 4 C3, 9 C2, 4 S6, 3 S4, 3 σh, 6 σd and a centre of
inversion

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2. Find the rotation axis with the highest n, the highest order Cn (or principal)
axis for the molecule.

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3. Does the molecule have any C2 axes perpendicular to the principal Cn axis?

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 4. Does the molecule have a mirror plane (σh horizontal plane) perpendicular
to the principal Cn axis?

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5. Does the molecule have any mirror planes that contain the principal Cn
axis?

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6. Is there an S2n axis collinear with the principal Cn axis?

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Ref: The slide of Prof. Marcetta Darensbourg 65
Ref: The slide of Prof. Marcetta Darensbourg 66
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Groups Related to ih, Oh, and Td Groups

W[N(CH3)2]6, a molecule with Th symmetry. 68

 Practice

Determine the point groups for

a. H ─ C ≡ C ─ F

b. Naphthalene

c. O2F2

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 Fluoroacetylene has only the C∞ axis through
H─C≡C─F all four atoms and an infinite number of mirror
planes, also through all four atoms. C∞v.

Naphthalene

Napthalene has three perpendicular C2 axes,

and a horizontal mirror plane (regardless of
which C2 is taken as the principal axis), making
it a D2h molecule.

O2F2 has a C2 axis perpendicular to the O–O

bond and perpendicular to a line connecting
the fluorines. With no other symmetry
elements, it is a C2 molecule

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Examples and Applications of Symmetry
Molecular Vibrations
Water (C2v Symmetry)

(tịnh tiến)
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 A
A C

Liquid water
(NIST source)
ita ce
ra

Symmetric
Stretching
bend

a e er c )
C e i tr e Boo ttp e oo i t o c e i tr )
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 FT-IR Spectroscopy
Symmetric Antisymmetric

Radial

Symmetric stretching (νs) Antisymmetric stretching (νas)

Latitudinal

Scissoring (δ) Rocking (ρ)

Longitudinal

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Wagging (ω) Twisting (τ) 93
 Car o io i e
itta ce
elati e ra A C

a e er c )
C e i tr e Boo ttp e oo i t o c e i tr )

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 t a ol
itta ce
elati e ra A C

a e er c )
C e i tr e Boo ttp e oo i t o c e i tr )

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 ita ce
ra A C

a e er c )
C e i tr e Boo ttp e oo i t o c e i tr )

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 et a e
itta ce
elati e ra A C

a e er c )
C e i tr e Boo ttp e oo i t o c e i tr )

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