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CHEM 1004 | Interfaces

SYMMETRY OF MOLECULES
Definitions

• Symmetry operation – an action, which when applied to a molecule, leaves the molecule
in an orientation indistinguishable from its original orientation

• Symmetry element – (associated with each symmetry operation) a point line or plane
with respect to which the symmetry operation is performed

5 Categories

1 Identity (‘do nothing’), E

• All molecules have at least 1 symmetry operation

2 Rotation, Cn

• An n-fold rotation is a symmetry operation if the molecule appears unchanged after

rotation by

• Symmetry element: line (n fold rotation axis)

• Example: For water, 180o = 360/2, n = 2 (two-fold rotation)

• For ammonia, three-fold rotation axis running through N atom, with 2 symmetry
operations associated with this symmetry element

1 120o clockwise rotation (C3 / C3–)

2 240o clockwise rotation / 120o anti-clockwise rotation (C32 / C3+)

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3 Reflection, σ

• Symmetry element: mirror plane

• 3 types of mirror planes

• Vertical mirror plane (σ v): contains the principal rotational axis (i.e. axis with the highest
n value)

• Horizontal mirror plane (σ h): perpendicular to principal axis of rotation

• Dihedral mirror plane (σ d): contains the principal rotation axis; a vertical plane that
bisects the angle between the two C2 axes that lie perpendicular to the principal axis

• Example: Benzene – C6 axis (perpendicular to the plane of molecule) while σ h plane is

the plane containing all atoms (perpendicular to C6 axis)

• Benzene has 3 σ v planes which contain C6 axis and diametrically opposite pairs of C–H
bonds

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4 Inversion, i

• Each atom is projected in a straight line through a single point and out on equal distance
on the other side

• Symmetry element: centre of inversion (i)

5 Improper rotation, Sn

• Rotation by a certain angle about a given axis followed by reflection in a plane

perpendicular to that axis
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• Example: CH4 – S4 improper rotation consists of a C4 rotation followed by a σ h

reflection, for which neither C4 nor σ h is a symmetry operation for CH4 on their own

• Note: S1 = 360o rotation followed by σ h = σ h and S2 = 180o rotation followed by σ h = i

Hence, no such thing as S1 or S2

• Note: Tetrahedral species of the type XY4 (all Y groups must be equivalent) possess
three S4 axes

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Point Groups

• Refer to a collection of symmetry operations

• To do this, it is usually unnecessary to identify all the symmetry operations and elements
within the molecule

• Note: Symbols at each decision refer to the symmetry element, not the operator
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Examples

• Water – possible symmetry operations: E, C2, σ v, σ v’

Point group with only these 4 operations: C2v

• Ammonia – possible symmetry operations: E, C3+, C3-, σ v, σ v’, σ v’’

C3v

• Benzene
From decision tree,
‘Are there 2 or more Cn, n>2?’ No (highest n value = 6 and there is only 1 C6 axis)
‘Are there 6 C2 perpendicular to C6?’ Yes, there are 6 C2
‘σ h?’ Yes there is horizontal mirror plane

Hence, D6h (E, C6+, C6-, C3+, C3-, C2, S6+, S6-, S3+, S3-, i, σ v x 3, σ h x 3, 6 C2 (aces
perpendicular to C6)

• BF3 – C3 axis running through B, perpendicular to plane of molecule

n=3, 3 C2 perpendicular to C3? Yes
‘σ h?’ Yes there is horizontal mirror plane (which is the plane of molecule itself)

Hence, D3h
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