SYMMETRY ELEMENTS and SYMMETRY OPERATIONS

Welcome to the world of symmetry!

Symmetry plays a central role in the analysis of the structure, bonding, and spectroscopy of molecules.

Table of Elements and Operations

Element Operation Symbol

Identity Identity E

Symmetry plane Reflection in the plane σ

Inversion center Inversion of a point x, y, z to -x,-y,-z i

Proper axis Rotation by (360/n)o Cn

1. Rotation by (360/n)o
Improper axis 2. Reflection in plane perpendicular to Sn
rotation axis

The Identity Operation (E)

 The identity operation is the simplest of all -- do nothing! It may seem pointless to have a symmetry operation
that consists of doing nothing, but it is very important. All objects (and therefore all molecules) at the very least
have the identity element. There are many molecules that have no other symmetry. Two examples are shown
below. Each of the following molecules contains no other symmetry other than identity:

 CHFClBr

 SOClBr

The Reflection Operation (σ)

 The reflection operation can be pictured as follows: take each atom in the molecule and move it toward the
reflection plane along a line perpendicular to that plane. Continue moving the atom through the plane to a point
equidistant from the plane on the opposite side of the plane. If the resulting configuration is
indistinguishable from the original, we say there exist a symmetry plane in the molecule.
Note the differences in the following examples:

 The ammonia molecule contains three identical reflection planes. All are designated as vertical symmetry
planes (σv) because they contain the principle rotation axis.

 The water molecule contains two different reflection planes.

 And benzene contains a total of seven reflection planes, one horizontal plane (σh) and six vertical planes (σv and
σd).
The Inversion Operation (i)
 The inversion operation occurs through a single point called the inversion center, i, located at the center of the
molecule. (Note that the inversion center may or may not coincide with an atom in the molecule.) Each atom in
the molecule is moved along a straight line through the inversion center to a point an equal distance from the
inversion center. If the resulting configuration is indistinguishable from the original, we say there exists an
inversion center in the molecule.

Each of the following molecules contains an inversion center:

 The tetrachloroplatinate(II) ion

 Benzene
 Ethane (staggered conformation)

Proper Rotation (Cn)

 The rotation operations (both proper and improper) occur with respect to line called an axis of rotation. A
proper rotation is performed by rotating the molecule 360°/n, where n is the order of the axis. If the resulting
configuration is indistinguishable from the original, we say there exists an n-fold proper rotation axis (or
Cn axis) in the molecule.
Each of the following molecules contains one or more proper axes:

 The water molecule contains a C2 axis

 Ethane contains both C2 and C3 axes

Improper Rotation (Sn)

 An improper rotation is performed by rotating the molecule 360°/n followed by reflection through the plane
perpendicular to the rotation axis. If the resulting configuration is indistinguishable from the original, we say
there exists an n-fold improper rotation axis (or Sn axis) in the molecule.
Each of the following molecules contains one or more improper axes:

 Staggered ethane contains an S6 axis

 Methane contains three S4 axes

 OTHER EXAMPLES

BH3
BrF5