Chemical STructure

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Chemical STructure

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

Element Operation Symbol

Identity Identity E

1. Rotation by (360/n)o

Improper axis 2. Reflection in plane perpendicular to Sn

rotation axis

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 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.

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.

Benzene

Ethane (staggered conformation)

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:

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:

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BH3

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