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Symmetry operation
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In the context of molecular symmetry, a symmetry operation is a permutation of
atoms such that the molecule or crystal is transformed into a state
indistinguishable from the starting state. Two basic facts follow from this
definition, which emphasize its usefulness.

Physical properties must be invariant with respect to symmetry operations.

Symmetry operations can be collected together in groups which are isomorphic to
permutation groups.
Wavefunctions need not be invariant, because the operation can multiply them by a
phase or mix states within a degenerate representation, without affecting any
physical property.

Contents
1 Molecules
1.1 Proper rotation operations
1.2 Improper rotation operations
1.3 Examples
2 Crystals
3 References
Molecules
Proper rotation operations
These are denoted by Cnm and are rotations of 360�/n, performed m times. The
superscript m is omitted if it is equal to one.

C1, rotation by 360�, is called the Identity operation and is denoted by E or I.

Cnn, n rotations 360�/n is also an Identity operation.

Improper rotation operations

These are denoted by Snm and are rotations of 360�/n followed by reflection in a
plane perpendicular to the rotation axis.

S1 is usually denoted as s, a reflection operation about a mirror plane.

S2 is usually denoted as i, an inversion operation about an inversion centre.

When n is an even number Snn = E, but when n is odd Sn2n = E.

Rotation axes, mirror planes and inversion centres are symmetry elements, not
operations. The rotation axis of highest order is known as the principal rotation
axis. It is conventional to set the Cartesian z axis of the molecule to contain the
principal rotation axis.

Examples
Methylene Chloride.PNG
Dichloromethane, CH2Cl2. There is a C2 rotation axis which passes through the
carbon atom and the midpoints between the two hydrogen atoms and the two chlorine
atoms. Define the z axis as co-linear with the C2 axis, the xz plane as containing
CH2 and the yz plane as containing CCl2. A C2 rotation operation permutes the two
hydrogen atoms and the two chlorine atoms. Reflection in the yz plane permutes the
hydrogen atoms while reflection in the xz plane permutes the chlorine atoms. The
four symmetry operations E, C2, s(xz)and s(yz) form the point group C2v. Note that
if any two operations are carried out in succession the result is the same as if a
single operation of the group had been performed.

Methane-2D-stereo.svg
Methane, CH4. In addition to the proper rotations of order 2 and 3 there are three
mutually perpendicular S4 axes which pass half-way between the C-H bonds and six
mirror planes. Note that S42 = C2.

Crystals
In crystals screw rotations and/or glide reflections are additionally possible.
These are rotations or reflections together with partial translation. The Bravais
lattices may be considered as representing translational symmetry operations.
Combinations of operations of the crystallographic point groups with the addition
symmetry operations produce the 230 crystallographic space groups.

References
F. A. Cotton Chemical applications of group theory, Wiley, 1962, 1971

Categories: Physical chemistrySymmetry

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