Molecular Symmetry

The systematic treatment of symmetry makes use of a branch of mathematics called group
theory .

A fundamental concept of the chemical application of group theory is the symmetry operation, Symmetry
operations are actions that leave the molecule apparently unchanged; each symmetry
operation is associated with a symmetry element. (symmetry operations byeshte8lo 3al symmetry element).

All these operations leave at least one point unchanged and hence
they are referred to as the operations of point-group symmetry. (the middle one) such that in H2O.

By convention, the highest order rotational axis, which is called

the principal axis , defines the z -axis (and is typically drawn vertically).

The n-fold rotational axis with the highest value of n is defined as the principal axis. When drawing
molecules, you always want to place the principal axis up and-down (or along the z-axis).

There are three types of mirror planes:

Because the mirror planes are vertical, in the sense of containing the rotational ( z ) axis of the molecule
(parallel), they are labelled with a subscript v, as in v and v.
a mirror plane h in the plane of the molecule. The subscript h signifi es that the plane is horizontalin the
sense that the vertical principal rotational axis of the molecule is perpendicular to it.

d for the planes that bisect the angle between the F atoms.
The d denotes dihedral(but same direction as sigma vertical).

In general, under inversion, an atom with

coordinates ( x , y , z ) moves to ( x , y , z ).
The symmetry element, the point through which
the projections are made, is called the centre of inversion , i . For SF 6 , the centre of inversion
lies at the nucleus of the S atom.
However, there need not be an atom at the centre of inversion: an N 2 molecule
has a centre of inversion midway between the two nitrogen nuclei and the S 4 2ion ( 1 ) has
a centre of inversion in the middle of the square ion. An H 2 O molecule does not possess a
centre of inversion, and no tetrahedral molecule can have a centre of inversion.

An improper rotation consists of a rotation of the molecule through a certain angle

around an axis followed by a refl ection in the plane perpendicular to that axis (Sn, the S coming from the
German word spiegal for mirror).

Neither the 90 ( C 4 ) operation nor the refl ection alone is a symmetry operation for CH 4

but their overall effect is a symmetry operation.

A four-fold improper rotation is denoted S 4 .
S1 = S2 = i
By identifying the symmetry elements of the molecule, and referring to Table 6.2 we can
assign a molecule to its point group .
Just because elements have the same molecular structure doesnt mean they have the same symmetry.
So even though CH4, CCl4, and CHCl3 are all tetrahedral in shape, only CH4 and CCl4 have the same
symmetry.
Because both CH4 and CCl4 have the exact same symmetry elements about a single point (the middle of
the C atom), we classify them as being in the same point group.