JOEL H.

VILLEGAS Assignment
MAED Science and Technology Date:

For your last assignment, please provide the following info. about water:
1) point group, please include the proof that it belongs to the point group
2) the molecular orbital diagram. Include symmetry and energy analysis.
3) bond order, magnetic properties
4) is the water molecule Raman or IR active based on symmetry considerations.

POINT GROUP

The water molecule possesses three symmetry operations in addition to the identify. These are
illustrated below. The principal symmetry axis is the rotational axis, which we designate as the z
direction. The rotation axis is along the intersection of the two mirror planes. There is no symmetry
specification for which mirror plane is in the xz and yz planes. This may lead to ambiguity in the
assignment of irreducible representations where the symmetry planes are poorly defined.
To identify the point group symmetry of the water molecule, we first identify all possible symmetry
operations. There are four (those shown here plus an identity operation). By using a symmetry identification
flow chart, or by examining the common point groups of molecules, we can identify these four operations
with the C2v point group.

First Molecular Orbital
This orbital is made up from s-contributions from all three atoms.
It is unchanged by any of the symmetry operations. We need to examine
the parity of teh wavefunction. Applying one of the four operations in this
example system will result in a molecular orbital which is identical to the
starting case, or sign of the wave function will be multiplied by -1 (the
positive lobes will become negative and visa versa). In the pictures of the
molecular orbitals, the positive lobes are indicated in blue and the
negative lobes in red. The parity under each operation corresponds in
the current example to the character in the table below. There is no
change of sign under any of the operations, so the characters must all
be 1: the irreducible representation of the first orbital is a1.

Bond Order of Water

This orbital change sign when rotated or reflected in the first

mirror plane, but does not change when reflected in the second mirror
plane. Looking at the irreducible representations of the point group
Second Molecular Orbital shows that the second orbital is b2.

This orbital does not change sign when rotated or reflected in the
either mirror plane. As with the first orbital, this is a1.

Third Molecular Orbital

This orbital changes sign with rotation, and when reflected in the
second mirror plane. It does not change under the first mirror plane.
Thus, the odd parity with the rotation and second mirror plane indicates
Fourth Molecular Orbital b1.

This orbital is invariant with all symmetry operations and is also

a1.

Fifth Molecular Orbital

This orbital changes sign with both the rotation and the first mirror
plane. This, as with the second orbital is b2.

Sixth Molecular Orbital