Вы находитесь на странице: 1из 10

Group Theory and the Molecular Orbitals of the water molecule.

The bonding in the water molecule can be approached from VSEPR as shown below,
which suggests that it should have two lone pairs of electrons, and an H-O-H angles of
less than 109.5o because of the strong repulsion of the lone pairs:
lone
pairs

.. ..
. O.

The parent geometry for two bonds plus two electron pairs (n = 4) is tetrahedral. In this
model, two of the coordination sites on the O-atom are occupied by H-atoms, and the
other two are occupied by lone pairs:

lone
pairs

water has tetrahedral


shape, with lone pairs
occupying two sites
on the tetrahedron

H H
A simple qualitative MO view of this bonding would have the 1s orbitals of the two H
atoms overlapping with the sp3 hybrid orbitals of the O-atom. This is shown on the next
page in Figure 1. One sees that two of the sp3 hybrid orbitals of the O-atom are involved
in overlap with the 1s orbitals of the two H-atoms, while the other two are left as n (nonbonding) orbitals, which are the lone pairs of the Lewis dot/VSEPR structure above.
This view of the water molecule is quite useful, but we can carry out a more sophisticated
analysis based on MO theory. We can use Hyperchem to calculate the energy levels for
the molecular orbitals for the H2O molecule, and then relate this quantitative MO diagram
to the character table for the C2v point group, to which H2O belongs.

Figure 1. Simple qualitative MO diagram representing the overlap of the 1s orbitals with
two sp3 hybrid orbitals on oxygen , with the other two sp3 hybrid orbitals being the lone
pairs on the oxygen atom. These are indicated as n (non-bonding) orbitals.
The MO diagram as calculated for the H2O molecule using the PM3 semi-empirical
approach is seen in Figure 2. Figure 2 shows six orbitals, just as seen in the qualitative
MO diagram for water in Fig. 1. However, we notice that the six levels are given labels,
which correspond to the symmetry labels in the character table for the C2v point group
(Figure 3). These labels derive from the effects of symmetry operations in the character
table for the C2v point group on the atomic orbitals on the O-atom (2s and 2px, 2py, 2pz)
and the two H-atoms ( two 1s orbitals) that might participate significantly in the bonding.
The 1s orbital on the O-atom will participate very slightly, but we do not consider it here.
Use of the character Table for a molecule allows one to determine which atomic orbitals
will overlap significantly with each other to produce the bonding in the resulting
molecule. Significant overlap only occurs between atomic orbitals with the same
symmetry labels. First, we put all the atomic orbitals on oxygen and on the two H-atoms
through the symmetry operations indicated in the character Table. If the sign of the
wavefunction of the orbitals does not change when the symmetry operation is carried out,
then this corresponds to a 1 in the representations in the column below that symmetry
operation. If the sign changes, then this corresponds to a -1 in the column of
representations.

Figure 2. Quantitative energy levels for the MOs of the water molecule, calculated using
the PM3 semi-empirical basis set in Hyperchem.

Figure 3. Character table for the C2v point group.

Symmetry properties of the atomic orbitals contributing to bonding in the H2O


molecule:
Consider the 2s orbital of the oxygen atom. We ignore the E (identity) operation column, as this is
always 1. It does nothing, so it has no effect. The C2 operation, and the v(xz) (Figure 4) and
v(yz) operations (not shown) do not change the sign of the wavefunction on the 2s orbital:

a)

b)
Figure 4. The effect on the 2s orbital (a) and the 2pz orbital (b) of oxygen of the symmetry
operations from the character Table for C2v. Note that these do not change the sign of the
wavefunction of the 2s or 2pz orbital, which shows that the symmetry of these orbitals is a1.

a)

b)
Figure 5. The effect on a) the 2py and b) the 2px orbital of oxygen of the symmetry operations
from the character Table for C2v. Note that for the 2py the C2 and v(xz) operation changes the
sign of the wavefunction, so the symmetry is b2. For the 2px the C2 operation changes the sign, but
the v(xz) does not, which shows that the symmetry of this orbital is b1.

The 1s orbitals of the two H atoms may similarly be assigned symmetries from the
character table. The two possibilities are that the 1s orbitals from both H atoms will have
the same sign of the wavefunction, or opposite signs. In Figure 6 is shown the C2
symmetry operation on the two H 1s orbitals where they have the same sign. The reader can
work out that the v(xz) operation will also leave the sign of the wavefunctions unchanged. The
symmetry for the situation where the sign of the two wavefunctions of the two H-atoms have the
same sign has a1 symmetry.

Figure 6. Effect of the C2 rotational operation on the signs of the wavefunctions of two H
1s orbitals having wavefunctions of the same sign. The reader can work out that this
pairing of H 1s orbitals has a1 symmetry.
Where the two H 1s orbitals have opposite signs, the C2 operation (Figure 7) changes the
sign of their wavefunctions. The reader can work out that this pairing of H 1s orbitals has
b2 symmetry.

Figure 7. Effect of the C2 rotational operation on the signs of the wavefunctions of two H
1s orbitals having wavefunctions of the opposite sign. The reader can work out that this
pairing of H 1s orbitals has b2 symmetry.

Construction of the MO diagram for the water molecule:


The important rule for constructing an MO diagram is that only atomic orbitals of the
same symmetry can overlap significantly. Thus, we place the atomic orbitals for oxygen
on the left of ten diagram, and the two sets of orbitals for the H-atoms, and label them
according to their symmetry:

Step 1. Place the four bonding atomic orbitals for Oxygen on the left, and the two atomic
1s bonding orbitals for the two H atoms on the right. The orbitals with a1 symmetry are
colored red.

Step 2. Now overlap all the orbitals that have a1 symmetry, highlighted in red. Note that
three orbitals have a1 symmetry, so only three orbitals having a1 symmetry can be
produced, hence there is only one antibonding a1* level. The 1s (a1) orbital is to some
extent a non-bonding orbital.

Step 3. Now construct a bonding b2 and an antibonding b2* level from the two b2
symmetry atomic orbitals present, shown in blue. Note that there are two b2 symmetry
atomic orbitals, so there will be two b2 symmetry molecular orbitals.

Step 4. The 2px orbital has b1 symmetry, but none of the H 1s orbitals have b1 symmetry,
so no overlap occurs. Place this lone b1 symmetry orbital as a non-bonding orbital which
is at the same energy as the original atomic orbital.

Step 5. Feed the electrons (6 from O and 2 from the 2 H atoms) into the molecular
orbitals. The bonding derives mainly from the overlap of the 2py and 2pz orbitals of O
with the 1s orbitals of the two H atoms. The 2s (a1) orbital of O is to some extent a nonbonding level, so that we have shown the overlaps of the 1s orbital of O with other
atomic orbitals with broken lines, indicating that the overlap is small.
The MOs for water are shown in Figure 8. None of them correspond to the bunny ears
lone pairs suggested by VSEPR. The only totally non-bonding orbital is the 2px orbital,
which is shown enlarged in Figure 9.

Figure 8. The energy levels of the molecular orbitals of the water molecule, together with
drawing of the corresponding molecular orbitals.

Figure 9. The non-bonding b1 MO of the O atom in water, which is essentially the 2px
orbital.
There are no bunny ears on water in the MO model. When the water forms, for example,
H-bonds, the interaction is a largely ionic interaction between the partial positive charges
on the H atoms, and the partial negative charge on the 2px orbital of the O atom of a
neighboring water, as shown in Figure 10. One can measure the predicted H---O-H angles
of the H-bond, and find that these are about 110o, giving the appearance of a tetrahedral
arrangement around the O-atom, comprised of two H atoms bonded to it, and two other
H-atoms from neighboring water molecules H-bonded to it.

Figure 10. PM3 generated structure of two water molecules H-bonded to a central water
molecule, showing how the H-bonds form at a spot suggesting the presence of bunny
ear lone pairs, as described in the text.

10