Example #4: Planar EH3 (e.g.

BH3 in D3h)

In order to easily determine the phases of the symmetry allowed linear combination of
orbitals for EHn or EXn (n = 3,4,5,6) we will need the following table, which can easily
be derived from the orbital phases of cyclic molecules with ring sizes n = 3, 4, 5.

Q. What do the equivalent MO’s look like for cyclic n = 4, 5, 6, etc.?

Q. What do these MO’s represent?

Q. How can we use these to build the MO’s of BH3? NH3? CH4? Etc.

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1) The three SALCs on the previous page are generated from the three H1s AO’s.

2) The 2s and three 2p orbitals of the central B atom will mix with these.

3) But first, we need to assign symmetries to all our orbitals.

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Example #5: Non-planar EH3 (e.g. NH3 in C3v)

• In NH3, the central atom sits out-of-plane of the H-SALCs.

• We use the same SALCs but a different character table.

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5.4 Walsh Diagrams

• Walsh diagrams track the energy of the MO’s as the shape of a molecule is changed.

• We can predict the shape of a molecule (e.g., linear vs. bent) based on the number of
electrons.

• The above Walsh diagram was created from the linear and bent EH2 MO diagrams
that we have already developed.

• The anti-bonding MO’s are not shown in the above diagram, but we could track them,
too.

Filling electrons into the above Walsh diagram:

• for EH2 (E = Be) : 4 valence electrons…most stable at far right side of diagram
… bond angle ca. 180° (linear!)

• for EH2 (E = O) : 8 valence electrons…most stable near the left side of diagram
… bond angle ca. 104° (bent!)

We can also predict that the first excited state of BeH2 will be bent and that BH2 should
have a linear first excited state!

HOMEWORK: Using the MO diagrams for BH3 and NH3, construct a Walsh diagram for
EH3. Use your diagram to predict whether OH3+ is D3h or C3v symmetry. Can you
construct an MO diagram for a hypothetical “T” shaped EH3 molecule?

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