Pi molecular orbitals

1. The number of molecular orbitals (n) for a pi-system is

equal to the number of contributing p orbitals. For the
allyl system, n=3. We had three contributing p orbitals and
thus three pi molecular orbitals.
2. The lowest-energy orbital always has zero nodes
between the p-orbitals (note that we say “no nodes
between the p-orbitals” because we’re not counting the
node between the individual lobes, which is inherent
to all p-orbitals). That is, in the lowest-energy orbital, all
phases of the contributing p-orbitals are aligned the same
way.
3. The number of nodes between p-orbitals
increases by 1 for each successive energy level, such
that the highest-energy orbital has (n-1) nodes (all
phases of contributing p-orbitals alternate).
4. The lowest and highest energy orbitals are always
the easiest pi molecular orbitals to draw. It’s helpful
to draw them first.
5. The trick to drawing the orbital(s) of intermediate
energy is to understand where to put the node(s).
Nodes are positioned in a way such that they
are symmetrical relative to the centre. A system
with 1 node has the node smack in the centre (right
on the central atom, in fact). A system with 2 nodes
will have the nodes at equal distance relative to the
centre.
6. It’s helpful to draw out all the orbitals of the pi
system first, and then add the pi-electrons to it.
• The Butadienyl Pi System (n = 4)
• As the name suggests, butadiene is composed of
4 carbons with two adjacent pi bonds. As we
showed in this earlier post on conjugation and
resonance, these two pi bonds are conjugated :
all four p orbitals are all aligned with each other,
and build up into a larger pi system. It’s for this
reason that we can describe the electron density
in butadiene with resonance forms, which show
alternative distributions of pi electrons in the
molecule.
Since butadiene consists of 4 individual p orbitals, the pi-system of
butadiene will contain 4 pi molecular orbitals.
Using the principles we learned from drawing out the pi molecular
orbitals of the allyl system, let’s try to draw out what each of these
four molecular orbitals should look like.
• The Lowest-Energy Molecular Orbital (π1)
• The lowest energy molecular orbital will have p orbitals with phases in complete alignment with each
other. This is very easy to draw: just draw four consecutive p-orbitals all aligned the same way.

We could have also drawn the pi-system with all the shaded lobes pointing up:
it’s the same thing. The constructive overlap between the lobes results in a pi
orbital that extends over the entire length of the pi system (above right); there
are zero nodes between the p orbitals themselves. A physical interpretation of
this orbital is that an electron in this orbital is delocalized over the length of the
pi system.
• The Highest-Energy Molecular Orbital (π4)
• The highest-energy molecular orbital is also very easy to draw. Just draw n (4 in our case) p
orbitals and alternate the phases of each. This creates a pi system with three nodes (areas
where the lobes change sign). We’ve drawn the nodes in as red dotted lines.
• The Second-Lowest-Energy Molecular Orbital (π2)
• The second-lowest-energy molecular orbital in butadiene will have 1 node. The trick is
knowing where to put it.
• As we saw with the allyl system, the node cannot just be placed anywhere; the mathematical
properties of the Schrödinger wave equation (which we don’t need to get into) dictate its
position. Thankfully, node placement for this orbital is pretty straightforward: just plunk it in

the middle.(This goes for all systems with a single node, by the way).

Note how the phases flip in the centre of the pi orbital. This
corresponds to the situation we’d expect to see for two adjacent non-
interacting pi bonds, where the electrons are each confined to pi
orbitals spanning two carbons each, with a node in the middle (above
right).
• The Third-Lowest-Energy Molecular Orbital (π3)
• Finally we come to the third-lowest-energy molecular orbital (or second-highest, if you prefer). This
has two nodes.
• Where to place them?
• The general principle is that they are placed symmetrically with respect to the centre. This is what
the orbital picture looks like:

This gives us a 2-carbon pi orbital in the centre flanked by two one-carbon orbitals on the
sides.
The Molecular Orbital Diagram For The Butadienyl System (n=4)
Now that we have all the pieces, all we need to do to construct the molecular orbital diagram for the butadienyl
system is to arrange the orbitals in order of increasing energy. That gives us the following figure (note that we
haven’t added any electrons to it yet).
A molecular orbital diagram without electrons is like an apartment building without people. So
let’s pick the simplest possible molecule to apply to this system: butadiene.
Butadiene has two double bonds with two electrons each, for a total of 4 pi electrons. We fill up
the lowest-energy molecular orbitals first, which gives us the following
• We’ve highlighted two molecular orbitals on this diagram as
being of particular interest, because, as we’ll see, they’re
where the action usually happens. The are sometimes called
the “frontier” orbitals.
• The highest occupied molecular orbital (HOMO) is π2. You
can think of the HOMO as being a little bit like the “valence
electrons” of the pi system: they’re the most readily lost. If
butadiene participates in a reaction where it is the electron-
donor (nucleophile), its electrons are going to come from that
orbital.
• The lowest-unoccupied molecular orbital (LUMO) is π3. The
LUMO is the lowest-energy unoccupied orbital. If butadiene
participates in a reaction where it is the electron acceptor
(electrophile), the electrons will be donated to that orbital.
 The Pi Molecular Orbitals of Benzene
• the molecular orbitals of the 6-electron pi systems, Here’s of what the molecular orbitals of benzene look
like.
• Six p orbitals in the pi systems of benzene will produce six pi
molecular orbitals.
• Drawing The “Penthouse”
• The Highest Like the ground floor, the highest-energy molecular orbital (the “penthouse”) of
a pi system is also straightforward to draw.
• Draw all the p orbitals with alternating phases. No two adjacent p orbitals should have lobes
with the same phase.
• For linear systems, we’ve seen that this gives the highest energy level (n–1) nodes. For
hexatriene (n=6) that means that the highest energy level will have 5 nodes.
• Energy molecular orbitals have p orbitals with completely alternating phases.
• This orbital has zero overlap between adjacent p orbitals and therefore electrons in this orbital have the minimum possible
delocalization. They are therefore the highest energy.

These two molecular orbitals (π2 and π3 ) have the same number of nodal
planes, and therefore have the same energy. The way we usually describe this
in chemistry is by saying the orbitals are degenerate.
This is really the key difference in the molecular orbital picture of a cyclic
system versus an acyclic system: two units can co-exist on the same floor. For
benzene, that results in a lowering of energy.
• Filling Out The Rest of The Picture
• Here’s the third, fourth, and fifth “floors” for the hexatriene pi system, which have two, three, and four nodes, respectively

For benzene, the next level up

has two nodal planes. Again,
there’s two ways to do it: cut
through the bonds, or cut
through the atoms. Again, these
are of the same energy.
5. Putting It All Together
The final step is to arrange all the pi orbitals together (by “floors”) and then to fill each level with
electrons (“tenants”).
Here’s the complete molecular orbital picture for hexatriene:
The complete molecular orbital picture for benzene was drawn at the top of the post, but here it is again for your
non-scrolling pleasure:
• . Why Is Benzene More Stable Than Hexatriene?
• A cyclic pi system allows for two ways to place a single nodal
plane: through-bond, or through-atom. In benzene, this
means that the second and third “floors” each have two units
with the same energy – they are “degenerate”.
• To follow our somewhat crude analogy, both buildings have
six “tenants”, but in benzene, those tenants aren’t as high off
the ground – and thus have less potential energy.
• In chemistry terms, the highest occupied molecular orbitals
(HOMO) of benzene are lower in energy than the highest
occupied molecular orbital (HOMO) of hexatriene. And for our
purposes, that lower energy of the pi-electrons translates into
lower reactivity.