ECEN 4005-5005 Organic Electronics • S19

Homework #2
Due date: 1/25/19 at the beginning of class.
Please submit a PDF file to Canvas, through the assignment submission system.
Each problem is worth 10 points unless otherwise noted.

1. Hückel Theory in practice. Using an online Hückel molecular orbital energy calculator
[1], calculate the HOMO-LUMO energy gap for benzene, naphthalene, and anthracene,
in units of eV. Note that α = 158 kcal/mol and β = 84 kcal/mol, where 1 kcal/mol =
0.043 eV.

Molecular structures:
benzene naphthalene anthracene

2. A quantum solution (15 points). Another way to examine the energies of π-electron
systems is to consider them as particles in a 1-dimensional box, which according to
quantum mechanics has energies of

where ħ = 1.05 x 10-34 J s, m is the electron mass = 9.11 x 10-31 kg, and n is the quantum
state. The HOMO can be considered as the n = N/2 state, where N is the number of
electrons. The LUMO can be considered as the n = N/2 + 1 state.

a. Calculate the HOMO-LUMO band gaps (in eV - watch the units) for the series of
ethylene chains consisting of 2, 4, and 8 carbon atoms as shown below, according to the
quantum particle-in-a-box equation. Assume the length of the box L is the length of the
molecular chain as given below.
b. Compare this to what you get from Hückel theory. Show your calculations, from the
formula for eigenvalues of a tridiagonal matrix as we discussed in class (do not use
online software for this part). Notice that the agreement becomes better as the length
increases.
Molecular structures:
ethylene butadiene octatetraene
H H H H
CH2 C CH2 C C C CH2
H2C C H2C C C C
H2C H H H H
L ~ 2.8 Å L ~ 5.6 Å L ~ 11.2 Å

c. For butadiene, illustrate how the molecular orbitals gain a node along the length of the
molecule for each increase in energy. Do that by plotting the four orbitals, orbitals, in
increasing energy, and indicating where the nodes are [2].

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 ECEN 4005-5005 Organic Electronics • S19

Footnotes:
[1] http://www.hulis.free.fr or https://www.ucalgary.ca/rauk/shmo. I mentioned SHMO in
class, but HuLiS runs better and has more features. You can download the .jar for free from
the site or from the course Canvas page.
Note on usage: In HuLiS, you draw molecules by hitting the Build button and then clicking
and dragging carbon atoms. Then hit the Opt button to optimize the bond lengths. The click
on each orbital in the energy diagram on the right to show the orbital and its energy. Ignore
the Lewis structure features on the far right.
[2] You can again use HuLiS or SHMO, but for fun you can also use chemtube3d, here:
http://www.chemtube3d.com/orbitalsbutadiene.htm, which plots in 3D. It also has a lot of
other of features, which you can open up by right-clicking on the molecular diagram.