Ch.

10 Homework

Modeling Conjugated Linear Polyenes

FEMO Theory
1. The free electron molecular orbital (FEMO) theory treats the electrons of a conjugated
molecule as independent particles in a 1-D box of length L (PIB model). The molecular orbitals
produced from this model can each accommodate 2 electrons.
a. Sketch the form of the two occupied molecular orbitals and the LUMO in butadiene predicted
by this model.
b. From the model, calculate the minimum excitation energy of the butadiene (LUMO HOMO). Use a box length of 4R where R = 140 pm (an extra half bond length is added to each
end of the box).
c. Calculate the minimum excitation energy of octatetraene using a box length of 8R. What
wavelength of light would this molecule absorb? Estimate the color of a sample of the
compound in white light.
d. Sketch the HOMO and LUMO of octatetraene.

HMO Theory
2. The FEMO theory of conjugated molecules is rather crude. Compare your results in 1 above
to the experimental results below.
Linear conjugated
polyene
ethene
butadiene
hexatriene
octatetraene

Observed * ultraviolet absorptions

(HOMO to LUMO) in cm-1
61,500
46,080
39,750
32,900

Better results can be obtained with the simple Huckel Molecular Orbital (HMO) theory.
a. Use the SHMO calculator at www.chem.ucalgary.ca/SHMO/ to calculate the total energy
(sum the energy of each electron), energies of the HOMO and LUMO, and the energy of the
HOMO to LUMO transition for each polyene in the table above. Record your results in a table.
b. Using your results from a. and the data in the table given above, determine a reasonable
empirical estimate (in eV) of the resonance integral for this series of molecules.

c. Calculate the electron delocalization energy Edeloc = E N ( + ) of octatetraene where E

is the total electron binding energy and N is the total number of electrons.
d. In the HMO theory, the molecular orbitals are linear combinations of the atomic 2p orbitals
on each C atom. In the SHMO calculator, obtain the coefficients of each of the six 2p orbitals in
each of the six molecular orbitals in hexatriene and match each set to the corresponding energies
of the molecular orbitals. Using the magnitudes and signs of the coefficients to infer the
contribution of each 2p orbital to the entire molecular orbital, sketch the shapes of the six
molecular orbitals. How does the shape of the molecular orbital relate to its energy?

Ab initio Molecular Orbital Calculations

Molecular orbital calculations using ab initio, semi-empirical, or density functional theory (DFT)
methods do a better job of describing the spectroscopic properties of molecules than the simple
HMO theory. Log onto the pchem desktop on SpartanGreen Sky to access the programs
GaussView and Gaussian. In GaussView you can build models of molecules and set up
computational methods that will run in Gaussian.
3. For ethene, butadiene, hexatriene, and octatetraene:
a. Using GaussView, build the molecule using the molecule builder. First select the desired
atom using the element fragment icon in the GaussView window. A periodic table window will
open and you can select the element and its bonding. When you click in the G1:M1:V1 window,
the fragment will be added. Continue to add appropriate fragments to create the molecule. Click
and hold and use the mouse to rotate the molecule to inspect the structure. Clean up the structure
by clicking on the broom icon on the tool bar.
b. Under Calculate, choose Gaussian calculation setup. Set up as follows:
Job type: Energy
Method: Ground state

Hartree-Fock Default spin

Basis set: 6-31G (d)

Charge: 0

Spin: Singlet

Title: name of molecule

Submit the job to start the calculation. You will be asked to save your input file.
c. After the calculation is complete, open the .chk file when prompted and a new window will
open with the optimized structure. In the GaussView window, select Edit and MOs. This will
open a new window in which the energies of the MOs are displayed and the orbitals can be

visualized. The energies of the MOs are displayed in an energy level diagram and electrons are
drawn in for the ground state configuration. The frontier orbitals are highlighted in yellow.
Record the HOMO and LUMO energies. These energies are in hartrees. A hartree is a unit of
energy used in computational chemistry which is equal to 4.3597 x 10-18 J, 2625.5 kJ/mol, 27.211
eV, and 219474.6 cm-1.
View the orbitals within the same window by clicking on the Visualize tab. The highlighted
orbitals are selected to be displayed. Click on Update. It may take a few seconds or minutes for
the orbitals to be calculated. By selecting on the desired orbital in the energy level diagram by
clicking on the small box on the right, you can view an individual MO. Observe the HOMO and
LUMO for each molecule. By clicking and dragging on the molecule, you can rotate the
structure to better view the MO. You can save the MO as a graphics file which can be inserted
into a Word or Excel document or you can use a screen capture to copy the image. In the
window, hold Alt and press Prnt Scrn. Paste the image into Paint, and then select the MO image
and paste into your document.
Other MOs can be calculated by either selecting them under Add list or Add type. Update will
begin the calculations which may take several minutes if many MOs were selected.
d. After you have completed a-c for each molecule, plot the LUMO-HOMO energies versus the
observed wavenumbers in Excel for this series of molecules. Use a fitting procedure to obtain an
equation for the relation. Use this equation to determine the predicted wavenumber for
decapentaene.