CHEM 238

UV-Vis Spectroscopy – The Aldol Condensation

UV-Visible Spectroscopy as a Characterization Technique

UV-Visible spectroscopy (UV-Vis) is a technique that measures the electronic transitions within a molecule in the ultraviolet
and visible regions of the electromagnetic spectrum. Molecules will have specific wavelengths they absorb light at due to
energy differences in their molecular orbitals. Since each molecule has a unique set of molecular orbitals, they will absorb
light at unique wavelengths. Compounds with color will absorb light in the visible region and many organic compounds
absorb light in the ultraviolet region. UV-Vis spectroscopy can be used to help confirm the formation of a colorful product
by determining the characteristic wavelength(s) of maximum absorbance (λmax). Also, the UV-Vis data for a product of a
reaction can be compared to that of the reactants to confirm that a chemical change occurred.

You will be comparing your own data that you collected in lab this week with published data. You will also be calculating
UV-Vis spectra in WebMO to compare to your experimental data.

For the analysis portion of your ILN Pro, in addition to the usual analysis, complete and answer the following
questions using the information provided and your own calculations.

1. Compare your experimental spectrum to the literature spectra in acetonitrile.

a. How do the λmax values compare?
b. Are there any peaks in the literature spectra that you did not see in your own spectrum?

2. Calculate the UV-Vis spectra for the starting materials and product for the experiment according to the directions
in this document.
a. For the product (TPCP):
i. List the five energy values (in nm) with the greatest intensities. These can be found in the table in
the “Excited States” section of the results.
ii. List three λmax values from the spectrum calculated. As a reminder, λmax values are the wavelengths
where a peak is found.
iii. Which values from the table match the closest with the ones on the UV-Vis spectrum?
b. For the starting materials (benzil and dibenzyl ketone):
i. List the three energy values (in nm) with the greatest intensities for each molecule.
ii. List one λmax value from the spectrum calculated for each molecule.
iii. Which value from the table match the closest with the peak in the UV-Vis spectrum? Answer for
each both benzil and dibenzyl ketone.

3. Compare your UV-Vis spectrum for TPCP to the calculated spectrum for TPCP. How do the λmax values and
intensities compare?

4. Based on the data collected in lab and calculated afterwards, how could you determine if the reaction occurred using
UV-Vis spectroscopy?

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UV-Vis Spectroscopy – The Aldol Condensation

Literature Data
Please use the following information from The Journal of Organic Chemistry from March 26, 2008, as literature data for
your ILN Pro. The relevant information has been compiled for you, but you can access the article at the following link
using TAMU Wi-Fi or VPN. Please cite this in your ILN Pro in the References section.
https://pubs.acs.org/doi/full/10.1021/jo701676x

Figure 1. This shows normalized UV-Vis spectra of TPCP in a variety of solvents. MeCN is acetonitrile, CH2Cl2 is dichloromethane, and MeOH is
methanol.

Table 1. The absorption maxima (λmax) of TPCP in acetonitrile. CPD1 refers to TPCP and
λmax are reported in nm. Note that this table is edited for clarity from the original source.

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Using WebMO to determine a calculated UV-Vis spectrum

In addition to comparing experimental UV-Vis spectra to one reported in literature, they can be compared to calculated
spectra. This might be useful if you are unsure of what wavelengths the absorbances will be or their relative intensities since
you can then adjust your experimental procedures accordingly. Calculated UV-Vis spectra also give information about the
energies of the molecule’s molecular orbitals.

1. Download the XYZ file titled “tpcpgeometry.xyz” from the “Aldol Condensation” page on Canvas. This is a starting
geometry for the TPCP molecule that you will use for your calculations.
2. Access WebMO through Canvas on the “Molecular Modeling” page.
a. Log in using your NetID
b. Select “chem237” as the group and use the password “organic”

Tetraphenylcyclopentadienone (TPCP)
1. Optimize the geometry of the TPCP molecule provided.
a. Create a new job
b. Upload the XYZ geometry file.
i. Click “File” then “Import Molecule”
ii. Change the format to “XYZ” in the drop-down menu
iii. Select the geometry file you downloaded from Canvas
iv. Check the box next to “Generate Bonds”
v. Click “OK”
c. Adjust the bonds so that the six-membered rings are phenyl groups.
i. To change to a double bond, use the cursor (select) tool to click a bond, then right click and go to “Bond
Properties” and select “Double”
d. Click the broom tool to clean up the molecule
e. Click the bottom right arrow to set up and run the rest of the calculation.
i. Select “Gaussian” then the next bottom right arrow
ii. Rename your job appropriately
iii. Choose “Geometry Optimization” for Calculation, “B3LYP” for Theory, and “Routine: 6-31G(d)” for
Basis Set. Make sure Charge is set to 0 and Multiplicity is set to Singlet.
iv. Click the bottom right arrow to run the calculation. This might take about 15 minutes to run.

2. Calculate the UV-Vis spectrum for your optimized TPCP.

a. Open the finished geometry optimization.
b. Click “New job using this geometry” in the center underneath the molecule. This will open a new job with the
already optimized geometry.
c. DO NOT click the broom tool in your new file. The geometry is already optimized, so we don’t need to clean
it up.
d. Click the bottom right arrow to set up and run the rest of the calculation.
i. Select “Gaussian” then the next bottom right arrow
ii. Rename your job appropriately
iii. Choose “Excited States and UV-Vis” for Calculation, “ZINDO” for the Excited State Method,
“Routine: 6-31G(d)” for the Basis Set. Make sure Charge is set to 0 and Multiplicity is set to Singlet.
iv. Click the bottom right arrow to run the calculation. This should take only a few minutes.

3. View the results for the UV-Vis calculation.

a. Open the finished job. You should see the TPCP molecule with labels on each atom.
b. Scroll down for information about the Excited States.
i. There will be a table of energies and intensities, which are the table version of the information found
in a UV-Vis.
ii. Click the magnifying glass icon to visualize the calculated spectrum.

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UV-Vis Spectroscopy – The Aldol Condensation

Dibenzyl Ketone
1. Optimize the geometry of dibenzyl ketone
a. Create a new job
b. Import the molecule from the WebMO database
i. Click “Look Up” in the top banner, then select “By name”
ii. Type in “dibenzyl ketone” and click “OK”
c. Use the broom tool to clean up the geometry
d. Click the bottom right arrow to set up and run the rest of the calculation
i. Select “Gaussian” then the next bottom right arrow
ii. Rename your job appropriately
iii. Choose “Geometry Optimization” for Calculation, “B3LYP” for Theory, and “Routine: 6-31G(d)” for
Basis Set. Make sure Charge is set to 0 and Multiplicity is set to Singlet.
iv. Click the bottom right arrow to run the calculation. This might take about 15 minutes to run.

2. Calculate the UV-Vis spectrum for your optimized dibenzyl ketone.

a. Open the finished geometry optimization.
b. Click “New job using this geometry” in the center underneath the molecule. This will open a new job with the
already optimized geometry.
c. DO NOT click the broom tool in your new file. The geometry is already optimized, so we don’t need to clean
it up.
d. Click the bottom right arrow to set up and run the rest of the calculation.
i. Select “Gaussian” then the next bottom right arrow
ii. Rename your job appropriately
iii. Choose “Excited States and UV-Vis” for Calculation, “ZINDO” for the Excited State Method,
“Routine: 6-31G(d)” for the Basis Set. Make sure Charge is set to 0 and Multiplicity is set to Singlet.
iv. Click the bottom right arrow to run the calculation. This should take only a few minutes.

3. View the results for the UV-Vis calculation.

a. Open the finished job. You should see the TPCP molecule with labels on each atom.
b. Scroll down for information about the Excited States.
i. There will be a table of energies and intensities, which are the table version of the information found
in a UV-Vis.
ii. Click the magnifying glass icon to visualize the calculated spectrum.

Benzil
1. Follow the same steps as dibenzyl ketone to optimize the geometry of benzil. The calculation should only take a few
minutes.
2. Follow the same steps as dibenzyl ketone to calculate the UV-Vis of benzil. The calculation should only take a few
minutes.
3. View the results of your UV-Vis calculation