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Infrared Spectrum of Acetone

This tutorial illustrates the steps required to calculate and display
the infrared spectrum of a molecule.

Molecules vibrate in response to their absorbing infrared light.

Absorption occurs only at specific wavelengths, which gives rise to
the use of infrared spectroscopy as a tool for identifying chemical
structures. The vibrational frequency is proportional to the square root
of a quantity called a “force constant” divided by a quantity called the
“reduced mass”.
force constant
frequency α
reduced mass

The force constant reflects the “flatness” or “steepness” of the energy

surface in the vicinity of the energy minimum. The steeper the energy
surface, the larger the force constant and the larger the frequency.
The reduced mass reflects the masses of the atoms involved in the
vibration. The smaller the reduced mass, the larger the frequency.
This tutorial shows you how to calculate and display the infrared
spectrum of acetone, and explore relationships between frequency
and both force constant and reduced mass. It shows why the carbonyl
stretching frequency is of particular value in infrared spectroscopy.
1. Click on to bring up the organic model kit. Select sp2 carbon
( ) and click anywhere on screen. Select sp2 oxygen ( ) and
click on the double free valence on carbon to make the carbonyl
group. Select sp3 carbon ( ) and, one after the other, click on the
two single free valences on carbon. Click on and then on .
2. Enter the Calculations dialog (Setup menu) and request
calculation of an equilibrium geometry using the HF/3-21G model.

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 Check IR to the right of “Compute” to specify calculation of
vibrational frequencies. Finally, click on the Submit button at the
bottom of the dialog, and provide the name “acetone”.
3. After the calculation has completed, bring up the Spectra dialog
(Display menu). This contains a list of vibrational frequencies
for acetone. First click on the top entry (the smallest frequency)
and, when you are done examining the vibrational motion, click
on the bottom entry (the largest frequency).

The smallest frequency is associated with torsional motion of the

methyl rotors. The largest frequency is associated with stretching
motion of CH bonds. Methyl torsion is characterized by a flat potential
energy surface (small force constant), while CH stretching is
characterized by a steep potential energy surface (large force constant).

Display the IR spectrum (click on Draw IR Spectrum at the

bottom of the dialog). Locate the frequency corresponding to the
CO stretch. The experimental frequency is around 1740 cm-1, but
the calculations will yield a higher value (around 1940 cm-1).

The CO stretching frequency is a good “chemical identifier” because

it “stands alone” in the infrared spectrum and because it is “intense”.

4. Change all the hydrogens in acetone to deuteriums to see the effect

which increased mass has on vibrational frequencies. First make
a copy of “acetone” (Save As... from the File menu or click on
the icon in the toolbar). Name the copy “acetone d6” Select
Properties from the Display menu and click on one of the
hydrogens. Select 2 deuterium from the Mass Number menu.
Repeat for the remaining five hydrogens.
5. Submit for calculation. When completed, examine the vibrational
frequencies. Note that the frequencies of those motions which
involve the hydrogens (in particular, the six vibrational motions
corresponding to “CH stretching”) are significantly reduced over
those in the non-deuterated system.
6. Close all molecules on screen in addition to any remaining dialogs.
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