Rotation-Vibration Spectroscopy of Carbon Monoxide

Purpose

Rotational and vibrational transitions are observed in infrared spectra of carbon monoxide.
Molecular properties are calculated from the spectra: the bond length, the fundamental vibration
frequency, the anharmonicity, the rotation constant, and the vibration-rotation coupling constant.
Quantum-chemical methods are tested by calculating properties.

Introduction

Infrared spectra are basically vibrational spectra. Infrared light excites vibrations from their
ground states (v=0) to excited states (v=1, fundamental, or v=2, the first overtone).
Simultaneously with vibration, rotations are excited. Spectra of some molecules, mainly small
and light molecules, display many infrared lines. Figure 1 shows an infrared spectrum of
deuterated ethene. Simultaneous vibrational
excitation and rotational transitions account
for the many sharp lines, which are grouped
in "branches." The branches resemble wings
about a central transition. The central
branch is the "Q" branch. Lower-
wavenumber lines are in the "P" branch,
higher-wavenumbers lines constitute the
"R" branch.

Carbon monoxide displays P and R

branches in infrared spectra. As with other
diatomic molecules, there is no Q branch. A
gap takes the place of the Q branch. Every
line in the infrared spectrum of CO can be Figure 1. P, Q, and R branches in the infrared spectrum
assigned to a change in vibrational state and of C2D3H. Adapted from L.L. Ng and T.L. Tan, J. Molec.
a change of ±1 in the rotational quantum Spec., 2020, Figure 2.
number. In the P branch, the ΔJ is -1; in the
R branch it is +1. Many lines are observed because CO
molecules are distributed over many rotational states.

Rotational lines in CO spectra are traditionally indexed

with the variable "m," which is negative on the P
branch, positive on the R branch, and has smallest
magnitude near the central gap. Several values of m are
shown on the spectrum that is sketched in Figure 2.

Figure 2. m values on P and R branches.

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Two spectra are analyzed in this experiment. In the fundamental spectrum, absorption of a
photon changes the vibrational quantum v from 0 to 1. In the overtone spectrum, v changes from
0 to 2. That is why the overtone is at approximately twice the wavenumber of the fundamental.

Quantitatively, the positions of lines are described by a third-order polynomial in m. The

coefficients of the polynomial depend on v, the vibrational quantum number. That is why ω, the
vibration frequency, and B, the rotation constant, carry v subscripts in equation 1. The last
parameter in equation 1, De, is the centrifugal distortion constant. (The symbol De is used for
dissociation energy in other experiments and literature.)
ω(v,m) = ωv + (Bv +B0) m + (Bv-B0) m2 - 4 De m3 (1)
The values of ω, B, and D at equilibrium are indicated with subscripts "e." Relationships
between equilibrium and v-dependent parameters are given below.
ωv = v ωe – v(v+1) xeωe (2)
Specifically, for the fundamental, v=1 and ω v = ω1 = ωe - 2 xeωe (3)
For the overtone, v=2 and ωv = ω2 = 2ωe - 6 xe ωe (4)
The constant xe is the anharmonicity constant. It describes the decrease of vibration frequency
with increasing vibrational quantum number. For rotation, the analogous constant is α e, the
rotation-vibration coupling constant.
Bv = Be – αe (v + ½) (5)
Specifically, B0 = Be - ½αe , B1 = Be – (3/2)αe, and B2 = Be – (5/2)αe. Equation 5 has the form of
a straight line. The intercept is Be. The slope is - αe. It is from a plot of Bv versus (v+1/2) that Be
and αe will be calculated in this experiment. The equilibrium rotation constant B e is closely
related to bond length Re, as shown in equation 6.
ℎ
𝐵 = (6)
8π 𝑐μ𝑅
It is with equation 6 that the bond length will be calculated from the rotation constant. The
reduced mass is μ = 𝑚 𝑚 /(𝑚 + 𝑚 ), c is the speed of light, and h is Planck's constant.

Quantum-chemical calculations

Diatomic molecules have been used as test cases for quantum-chemical methods. In this lab,
restricted Hartree-Fock (RHF) theory and density functional theory (DFT, with the B3LYP
functional) will be used to calculate ωe, Be, and Re, which should be compared with the
experimental results obtained from analyzing infrared spectra. DFT, unlike RHF, includes
electron correlation. Electron correlation refers to the instantaneous repulsion between two
electrons. Uncorrelated methods such as RHF include electron-electron repulsion only in a
spatially-averaged way. Including electron correlation tends to lengthen bonds and lower
vibration frequencies and rotation constants. Calculations done for this lab will test that
generalization.

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Experimental Procedure

This experiment uses three pieces of equipment.

• A gas cell. The path length is 10 cm. Windows are
sodium chloride.
• A Fourier-transform Infrared (FTIR)
Spectrophotometer
• A gas manifold with a pump, pressure gauge and CO
tank
Figure 3. gas cell in FTIR
Figure 3 shows the gas cell inside the FTIR's sample
compartment. Because our gas cell fits only loosely in the FTIR's sample holder, it must be
supported. Put the two-inch plastic insert or other equivalent support below the cell when it is in
the sample compartment.

To evacuate the cell and then fill it with carbon monoxide gas, use the manifold that is in the
hood and the pump that is under the hood. Filling the cell involves slowly opening a closed glass
system to a pressurized gas, so
 wear goggles
 check that the hood is working (look at its gauge) before opening the CO tank
 keep the hood sash down as far as possible
 open valves carefully

To attach the cell to the manifold, slide the plastic

hose from the manifold loosely onto the cell's
ground-glass fitting. Vacuum will make the
connection tight. Figure 4 shows the cell attached
to the hose that is attached to the manifold.

Figure 4. gas cell with hose to manifold

The cell is evacuated by opening the

stopcock that connects the manifold to the
pump, and the stopcock that connects the
manifold to the cell. Another stopcock opens
Figure 5. The manifold and its connections.
the manifold to the hood, useful for
introducing air. A fourth stopcock opens the manifold to a line from the carbon monoxide tank.
Finally, a vacuum hose at the top of the manifold leads to a pressure gauge. Figure 5 shows the
manifold and lines.

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Hazard:
Carbon monoxide gas is poisonous. It should be released only in the hood, not in the open lab.

Recording spectra

Evacuate the cell. Close its stopcock. Disconnect it from the manifold and place it in the FTIR's
sample compartment. Record a background spectrum with these settings:
range: 4500 to 500 cm-1
resolution: 0.5 cm-1
average 4 scans

Reattach the cell to the manifold. Check that the needle valve on the CO tank is closed. Open the
main valve on the top of the CO tank. With the stopcock to the pump closed, introduce CO gas
by slowly opening the needle valve. Fill the manifold until the desired gas pressure is reached
(but not over 1000 mbar, 1 bar). For the fundamental spectrum, use a pressure of 200 mbar.

Return the gas cell to the FTIR sample compartment. Record the infrared spectrum of the
fundamental transition. Record from 2250 to 2050 cm-1. Label peaks. Print the spectrum or save
it as an image (e.g., screen-print). You may also save the spectrum to a flash drive as an ascii
(*.ASC) file if you want to open it later in a spreadsheet.

Reattach the gas cell to the manifold. Bring its CO pressure to 800 mbar. Return the gas cell to
the FTIR and record the overtone spectrum from 4350 to 4150 cm -1. Label peaks. Save.

Include the fundamental spectrum and the overtone spectrum in your lab report.

After taking spectra, reconnect the cell to the manifold. Rinse it with air a few times to remove
carbon monoxide. Put the cell away in a desiccator.

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Spectrum-Based Calculations

Enter into a spreadsheet the wavenumbers of about thirty lines each of the fundamental spectrum
and the overtone spectrum. Recall that the R branch is the higher-wavenumber branch in each
spectrum, and that m is positive in the R branch. Enter the m value of each line. Plot
wavenumbers versus m for the fundamental and again for the overtone. Include those two plots
as figures in your lab report.

Fit the fundamental lines to equation 1. Letting c0, c1, c2 and c3 represent the constants in the
cubic equation 1 produces equation 7.
ω(v,m) = c0 + c1 m + c2 m2 +c3 m3 (7)
2 3
Do a linear regression calculation (e.g., Excel's data analysis/regression with m, m , and m as the
"x" variables) to obtain the values of the intercept c0 and the three coefficients c1, c2 and c3. From
the coefficients, calculate ω1, B0, and B1. Units are wavenumbers (cm-1) for each quantity.
ω1 = c0 , the intercept (8)
B0 = ½(c1 - c2) (9)
B1= ½(c1 + c2) (10)
The centrifugal distortion coefficient De = -c3/4.

Fit the overtone lines to equation 1. Do a linear regression calculation to obtain the intercept and
three coefficients. From the intercept and coefficients, calculate ω 2, B0, B2, and De.
ω2 = c0 , B0 = ½(c1 - c2) , B2= ½(c1 + c2), De = -c3/4 (11)

Combine fundamental and overtone results to calculate ωe, xeωe, Be, αe and De, all in
wavenumbers (cm-1).
ωe = 3 ω1 - ω2 (12)
xe ωe = ( 2ω1 - ω2 )/2 (13)
Recall equation 5, a linear equation for rotation constants versus (v+1/2). The experiment has
provided four "y" values: B0, B0, B1, and B2. Graph these versus the "x" values 1/2, 1/2, 3/2 and
5/2. The intercept is Be. The slope equals -αe. Include the graph in your lab report. Take
uncertainties for Be and αe from the regression statistics.

From Be, calculate the bond length, Re. (Equation 6 relates the two.)

Finally, calculate the centrifugal distortion constant D e as the average of its fundamental and
overtone values.

In your report, compare at least some of your results to published values. References 2-4 are
possible sources.

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Quantum-Chemical Calculations

Do two quantum-chemical calculations on the CO molecule. Each calculation should be a

geometry optimization and vibration frequency calculation. Use two theories, Hartree-Fock
(RHF) and density functional theory (DFT) with the B3LYP functional.

For each calculation, use the 6-311+G(d,p) basis set. That basis set is on WebMO's menu of
basis sets. When you preview the GAMESS input file you will see the basis set specified as
$BASIS GBASIS=N311 NGAUSS=6 NDFUNC=1 NPFUNC=1 DIFFSP=.TRUE. $END.
The command "DIFFSP" corresponds to the "+" in the basis set name, NDFUNC=1 to the "d", and
NPFUNC=1 to the "p".

For each calculation, report total energy, vibration frequency, bond length, and rotation constant.
Quantum-Chemical Hartree Fock DFT
Results (RHF) B3LYP
6-311+G(d,p) 6-311+G(d,p)
E (Hartree)
ωe (cm-1)
Re (Angstroms)
Be (cm-1)

Compare RHF and DFT-B3LYP results. Because correlation energy is negative (i.e., stabilizing),
you should find the DFT energy to be lower than the RHF energy. Compare the better of the two
theoretical calculation's results to your experimental results.

References

1. Ng, L. L.; Tan, T. L. " High-resolution FTIR spectroscopy of 12C2HD3 in the 830–1110
cm-1 region: A study of the Coriolis and anharmonic interactions within the ν 3 = 1, ν6 = 1
and ν8 = 1 triad," Journal of Molecular Spectroscopy, 2020, 371, 111299.
2. Rank, D. H.; Guenther, A. H.; Saksena, G. D.; Shearer, J. N.; Wiggins, T. A. “Tertiary
interferometric wavelength standards from measurements on lines of the 2-0 band of
carbon monoxide and derived wavelength standards for some lines of the 1-0 band of
carbon monoxide. The velocity of light derived from a band spectrum method. IV.”
Journal of the Optical Society of America, 1957, 47(8), 686-689.
3. Mina-Camilde, Nairmen; Manzanares I; Caballero, Julio F. “Molecular constants of
carbon monoxide at v=0, 1, 2 and 3.” Journal of Chemical Education, 1996, 73(8), 804-
807.
4. Sinnokrot, Mutasem Omar; Sherrill, C. David. "Density functional theory predictions of
anharmonicity and spectroscopic constants for diatomic molecules," Journal of Chemical
Physics, 2001, 115(6), 2439-2448 .

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