Vibrational Spectra of Carbon Dioxide and Carbon Disulfide

Sarah Gamp

University of Minnesota Duluth

CHEM 4644
11 February 2022
Introduction

Vibration frequencies of CO2 and CS2 were observed in infrared (IR) and Raman spectra.
For IR spectra, samples were gases. Raman spectra of solid CO 2 and liquid CS2 were recorded.
The symmetry group of both molecules is D∞h. Symmetry divides the vibrational normal modes
into Raman-active modes and IR-active modes. The Raman-active symmetric-stretching
vibration of carbon dioxide was split into two peaks. The splitting, called "Fermi resonance," is
interpreted as due to interaction of the symmetric-stretching vibration with an overtone of the
bending vibration.
Geometries and vibration frequencies were calculated with quantum-chemical density
functional theory (DFT). The B3LYP functional was used with a large basis set. Calculations
were done in the D4h symmetry group. Although D4h is but a subgroup of D∞h, it suffices to
distinguish Raman-active modes from IR-active modes. The calculated symmetric-stretching
frequency, the mode that is split by Fermi resonance in Raman spectra, will be compared to the
frequency calculated by analysis of spectra.
The two molecules are similar in that they are linear and are symmetric about carbon. Both
molecules have three vibrational modes: (1) symmetric stretching, (2) bending, which is two-fold
degenerate, and (3) asymmetric stretching. Mode 1 is Raman-active, modes 2 and 3 are IR-
active. Lewis-dot structures of the two molecules are identical, so bonding and spectra should be
similar. The sulfur-bearing molecule is expected to have lower vibration frequencies and longer
bonds.
Fermi resonance is due to mixing of vibrational states that are nearly degenerate. Those
states are the first excited state of the symmetric stretching mode, ψ , and the second excited
state of the bending mode, ψ . The two wavefunctions mix, forming ψ+ and ψ- that have
energies E+ and E-. Equation 1 shows the linear combinations; constants c1 and c2 to be
determined.
ψ± = 𝑐 ψ + 𝑐 ψ (1)
The energy level diagram in Figure 1 shows the states and indicates Raman and IR
transitions.
 Figure 1. States and transitions involved in Fermi resonance of carbon dioxide.

The mixing coefficients, c1 and c2, are found as solutions to the secular equation, Equation
2. An additional condition needed to calculate the coefficients is normalization: 𝑐 + 𝑐 = 1.
( )
𝐸 −𝐸 𝐹 𝑐
( ) 𝑐 =0 (2)
𝐹 𝐸
In equation 2 and in Figure 1, the superscript "(0)" means zeroth-order, before mixing
occurs. The subscript "100" means mode 1 is in its v=1 level; "020" means mode 2 is in its v=2
level. F is an interaction energy; the energy of the interaction of ψ and ψ . The energy, E,
in equation 2 may be either E+ or E-, which are read from the Raman spectrum of carbon dioxide.
Those two cases of equation 2 lead to the equations 3, which will be solved simultaneously for F
( ) ( )
and 𝐸 . The fundamental bending energy, 𝐸 , will be taken from an IR spectrum. The
( ) ( )
bending overtone energy, 𝐸 , equals twice 𝐸 .
( ) ( )
E- + E+ = E +E
( ) ( ) (3)
(𝐸- – 𝐸+ ) = 𝐸 –𝐸 + 4𝐹
Results

The Raman spectrum of dry ice is

Figure 2. Because dry ice is a molecular solid
and is nearly pure carbon dioxide, Figure 2 is
supposed to approximate the spectrum of the
carbon dioxide molecule. Figure 2 has two
prominent peaks. They are at 1275 and 1382
wavenumbers. Directly from those peaks,
E+=1275 and E-=1382 cm-1.
Figure 2. Raman spectrum of solid carbon dioxide.

The Raman spectrum of liquid carbon disulfide is Figure 3. It has only one large peak.
That represents the fundamental symmetric-
stretching energy for CS2: ν = 639.5 𝑐𝑚 .
The weaker peak at 780 cm-1 suggests that
carbon disulfide is also somewhat affected by
Fermi resonance. In this report, the weaker peak
(and so any near-resonance in CS2) will be
neglected.

Figure 3. Raman spectrum of liquid carbon

disulfide.

The infrared spectrum of gaseous carbon dioxide, which was collected from the head
space over dry ice, is in Figure 4. Two bands appear, asymmetric stretching at ν =2347.0 cm-1
( )
and bending at ν =668.8 = 𝐸 for CO2. Bands, rather than simple peaks, are due to rotational
transitions that are excited along with vibrations.

Figure 4. Infrared spectrum of carbon dioxide gas.

 The infrared spectrum of gaseous carbon disulfide, which was collected from the head
space over liquid CS2, is in Figure 5. Only one prominent peak appears, ν =1534.7 cm-1 for CS2.
No bending transition is seen. Quantum-chemical calculations, below, give ν =378 for CS2,
which is lower than the spectrometer and cell could reach.

Figure 5. Infrared spectrum of carbon disulfide.

Fermi-resonance calculation for CO2

From spectra, above, the following are known:
( ) ( )
𝐸 = 2𝐸 = 2 × 668.8𝑐𝑚 = 1338 𝑐𝑚 .
𝐸 = 1382 𝑐𝑚
𝐸+ = 1275 𝑐𝑚
Substituting those values into equation 3 results in equation 4.
( )
2657 = 1338 + E
( ) (4)
(107) = 1338– 𝐸 + 4𝐹
( )
Solving equation 4 yields these results: F= -53 cm -1, and 𝐸 = 1319 cm-1.
Substituting those values into equation 2 gives the following two equations, one for the
lower-energy E+ state and one for the higher-energy E- state:
( )
𝐸 −𝐸 𝑐 + 𝐹𝑐 = 0, so = = 1.20.
( )
𝐸 −𝐸 𝑐 + 𝐹𝑐 = 0 so = = −0.84
 Applying the normalization condition finally leads to the values of the coefficients. They
are listed in Table 1. As expected, the zero-order states are approximately equally mixed in the
Fermi-resonance states. It is also apparent that ψ is orthogonal to ψ .
Table 1. Energies and coefficients of the mixed Fermi-resonance states of CO2.
energy (cm-1) c1 c2
E+ =1275 0.64 0.77
E- = 1382 0.77 -0.64

Quantum Chemistry
Density functional theory was used with the 6-311++G(d,p) basis set. Calculations were
done with the quantum-chemical program GAMESS running under the WebMO graphical
interface. Geometries of CO2 and CS2 were optimized, then vibration frequencies were
calculated. D4h symmetry was used. Results are in Table 2.
Table 2. vibration frequencies and bond lengths of CO2 and CS2. Frequencies
are in cm-1. Bond lengths are in Angstroms.
D4h symmetry A1g A2u Eu experimental (Ref. 1)
molecule ν ν ν bond length bond length
CO2 1371 656 2404 1.161 1.162
CS2 644 378 1501 1.575 1.554

Discussion

Quantum-chemical frequencies and bond lengths are in Table 2. Published experimental

bond lengths are also given in Table 2. The error in the DFT/B3LYP calculated bond lengths is
less than 0.02Å. That error is smaller for C-O than for C-S may be due to the usual greater
quantum-chemical accuracy for molecules containing lighter atoms.
Two vibrational modes have ungerade symmetry, so should be IR active, and they are.
The gerade mode of CS2 was observed in the Raman spectrum, Figure 3. Calculated frequencies
differ from the four directly observed IR and Raman peaks by 5 to 60 cm -1. Because of Fermi
resonance, the gerade mode of CO2 was not observed in the Raman spectrum. The quantum-
( )
chemical ν differs from the Fermi-resonance calculated 𝐸 by 52 cm-1, an error comparable to
those for non-resonance-split peaks. The difference between the Raman peaks has been labeled Δ
by some authors. The Δ measured here, 107 cm-1, differs by less than 5% from published
values.2,3
References

1. Computational Chemistry Comparison and Benchmark DataBase, National Institutes of

Standards and Technology, Release 21, August 2020, viewed 30 November, 2021. URL
https://cccbdb.nist.gov/exp2x.asp?casno=75150 for CS2 and
https://cccbdb.nist.gov/exp2x.asp?casno=124389 for CO2.

2. A. Hakura, A. Brodka, L. Nikiel, and F. G. Baglin, High pressure Raman study of Fermi
resonance spectrum in gaseous carbon dioxide, Journal of Molecular Structure, 218, 297-302,
1990.

3. Yoko Kawakami, Junji Yamamoto, and Hiroyuki Kage, Micro-Raman Densimeter for
CO2 Inclusions in Mantle-Derived Minerals, Applied Spectroscopy, 57(11), 1333-1339, 2003.
DOI: 10.1366/000370203322554473