Symmetry breaking of the bending mode of CO<sub>2</sub> in the presence of Ar

Gartner, Travis; Barclay, A. J.; McKellar, A. R. W.; Moazzen‐Ahmadi, N.

doi:10.1039/d0cp02674c

Cited by 15 publications

(11 citation statements)

References 26 publications

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“…We have previously reported spectra in the region of the CO 2 (v 1 , v 2 l2 , v 3 ) = (01 1 1) ! (01 1 0) hot band near 2337 cm À 1 for CO 2 -Ar, [8] À Ne, [9] À Xe, [5] À N 2 [10] and À CO. [11] Transitions from this excited state (01 1 0) to the combination state (01 1 1) exhibit b-type selection rules, like the ν 3 fundamental. The (01 1 0) lower state bends have A 1 (i-p) and B 1 (o-p) symmetry with allowed even or odd K a levels respectively.…”

Section: Chemistryselectmentioning

confidence: 94%

Spectra of CO₂‐Kr in the 4.3 μm region: Intermolecular Bend and Symmetry Breaking of the Intramolecular CO₂ Bend

et al. 2022

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The infrared spectrum of CO 2 -Kr complex is studied in the region of the carbon dioxide ν 3 fundamental vibration ( � 2350 cm À 1 ). Tunable IR radiation from an OPO is employed to record absorption spectrum of the complex generated in a pulsed supersonic slit jet. The spectrum exhibits broadening and splitting of transitions due to mass dependence of the five Kr isotopes with natural abundances exceeding 2 %. Good simulation of the spectrum is achieved by scaling the vibrational and rotational parameters. This scaling model is partic-ularly important for the combination band involving the intermolecular bending mode where many isotope splittings are observed. As with other CO 2 -rare gas complexes, we also observe weak hot bands of CO 2 -Kr transitions corresponding to the hot band originating in the CO 2 intramolecular bend. From these we determine a splitting of 1.418 cm À 1 between the inplane and out-of-plane bend of CO 2 , due to the neighboring Kr atom.

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Section: Chemistryselectmentioning

confidence: 94%

Spectra of CO₂‐Kr in the 4.3 μm region: Intermolecular Bend and Symmetry Breaking of the Intramolecular CO₂ Bend

et al. 2022

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“…While we reproduced this splitting in argon matrixes, in neon matrixes we observe only a splitting for the CO 2 ν 2 (E 1u ) transition . It has been shown that the matrix environment makes the two degenerate bending vibrations distinguishable, leading to the observed splitting of the band that corresponds to the bending vibration. − …”

Section: Resultsmentioning

confidence: 49%

“… 11 It has been shown that the matrix environment makes the two degenerate bending vibrations distinguishable, leading to the observed splitting of the band that corresponds to the bending vibration. 37 − 39 …”

Section: Resultsmentioning

confidence: 99%

Increase of Radiative Forcing through Midinfrared Absorption by Stable CO₂ Dimers?

et al. 2022

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We performed matrix-isolation infrared (MI-IR) spectroscopy of carbon dioxide monomers, CO 2 , and dimers, (CO 2 ) 2 , trapped in neon and in air. On the basis of vibration configuration interaction (VCI) calculations accounting for mode coupling and anharmonicity, we identify additional infrared-active bands in the MI-IR spectra due to the (CO 2 ) 2 dimer. These bands are satellite bands next to the established CO 2 monomer bands, which appear in the infrared window of Earth’s atmosphere at around 4 and 15 μm. In a systematic carbon dioxide mixing ratio study using neon matrixes, we observe a significant fraction of the dimer at mixing ratios above 300 ppm, with a steep increase up to 1000 ppm. In neon matrix, the dimer increases the IR absorbance by about 15% at 400 ppm compared to the monomer absorbance alone. This suggests a high fraction of the (CO 2 ) 2 dimer in our matrix experiments. In atmospheric conditions, such increased absorbance would significantly amplify radiative forcings and, thus, the greenhouse warming. To enable a comparison of our laboratory experiment with various atmospheric conditions (Earth, Mars, Venus), we compute the thermodynamics of the dimerization accordingly. The dimerization is favored at low temperatures and/or high carbon dioxide partial pressures. Thus, we argue that matrix isolation does not trap the gas composition “as is”. Instead, the gas is precooled to 40 K, where CO 2 dimerizes before being trapped in the matrix, already at very low carbon dioxide partial pressures. In the context of planetary atmospheres, our results improve understanding of the greenhouse effect for planets of rather thick CO 2 atmospheres such as Venus, where a significant fraction of the (CO 2 ) 2 dimer can be expected. There, the necessity of including the mid-IR absorption by stable (CO 2 ) 2 dimers in databases used for modeling radiative forcing, such as HITRAN, arises.

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“…A T-shaped structure was established, with the Ar atom located to the “side” of the CO 2 molecule, adjacent to the C atom at an intermolecular separation of about 3.5 Å. Since then, there have been many more microwave , and infrared − studies. The trimer CO 2 -Ar 2 has also been detected in the microwave and infrared regions.…”

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confidence: 99%

“…Our spectra were recorded as described previously, , using a pulsed supersonic slit jet expansion probed by a rapid-scan optical parametric oscillator source. The slit width was set at 12.5 μm, narrower than we have previously used in order to encourage the formation of larger clusters.…”

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Observing the Completion of the First Solvation Shell of Carbon Dioxide in Argon from Rotationally Resolved Spectra

Barclay

McKellar

Moazzen‐Ahmadi

2022

J. Phys. Chem. Lett.

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Widespread interest in weakly bound molecular clusters of medium size (5 ~ 50 molecules) is motivated by their complicated energy landscapes, which lead to hundreds or thousands of distinct isomers. But most studies are theoretical in nature, and there are no experimental results which provide definitive structural information on completion of the first solvation shell. Here we assign rotationally resolved mid-infrared spectra to argon clusters containing a single carbon dioxide molecule, CO2-Ar15 and CO2-Ar17. These mark completion of the first solvation shell for CO2 in argon. The assignments are confirmed by nuclear spin intensity alternation in the spectra, a marker of highly symmetric structures for these clusters. Precise values are determined for rotational parameters, and for shifts of the CO2 vibrational frequency induced by the argon atoms.The spectra indicate possible low frequency (2 cm -1 ) vibrational modes in these clusters, posing a challenge for future cluster theory.

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Symmetry breaking of the bending mode of CO₂ in the presence of Ar

Abstract: The weak infrared spectrum of CO2-Ar corresponding to the (0111) <-- (0110) hot band of CO2 is detected in the region of the carbon dioxide ν3 fundamental vibration (~2340 cm-1),...

Cited by 15 publications

References 26 publications

Spectra of CO₂‐Kr in the 4.3 μm region: Intermolecular Bend and Symmetry Breaking of the Intramolecular CO₂ Bend

Spectra of CO₂‐Kr in the 4.3 μm region: Intermolecular Bend and Symmetry Breaking of the Intramolecular CO₂ Bend

Increase of Radiative Forcing through Midinfrared Absorption by Stable CO₂ Dimers?

Observing the Completion of the First Solvation Shell of Carbon Dioxide in Argon from Rotationally Resolved Spectra

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Symmetry breaking of the bending mode of CO2 in the presence of Ar

Abstract: The weak infrared spectrum of CO2-Ar corresponding to the (0111) <-- (0110) hot band of CO2 is detected in the region of the carbon dioxide ν3 fundamental vibration (~2340 cm-1),...

Cited by 15 publications

References 26 publications

Spectra of CO2‐Kr in the 4.3 μm region: Intermolecular Bend and Symmetry Breaking of the Intramolecular CO2 Bend

Spectra of CO2‐Kr in the 4.3 μm region: Intermolecular Bend and Symmetry Breaking of the Intramolecular CO2 Bend

Increase of Radiative Forcing through Midinfrared Absorption by Stable CO2 Dimers?

Observing the Completion of the First Solvation Shell of Carbon Dioxide in Argon from Rotationally Resolved Spectra

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Symmetry breaking of the bending mode of CO₂ in the presence of Ar

Spectra of CO₂‐Kr in the 4.3 μm region: Intermolecular Bend and Symmetry Breaking of the Intramolecular CO₂ Bend

Spectra of CO₂‐Kr in the 4.3 μm region: Intermolecular Bend and Symmetry Breaking of the Intramolecular CO₂ Bend

Increase of Radiative Forcing through Midinfrared Absorption by Stable CO₂ Dimers?