Theoretical investigation of the vibrational structure of the Ar–CO2 complex

Sode, Olaseni; Ruíz, Jesús Cuadrado; Peralta, Steve

doi:10.1016/j.jms.2021.111512

Cited by 4 publications

(33 citation statements)

References 46 publications

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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%

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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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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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“…For the CO 2 ·Ar dimer, the first 15 vdW vibrational states have been determined with the seven models of Table . The 6D computations took advantage of a PES that was fitted to aug-cc-pVTZ CCSD(T)-F12b interaction energies without counterpoise correction. In these 6D computations, nine Hermite-type basis functions were employed for the r 1 and r 2 coordinates (see Figure ), sufficient to extract the intramonomer stretch fundamentals within a few cm –1 .…”

Section: Assessment Of the Reduced-dimensional Modelsmentioning

confidence: 99%

Unusual Dynamics and Vibrational Fingerprints of van der Waals Dimers Formed by Linear Molecules and Rare-Gas Atoms

Tóbiás,

Simkó,

Császár

2023

J. Chem. Theory Comput.

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“…There are numerous theoretical investigations of the CO2-Ar interaction potential. [19][20][21][22][23][24][25] Experimental information on doped rare gas clusters with n > 3 is in short supply with the notable exception of helium, whose superfluid nature has allowed spectroscopy of a whole range of cluster sizes and dopant molecules. Thus for CO2-(He)n, spectra have been observed for n = 1 to noted: "… the resulting [cluster] structures can be quite different from those obtained from gas phase nucleation".…”

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confidence: 99%

“…Its structure locates the second Ar atom in a position equivalent to the first, giving a C 2 v point group structure with an Ar–Ar distance of about 3.8 Å. There are numerous theoretical investigations of the CO 2 –Ar interaction potential. − …”

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confidence: 99%

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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Theoretical investigation of the vibrational structure of the Ar–CO2 complex

Cited by 4 publications

References 46 publications

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

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

Unusual Dynamics and Vibrational Fingerprints of van der Waals Dimers Formed by Linear Molecules and Rare-Gas Atoms

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

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Theoretical investigation of the vibrational structure of the Ar–CO2 complex

Cited by 4 publications

References 46 publications

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

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

Unusual Dynamics and Vibrational Fingerprints of van der Waals Dimers Formed by Linear Molecules and Rare-Gas Atoms

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

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

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