Spectra of CO<sub>2</sub>‐Kr in the 4.3 μm region: Intermolecular Bend and Symmetry Breaking of the Intramolecular CO<sub>2</sub> Bend

Gartner, Travis; Ghebretnsae, Sye; McKellar, A. R. W.; Moazzen‐Ahmadi, N.

doi:10.1002/slct.202202601

Cited by 3 publications

(4 citation statements)

References 17 publications

(61 reference statements)

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“…At the VCI level, the difference between the bend and stretch frequencies is 2.77 cm –1 . This matches with the differences observed experimentally of 2.80 and >2.5 cm –1 , , however, our computed results are shifted lower in energy by about 2 cm –1 compared to the experiment. Chen et al report the two fundamental intermolecular frequencies at 30.027 and 32.233 cm –1 for the bend and stretch, respectively .…”

Section: Resultssupporting

confidence: 92%

“…For the neon complex, these frequencies have been observed at 17.9 and 38.6 cm –1 , respectively . For krypton, the van der Waals bend and stretch energy levels were reported at 29.4 and 34.4 cm –1 , respectively. − Similarly, recent theoretical studies align with these experimental findings . Importantly, the intramolecular frequency shifts within these complexes have been a focus of exploration.…”

Section: Introductionmentioning

confidence: 67%

“…Table shows the experimental and theoretical CO 2 ν 2 splitting values for the neon, argon, and krypton complexes . For Kr–CO 2 , we compute a splitting of 1.95 cm –1 compared to the 1.418 cm –1 experimentally determined value …”

Section: Resultsmentioning

confidence: 99%

“…6 For Kr−CO 2 , we compute a splitting of 1.95 cm −1 compared to the 1.418 cm −1 experimentally determined value. 4 In the symmetric stretch region, the upper and lower Fermi dyad peaks (denoted again as 2ν 2 o /2ν 2 i and ν 1 ) are found at 1284.39 and 1388.21 cm −1 , respectively. Again, this represents a weak perturbation from the isolated monomer.…”

Section: Krypton Intermolecular Vibrational Frequencymentioning

confidence: 96%

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Theoretical Insights into the Vibrational Structure of Carbon Dioxide Rare-Gas Complexes

Rodriguez,

Natalizio,

Sode

2024

J. Phys. Chem. A

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Two new flexible-monomer two-body ab initio potential energy surfaces (PESs) for the neon and krypton van der Waals complexes with carbon dioxide were developed, extending our previous work on the Ar–CO2 molecule. The accuracy of the PESs was validated by their agreement with the vibrational spectrum of the rare-gas complexes. The intermolecular and intramolecular vibrational excitation energies were computed at the vibrational self-consistent field and vibrational configuration interaction levels of theory. Overall, the agreement between theory and experiment is excellent throughout the vibrational spectra. The observed slight splitting of the bending modes, resulting from their nondegeneracy in the complexes, is confirmed by our computations, and the results qualitatively agree with the experiment. The splitting increases with increasing polarizability of the rare-gas atom. Additionally, we explain a discrepancy in the mode assignment in the intermolecular region of the neon complex with our VCI character assignment.

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Section: Resultssupporting

confidence: 92%

Section: Introductionmentioning

confidence: 67%

Section: Resultsmentioning

confidence: 99%

Section: Krypton Intermolecular Vibrational Frequencymentioning

confidence: 96%

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Theoretical Insights into the Vibrational Structure of Carbon Dioxide Rare-Gas Complexes

Rodriguez,

Natalizio,

Sode

2024

J. Phys. Chem. A

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Spectra of CO2-Rg2 and CO2-Rg-He trimers (Rg = Ne, Ar, Kr, and Xe): Intermolecular CO2 rock, vibrational shifts and three-body effects

Barclay

McKellar

Moazzen‐Ahmadi

2022

The Journal of Chemical Physics

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Weakly-bound CO2-Rg2 trimers are studied by high resolution (0.002 cm-1) infrared spectroscopy in the region of the CO2 n3 fundamental band (»2350 cm-1), using a tunable OPO to probe a pulsed supersonic slit jet expansion with an effective rotational temperature of about 2 K. CO2-Ar2 spectra have been reported previously, but are extended here to include Rg = Ne, Kr, and Xe as well as new combination and hot bands. For Kr and Xe, a unified scaled parameter scheme is used to account for the many possible isotopic species. Vibrational shifts of CO2-Rg2 trimers are compared to those of CO2-Rg dimers, and in all cases the trimer shifts are slightly more positive (blue-shifted) than expected on the basis of linear extrapolation from the dimer. Combination bands directly measure an intermolecular vibrational mode (the CO2 rock), and gives values of about 32.2, 33.8, and 34.7 cm-1 for CO2-Ar2, -Kr2, and -Xe2. Structural parameters derived for CO2-Rg2 trimers are compared with those of CO2-Rg and Rg2 dimers. Spectra of the mixed trimers CO2-Rg-He are also reported.

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Doped rare gas clusters up to completion of first solvation shell, CO2–(Rg)n, n = 3–17, Rg = Ar, Kr, Xe

Barclay

McKellar

Moazzen‐Ahmadi

2023

The Journal of Chemical Physics

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Spectra of rare gas atom clusters containing a single carbon dioxide molecule are observed using a tunable mid-infrared (4.3 µm) source to probe a pulsed slit jet supersonic expansion. There are relatively few previous detailed experimental results on such clusters. The assigned clusters include CO2-Arn with n = 3, 4, 6, 9, 10, 11, 12, 15, and 17, as well as CO2-Krn and -Xen with n = 3, 4, and 5. Each spectrum has (at least) partially resolved rotational structure, and each yields precise values for the shift of the CO2 vibrational frequency (ν3) induced by the nearby rare gas atoms, together with one or more rotational constants. These results are compared with theoretical predictions. The more readily assigned CO2-Arn species tend to be those with symmetric structures, and CO2-Ar17 represents completion of a highly symmetric (D5h) solvation shell. Those not assigned (e.g. n = 7, 13) are probably also present in the observed spectra, but with band structures which are not well-resolved and thus not recognizable. The spectra of CO2-Ar9, -Ar15, and -Ar17 suggest the presence of sequences involving very low frequency (~2 cm‑1) cluster vibrational modes, an interpretation which should be amenable to theoretical confirmation (or rejection).

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

Cited by 3 publications

References 17 publications

Theoretical Insights into the Vibrational Structure of Carbon Dioxide Rare-Gas Complexes

Theoretical Insights into the Vibrational Structure of Carbon Dioxide Rare-Gas Complexes

Spectra of CO2-Rg2 and CO2-Rg-He trimers (Rg = Ne, Ar, Kr, and Xe): Intermolecular CO2 rock, vibrational shifts and three-body effects

Doped rare gas clusters up to completion of first solvation shell, CO2–(Rg)n, n = 3–17, Rg = Ar, Kr, Xe

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

Cited by 3 publications

References 17 publications

Theoretical Insights into the Vibrational Structure of Carbon Dioxide Rare-Gas Complexes

Theoretical Insights into the Vibrational Structure of Carbon Dioxide Rare-Gas Complexes

Spectra of CO2-Rg2 and CO2-Rg-He trimers (Rg = Ne, Ar, Kr, and Xe): Intermolecular CO2 rock, vibrational shifts and three-body effects

Doped rare gas clusters up to completion of first solvation shell, CO2–(Rg)n, n = 3–17, Rg = Ar, Kr, Xe

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