Spectroscopic identification of carbon dioxide clusters: (CO2)6to (CO2)13

Oliaee, J. Norooz; Dehghany, M.; Moazzen‐Ahmadi, N.; McKellar, A. R. W.

doi:10.1039/c0cp02311f

Cited by 42 publications

(31 citation statements)

References 34 publications

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“…These pioneering works opened the way to high-resolution spectroscopy in the microwave and infrared spectral ranges [2][3][4][5]. It proved to be a challenging field, experimentally because these weakly bound species are difficult to produce with sufficient density, and theoretically because these complexes show large amplitude motions.…”

Section: Introductionmentioning

confidence: 99%

Experimental 2CH excitation in acetylene-containing van der Waals complexes

et al. 2012

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Section: Introductionmentioning

confidence: 99%

Experimental 2CH excitation in acetylene-containing van der Waals complexes

et al. 2012

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“…In gaseous phase, investigations have been mainly devoted to the analysis of the Fermi resonance coupling of vibrational modes of the isolated molecule, [1][2][3] and to the characterisation of the structure of weakly bounded clusters. [4][5][6][7][8][9][10][11][12][13][14][15][16][17] In dense phase, the aim was to provide insight on the nature and time scale of the intermolecular interactions from "allowed" vibrational spectra or from the analysis of collision induced (CI) spectra which are unique probes of the multi-body interactions. [18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36] The study of the interaction of carbon dioxide with molecular liquids and complex fluids as ionic liquids is a field of current interest, motivated not only from the fundamental point of view but mainly under the impetuous motivation of understanding the interactions of CO 2 in the field of environmental studies.…”

Section: Introductionmentioning

confidence: 99%

Assessing the non-ideality of the CO2-CS2 system at molecular level: A Raman scattering study

Besnard

Cabaço²,

Coutinho

et al. 2013

The Journal of Chemical Physics

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The dense phase of CO 2 -CS 2 mixtures has been analysed by Raman spectroscopy as a function of the CO 2 concentration (0.02-0.95 mole fractions) by varying the pressure (0.5 MPa up to 7.7 MPa) at constant temperature (313 K). The polarised and depolarised spectra of the induced (ν 2 , ν 3 ) modes of CS 2 and of the ν 1 -2ν 2 Fermi resonance dyad of both CO 2 and CS 2 have been measured. Upon dilution with CO 2 , the evolution of the spectroscopic observables of all these modes displays a "plateau-like" region in the CO 2 mole fraction 0.3-0.7 never previously observed in CO 2 -organic liquids mixtures. The bandshape and intensity of the induced modes of CS 2 are similar to those of pure CS 2 up to equimolar concentration, after which variations occur. The preservation of the local ordering from pure CS 2 to equimolar concentration together with the non-linear evolution of the spectroscopic observables allows inferring that two solvation regimes exist with a transition occurring in the plateau domain. In the first regime, corresponding to CS 2 concentrated mixtures, the liquid phase is segregated with dominant CS 2 clusters, whereas, in the second one, CO 2 monomers and dimers and CO 2 -CS 2 hetero-dimers coexist dynamically on a picosecond time-scale. It is demonstrated that the subtle interplay between attractive and repulsive interactions which provides a molecular interpretation of the non-ideality of the CO 2 -CS 2 mixture allows rationalizing the volume expansion and the existence of the plateau-like region observed in the pressure-composition diagram previously ascribed to the proximity of an upper critical solution temperature at lower temperatures.

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“…More recent references report mass spectrometric, IR, and photoelectron work on clusters like (CO 2 ) n 1-and O -(CO 2 ) n ; 2 Cl -(CO 2 ) n ; 3 F -(CO 2 ) n ; 4 CO 3 1-(CO 2 ) n ; O 2 -(CO 2 ) n ; NO 2 1-(CO 2 ) n , 5 O -(CO 2 ) n , (CO 2 ) n 1-; 6 X -(CO 2 ) with X = F, Cl, Br, and I; 7,8 I 2 1-(CO 2 ) n ; 9 H 2 O 1-(CO 2 ) n ; 10 and (CO 2 ) n . 11 The present paper, dealing with anionic clusters of carbonate with carbon dioxiode and of type CO 3 1-/2-(CO 2 ) n , serves several purposes. For one, monoanionic clusters play an important role in the negative ion chemistry of the lower atmosphere.…”

Section: Introductionmentioning

confidence: 99%

Theoretical studies on clusters of carbonate with carbon dioxide, CO₃^1–/2–(CO₂)_n, forn= 1–5 — Comparison of carbonate clusters with sulfate clusters

GreinFriedrich

Chevrier

2012

Can. J. Chem.

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Density functional theory (DFT) calculations were performed on the geometries and energies of CO3 1-/2-(CO2)n clusters with n = 1-5. For small clusters (n = 1 or 2), coupled cluster energies were obtained. Up to three CO2 molecules are bound covalently to the dianion. Only weak electrostatic bonds were found in the monoanions. Calculated binding energies for the monoanions are in reasonable agreement with experimental values. The calculated adiabatic electron detachment energy for the dianion is -0.07 eV at n = 5, indicating that at least six CO2 molecules will have to be added to CO3 2-before the dianionic cluster becomes, in the gas phase, more stable than the monoanionic one. In comparison, for sulfate -carbon dioxide clusters, stabilization occurs at n = 2. Carbonate clusters are compared with sulfate clusters for three solvent molecules: CO2, SO2, and H2O. Carbonate clusters have larger binding energies than sulfate clusters. For a given dianion, binding energies are largest for SO2 and smallest for H2O. However, in all cases, stabilization of the carbonate dianion by clustering is more difficult to achieve than stabilization of the sulfate dianion.Résumé : On a effectué des calculs suivant la théorie de la fonctionnelle de la densité sur les géométries et les énergies d'agrégats CO3 1-/2-(CO2)n dans lesquels n = 1-5. Pour les petits agrégats (n = 1 ou 2), il a été possible d'évaluer les énergies de couplage des agrégats. Le dianion peut se lier d'une façon covalente avec un maximum de trois molécules de CO 2 . On n'a trouvé que de faibles liaisons électrostatiques dans les monoanions. Les énergies de liaisons calculées pour les monoanions sont en accord raisonnable avec les valeurs expérimentales. L'énergie calculée pour le détachement adiabatique d'un électron est de -0,07 eV pour n = 5; ceci indique que, en phase gazeuse, il faut ajouter au moins six molécules de CO 2 à l'anion CO 2 2-avant que l'agrégat dianionique devienne plus stable que l'agrégat monoanionique. Par comparaison, pour les agrégats sulfate -dioxyde de carbone, la stabilisation se produit avec n = 2. On a comparé les agrégats du carbonate avec ceux du sulfate pour trois molécules de solvant : CO 2 , SO 2 et H 2 O. Les énergies de liaison des agrégats du carbonate sont plus élevées que celles des agrégats du sulfate. Pour un dianion donné, les énergies de liaison sont les plus élevées pour le SO 2 et les plus faibles avec H 2 O. Toutefois, dans tous les cas, la stabilisation du dianion carbonate par le biais de la formation d'agrégat se fait plus difficilement que la stabilisation du dianion sulfate.Mots-clés : agrégats carbonate -dioxyde de carbone, monoanions, dianions, théorie de la fonctionnelle de la densité, stabilisation du dianion, énergies de solvatation, énergies de liaison, comparaison avec les agrégats du sulfate.[Traduit par la Rédaction]

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Spectroscopic identification of carbon dioxide clusters: (CO₂)₆to (CO₂)₁₃

Cited by 42 publications

References 34 publications

Experimental 2CH excitation in acetylene-containing van der Waals complexes

Experimental 2CH excitation in acetylene-containing van der Waals complexes

Assessing the non-ideality of the CO2-CS2 system at molecular level: A Raman scattering study

Theoretical studies on clusters of carbonate with carbon dioxide, CO₃^1–/2–(CO₂)_n, forn= 1–5 — Comparison of carbonate clusters with sulfate clusters

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Spectroscopic identification of carbon dioxide clusters: (CO2)6to (CO2)13

Cited by 42 publications

References 34 publications

Experimental 2CH excitation in acetylene-containing van der Waals complexes

Experimental 2CH excitation in acetylene-containing van der Waals complexes

Assessing the non-ideality of the CO2-CS2 system at molecular level: A Raman scattering study

Theoretical studies on clusters of carbonate with carbon dioxide, CO31–/2–(CO2)n, forn= 1–5 — Comparison of carbonate clusters with sulfate clusters

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Spectroscopic identification of carbon dioxide clusters: (CO₂)₆to (CO₂)₁₃

Theoretical studies on clusters of carbonate with carbon dioxide, CO₃^1–/2–(CO₂)_n, forn= 1–5 — Comparison of carbonate clusters with sulfate clusters