Bent valence excited states of CO2

Spielfiedel, A.; Feautrier, N.; Cossart‐Magos, Claudina; Chambaud, Gilberte; Rosmus, P.; Werner, Hans‐Joachim; Botschwina, Peter

doi:10.1063/1.463408

Cited by 71 publications

(105 citation statements)

References 17 publications

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“…Ab initio calculations demonstrate that the electronic energy and the geometric parameters of the nuclear configuration, such as the C-O bond distances and OCO bond angle, are strongly correlated [19]. Using large-scale multireference configuration interaction, the ordering of the lowest valence excited states of CO 2 …”

Section: The Ground State Of Carbon Dioxide and Its Lowest Excited Stmentioning

confidence: 99%

The Carbon Dioxide Molecule and the Effects of Its Interaction with Electrophiles and Nucleophiles

Aresta

Angelini

2015

Topics in Organometallic Chemistry

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This chapter discusses the CO 2 molecule in its ground and excited states, correlating the energy to the molecular geometry. The effect of adding or taking out an electron is illustrated, opening the way to the coordination of CO 2 to metal centers. Several modes of bonding of CO 2 are presented and the IR and multinuclear NMR spectroscopic data of transition metal complexes or adducts with Lewis acids and bases are commented. The reactivity of the coordinated heterocumulene is presented through several examples. The use of IR and NMR techniques for determining the molecular behavior of transition metal complexes in solution is exemplified.

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Section: The Ground State Of Carbon Dioxide and Its Lowest Excited Stmentioning

confidence: 99%

The Carbon Dioxide Molecule and the Effects of Its Interaction with Electrophiles and Nucleophiles

Aresta

Angelini

2015

Topics in Organometallic Chemistry

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“…22 However, some low-lying optically allowed excited states have been studied with the thresholds, electronic excitation: 1 ⌺ u ϭ11.04-11.05 eV, 1 ⌸ u ϭ11.38-11.40 eV.…”

Section: Introductionmentioning

confidence: 99%

Remarks on total and elastic cross sections for electron and positron scattering from CO2

Kimura

Sueoka

Hamada

et al. 1997

The Journal of Chemical Physics

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There remain discrepancies in the determination of the total and elastic cross sections for electron and positron collisions with carbon dioxide at impact energies from 0.3 to 100 eV. We have carried out a joint experimental and theoretical study in an attempt to resolve the differences. Our measurements for total cross sections for electron impact agree extremely well with those of Hoffman et al. ͓Phys. Rev. A 25, 1393 ͑1982͔͒ above 2 eV, while those for positron impact agree to better than 15% in magnitude, and are in an excellent accord for the energy-dependence. The present observations, along with an analysis using a knowledge of the dominant inelastic processes, lead us to conclude that the total cross section determined in earlier studies is a considerable underestimate at intermediate energies, where inelastic processes are not negligible. The analysis provides a rationale for understanding the discrepancies. Furthermore, we present that the total cross section by positron impact below 2 eV becomes larger by 20% than that of electron impact, and provide a rationale as well as implication to a possible application.

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“…The electronic structure of CO 2 has been the subject of several theoretical studies (7)(8)(9). The first quantum dynamics analysis of the UV photoabsorption of CO 2 was provided only recently by Grebenshchikov (10).…”

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Carbon dioxide photolysis from 150 to 210 nm: Singlet and triplet channel dynamics, UV-spectrum, and isotope effects

Schmidt

Schinke

2013

Proc. Natl. Acad. Sci. U.S.A.

109

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We present a first principles study of the carbon dioxide (CO 2 ) photodissociation process in the 150-to 210-nm wavelength range, with emphasis on photolysis below the carbon monoxide + O( 1 D) singlet channel threshold at ∼167 nm. The calculations reproduce experimental absorption cross-sections at a resolution of ∼0.5 nm without scaling the intensity. The observed structure in the 150-to 210-nm range is caused by excitation of bending motion supported by the deep wells at bent geometries in the 2 1 A′ and 1 1 A″ potential energy surfaces. Predissociation below the singlet channel threshold occurs via spin-orbit coupling to nearby repulsive triplet states. Carbon monoxide vibrational and rotational state distributions in the singlet channel as well as the triplet channel for excitation at 157 nm satisfactorily reproduce experimental data. O) are calculated, demonstrating that strong isotopic fractionation will occur as a function of wavelength. The calculations provide accurate, detailed insight into CO 2 photoabsorption and dissociation dynamics, and greatly extend knowledge of the temperature dependence of the cross-section to cover the range from 0 to 400 K that is useful for calculations of propagation of stellar light in planetary atmospheres. The model is also relevant for the interpretation of laboratory experiments on massindependent isotopic fractionation. Finally, the model shows that the mass-independent fractionation observed in a series of Hg lamp experiments is not a result of hyperfine interactions making predissociation of 17 O containing CO 2 more efficient.mass-independent fractionation | photodissociation dynamics | fine interaction | magnetic isotope effect | Mars C arbon dioxide (CO 2 ) is the main component of the atmospheres of Mars, Venus, and the Hadean Earth (1). Its photoabsorption screens solar UV light, determining altitude-dependent photolysis rates, and its concentrations and infrared absorptions make it a powerful greenhouse gas. CO 2 photodissociation is the basis of these atmospheres' photochemistry and is the primary source of carbon monoxide (CO) and O 2 . Although the initially high concentration of CO 2 during Earth's Hadean era decreased as carbonate rocks accumulated, CO 2 continued to be a prominent atmospheric gas, enhancing surface temperature and attenuating UV light, with a partial pressure >10 mbar in the Archean (2) and >1 mbar in the Proterozoic (3). Its influence on the radiative properties and chemical composition of Earth's atmosphere has continued to the present day; one example is that CO 2 photolysis is the main source of mesospheric CO (4). Variations in the abundances of naturally occurring stable isotopes, including reaction mechanisms exhibiting mass-independent fractionation, are central to efforts to interpret environmental records ranging from sedimentary rocks to oceanic carbonates to glacial ice (5). Thus, CO 2 photolysis is both directly and indirectly linked to isotopic variations found in the environment.The UV absorption band of CO 2 ð120 nm < ...

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Bent valence excited states of CO2

Cited by 71 publications

References 17 publications

The Carbon Dioxide Molecule and the Effects of Its Interaction with Electrophiles and Nucleophiles

The Carbon Dioxide Molecule and the Effects of Its Interaction with Electrophiles and Nucleophiles

Remarks on total and elastic cross sections for electron and positron scattering from CO2

Carbon dioxide photolysis from 150 to 210 nm: Singlet and triplet channel dynamics, UV-spectrum, and isotope effects

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