Ab initio study of spin-forbidden unimolecular decomposition of carbon dioxide

Hwang, Der-Yan; Mebel, Alexander M.

doi:10.1016/s0301-0104(00)00108-7

Cited by 43 publications

(38 citation statements)

References 27 publications

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“…The central donutshaped ring structures of the C( 3 P 2 ) ion images originate from the formation of C( Fig. 1), which is predicted to have no potential energy barrier by the theoretical calculations (7,8).…”

Section: Research | Reportsmentioning

confidence: 94%

“…Decades of experimental and theoretical photochemical studies of CO 2 have been focused on the detection and understanding of the CO + O photoproduct channels. Recent theoretical calculations (7,8) suggest that an exit channel to produce C + O 2 upon VUV photoexcitation of the CO 2 molecule is possible. The ab initio calculation (7) has provided the dissociation pathway on the ground-state singlet potential energy surface of CO 2 , leading to the formation of the C(…”

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confidence: 99%

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Evidence for direct molecular oxygen production in CO ₂ photodissociation

Lü

Chang

Yin

et al. 2014

Science

120

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Photodissociation of carbon dioxide (CO2) has long been assumed to proceed exclusively to carbon monoxide (CO) and oxygen atom (O) primary products. However, recent theoretical calculations suggested that an exit channel to produce C + O2 should also be energetically accessible. Here we report the direct experimental evidence for the C + O2 channel in CO2 photodissociation near the energetic threshold of the C(3P) + O2(X3Σg–) channel with a yield of 5 ± 2% using vacuum ultraviolet laser pump-probe spectroscopy and velocity-map imaging detection of the C(3PJ) product between 101.5 and 107.2 nanometers. Our results may have implications for nonbiological oxygen production in CO2-heavy atmospheres.

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Section: Research | Reportsmentioning

confidence: 94%

mentioning

confidence: 99%

Evidence for direct molecular oxygen production in CO ₂ photodissociation

Lü

Chang

Yin

et al. 2014

Science

120

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“…This minimum is located 6.03 eV above the global one, again in good agreement with the previous findings. 23,24 The fundamental excitations in the OCO well, calculated for N CO2 = 0, are ω a = 680 cm −1 , ω b = 720 cm −1 , and ω s = 1550 cm −1 . For the linear COO, the calculated CO and OO bond lengths are identical to the ones given in Ref.…”

Section: Electronic Structure Calculationsmentioning

confidence: 99%

Photodissociation of carbon dioxide in singlet valence electronic states. I. Six multiply intersecting ab initio potential energy surfaces

Grebenshchikov

2013

The Journal of Chemical Physics

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The global potential energy surfaces of the first six singlet electronic states of CO2, 1-3(1)A', and 1-3(1)A" are constructed using high level ab initio calculations. In linear molecule, they correspond to X̃(1)Σg (+), 1(1)Δu, 1(1)Σu (-), and 1(1)Πg. The calculations accurately reproduce the known benchmarks for all states and establish missing benchmarks for future calculations. The calculated states strongly interact at avoided crossings and true intersections, both conical and glancing. Near degeneracies can be found for each pair of six states and many intersections involve more than two states. In particular, a fivefold intersection dominates the Franck-Condon zone for the ultraviolet excitation from the ground electronic state. The seam of this intersection traces out a closed loop. All states are diabatized, and a diabatic 5 × 5 potential matrix is constructed, which can be used in quantum mechanical calculations of the absorption spectrum of the five excited singlet valence states.

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“…In the past, it was observed that dissociation of CO 2 via absorption of photons leads to carbon monoxide (CO) and oxygen atoms (O) [3]. However, theoretical simulations suggested the possibility of generating O 2 through the dissociation of a CO 2 molecule [4]. A recent experiment showed the evidence of O 2 formation from CO 2 molecules after UV excitation through the detection of C + [5].…”

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confidence: 99%

Molecular oxygen observed by direct photoproduction from carbon dioxide

et al. 2017

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Oxygen (O2 ) is one of the most important elements required to sustain life. The concentration of O2 on Earth has been accumulated over millions of years and has a direct connection with that of CO2 . Further, CO2 plays an important role in many other planetary atmospheres. Therefore, molecular reactions involving CO2 are critical for studying the atmospheres of such planets. Existing studies on the dissociation of CO2 are exclusively focused on the C-O bond breakage. Here we report first experiments on the direct observation of molecular Oxygen formation from CO2 in strong laser fields with a reaction microscope. Our accompanying simulations suggest that CO2 molecules may undergo bending motion during and after strong-field ionization which supports the molecular Oxygen formation process. The observation of the molecular Oxygen formation from CO2 may trigger further experimental and theoretical studies on such processes with laser pulses, and provide hints in studies of the O2 and O + 2 abundance in CO2 -dominated planetary atmospheres.PACS numbers: 33.80. Gj, 42.50.Hz, O 2 production is one of the most important processes for the biosphere of the Earth.Oxygen molecules are mainly generated via the photosynthesis by green plants and algae from carbon dioxide and water:. CO 2 is not only important for the atmosphere on Earth, it is also the dominant compound of the atmosphere on other planets, such as Mars and Venus. One of the most crucial tasks for the quest to establish a human settlement on Mars is the production of O 2 [2]. Because more than 95% of the atmosphere on Mars is CO 2 , it will be extremely helpful if O 2 can be produced directly from CO 2 . In the past, it was observed that dissociation of CO 2 via absorption of photons leads to carbon monoxide (CO) and oxygen atoms (O) [3]. However, theoretical simulations suggested the possibility of generating O 2 through the dissociation of a CO 2 molecule [4]. A recent experiment showed the evidence of O 2 formation from CO 2 molecules after UV excitation through the detection of C + [5]. So far, O 2 formation from CO 2 has not been directly observed.In the past decade, intense ultrashort laser pulses have been successfully applied to trigger and control molecular reactions such as dissociation and isomerization [6][7][8][9][10][11][12][13][14][15]. When a molecule interacts with a strong laser field, electrons from outer molecular orbitals can be excited or removed through tunneling or over-the-barrier ionization which may prepare the molecule in an excited state or a state with a certain charge. As a consequence, the excited or ionized molecule may undergo severe geometrical reconfiguration and may also break into several fragments or form new chemical bonds. Because of the importance of CO 2 in many research disciplines, strongfield induced reactions of CO 2 have been experimentally studied with ultrashort lasers by several research groups.However, these studies mainly focused on the topic of ionization and dissociation [16]. In this paper, for the first...

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Ab initio study of spin-forbidden unimolecular decomposition of carbon dioxide

Cited by 43 publications

References 27 publications

Evidence for direct molecular oxygen production in CO ₂ photodissociation

Evidence for direct molecular oxygen production in CO ₂ photodissociation

Photodissociation of carbon dioxide in singlet valence electronic states. I. Six multiply intersecting ab initio potential energy surfaces

Molecular oxygen observed by direct photoproduction from carbon dioxide

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Ab initio study of spin-forbidden unimolecular decomposition of carbon dioxide

Cited by 43 publications

References 27 publications

Evidence for direct molecular oxygen production in CO 2 photodissociation

Evidence for direct molecular oxygen production in CO 2 photodissociation

Photodissociation of carbon dioxide in singlet valence electronic states. I. Six multiply intersecting ab initio potential energy surfaces

Molecular oxygen observed by direct photoproduction from carbon dioxide

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Evidence for direct molecular oxygen production in CO ₂ photodissociation

Evidence for direct molecular oxygen production in CO ₂ photodissociation