Photo-stationary state of UV pumped matrix isolated O2

Danilychev, A. V.; Apkarian, V. A.

doi:10.1016/0009-2614(95)01078-n

Cited by 11 publications

(8 citation statements)

References 27 publications

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“…Studies on O 2 in crystalline Ar showed increased probability for permanent dissociation at defect sites, whereas substitutionally isolated O 2 did not dissociate at excess energies ഛ2.5 eV. 3 The small embedded Ar clusters investigated in our work are likely to possess an amorphous structure and should therefore exhibit a large number of defect sites inherent to the formation process. This could explain to some extent the fact that the first 40-50 Ar atoms had almost no effect on the dissociation.…”

Section: -7mentioning

confidence: 58%

“…2 were assigned to the ArO transition 2 1 54 which is also known as the Herzberg III band. 68 The Herzberg III band is forbidden for free molecules by dipole-radiation selection rules and is therefore extremely weak, 3 however, in a matrix environment the Herzberg III band emission is known to be enhanced by several orders of magnitude and so can serve as a sensitive probe of local interactions and dynamics ͑see, e.g., Refs. 1-4 and references therein͒.…”

Section: A Coexpansion Experimentsmentioning

confidence: 99%

“…[1][2][3][4][5][6] The matrix atoms act like a cage and prevent the dissociation products breaking through the first solvation shell. As a consequence the dissociation of a molecule may be completely suppressed.…”

Section: Introductionmentioning

confidence: 99%

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Photochemical processes in doped argon-neon core-shell clusters: The effect of cage size on the dissociation of molecular oxygen

Laarmann

Wabnitz

Haeften

et al. 2008

The Journal of Chemical Physics

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The caging effect of the host environment on photochemical reactions of molecular oxygen is investigated using monochromatic synchrotron radiation and spectrally resolved fluorescence. Oxygen doped clusters are formed by coexpansion of argon and oxygen, by pickup of molecular oxygen or by multiple pickup of argon and oxygen by neon clusters. Sequential pickup provides radially ordered core-shell structures in which a central oxygen molecule is surrounded by argon layers of variable thickness inside large neon clusters. Pure argon and core-shell argon-neon clusters excited with ϳ12 eV monochromatic synchrotron radiation show strong fluorescence in the vacuum ultraviolet ͑vuv͒ spectral range. When the clusters are doped with O 2 , fluorescence in the visible ͑vis͒ spectral range is observed and the vuv radiation is found to be quenched. Energy-resolved vis fluorescence spectra show the 2 1 ⌺ + → 1 1 ⌺ + ͑ArO͑ 1 S͒ → ArO͑ 1 D͒͒ transition from argon oxide as well as the vibrational progression A Ј 3 ⌬ u ͑ Ј=0͒ → X 3 ⌺ g − ͑ Љ͒ of O 2 indicating that molecular oxygen dissociates and occasionally recombines depending on the experimental conditions. Both the emission from ArO and O 2 as well the vuv quenching by oxygen are found to depend on the excitation energy, providing evidence that the energy transfer from the photoexcited cluster to the embedded oxygen proceeds via the O 2 + ground state. The O 2 + decays via dissociative recombination and either reacts with Ar resulting in electronically excited ArO or it recombines to O 2 within the Ar cage. Variation of the Ar layer thickness in O 2 -Ar-Ne core-shell clusters shows that a stable cage is formed by two solvation layers.

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Section: -7mentioning

confidence: 58%

Section: A Coexpansion Experimentsmentioning

confidence: 99%

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Photochemical processes in doped argon-neon core-shell clusters: The effect of cage size on the dissociation of molecular oxygen

Laarmann

Wabnitz

Haeften

et al. 2008

The Journal of Chemical Physics

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“…Nowadays, many rovibronic bands in the Herzberg systems are well studied in gas phase, but information about condensed phase spectra, especially on the “Herzberg III” band system is rather confusing . Even the regular spin‐orbit multiplet splitting for the A ′ 3 Δ u state has been inferred from O 2 spectra in solid deuterium in contrast with the accepted scheme in the gas phase, which seems to be rather strange. In the present paper, we will model the influence of intermolecular interaction on the splitting of the A ′ 3 Δ u multiplet and enhancement of all Herzberg bands and oxygen atmospheric bands in water solvent.…”

Section: Introductionmentioning

confidence: 99%

Dioxygen spectra and bioactivation

Minaev

Murugan

Ågren

2013

Int J of Quantum Chemistry

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Intensities of spin-forbidden transitions in electronic absorption and emission spectra of molecular oxygen are analyzed in order to understand the key mechanisms of spinstates mixing induced by spin-orbit coupling (SOC) and the ways to overcome spin prohibition for various photophysical and biochemical processes. Multireference configuration interaction calculations with SOC account are used to generalize spin-selection rules for the oxygen atmospheric and Herzberg bands in free O 2 molecule and in collision complexes. Intensity enhancement of the atmosphericupon bimolecular collisions are compared with those for Herzberg III transitions A 0 3 D u / X 3 R À g . Electric quadrupole, dipole, and magnetic approximations are used for transition probability calculations. Intensity distribution in rotational lines is also considered. With this background, we propose some simple spin-selection rules for dioxygen activation in enzymatic reactions.

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“…Several investigations of spectra and reactions of dioxygen molecules and oxygen atoms have been made in solid argon, krypton and xenon, [8][9][10][11][12][13][14][15] and also dideuterium, 16,17 but little knowledge is available about these properties of O 2 in solid neon; the use of neon typically yields spectral lines for both vibrational and electronic transitions narrower and with smaller shifts of wavenumber from the gaseous phase than for other noble-gas dispersants, 18 and enables the observations of effects even qualitatively different from those in other matrix materials.…”

Section: Introductionmentioning

confidence: 99%

Photolysis of O₂ dispersed in solid neon with far-ultraviolet radiation

Chou

Peng

et al. 2018

Phys. Chem. Chem. Phys.

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Irradiation at 173 or 143 nm of samples of O or O in solid Ne near 4 K produced many new spectral lines in absorption and emission from the mid-infrared to the near-ultraviolet regions. The major product was ozone, O, that was identified with its mid-infrared and near-ultraviolet absorption lines. Oxygen atoms were formed on photolysis of O and stored in solid neon until the temperature of a sample was increased to 9 K, which enabled their migration and combination to form O and likely also O. O in five excited states and O in two excited states detected through the emission spectra indicate that complicated processes occurred in solid Ne after far-ultraviolet excitation. For the transition D → P of O, the lifetime was determined to be 5.87 ± 0.10 s; the lifetime of the upper state of an unidentified transition associated with an emission feature at 701.7 nm was determined to be 2.34 ± 0.07 s.

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Photo-stationary state of UV pumped matrix isolated O2

Cited by 11 publications

References 27 publications

Photochemical processes in doped argon-neon core-shell clusters: The effect of cage size on the dissociation of molecular oxygen

Photochemical processes in doped argon-neon core-shell clusters: The effect of cage size on the dissociation of molecular oxygen

Dioxygen spectra and bioactivation

Photolysis of O₂ dispersed in solid neon with far-ultraviolet radiation

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Photo-stationary state of UV pumped matrix isolated O2

Cited by 11 publications

References 27 publications

Photochemical processes in doped argon-neon core-shell clusters: The effect of cage size on the dissociation of molecular oxygen

Photochemical processes in doped argon-neon core-shell clusters: The effect of cage size on the dissociation of molecular oxygen

Dioxygen spectra and bioactivation

Photolysis of O2 dispersed in solid neon with far-ultraviolet radiation

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Product

Resources

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Photolysis of O₂ dispersed in solid neon with far-ultraviolet radiation