Concentration dependence of the spectroscopic and photochemical properties of atomic and molecular oxygen in argon matrices

Gudipati, Murthy S.; Schouren, Frank; Kalb, Martin; Wagner, Robert

doi:10.1016/s1386-1425(00)00366-8

Cited by 6 publications

(6 citation statements)

References 27 publications

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“…Its presence shows that electronically excited oxygen molecules are embedded in the interior of argon clusters. Moreover, this emission is not seen from O 2 dimers, 53,54 giving evidence that our clusters are doped with single molecules.…”

Section: A Coexpansion Experimentsmentioning

confidence: 74%

“…Van-der-Waals bonded O 2 dimers and oligomers decay predominantly via nonradiative channels upon photoexcitation in the relevant energy range ͑Ϸ12 eV͒. 53,54 This property is quite useful for optimizing the experimental conditions for single molecule doping. Another important property of oxygen is that photoexcited-free O 2 does not emit in the time frame of the present experiment.…”

Section: Spectroscopic Characterization Of Photoreactionsmentioning

confidence: 99%

“…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.…”

Section: A Coexpansion Experimentsmentioning

confidence: 99%

“…73 It is important to note that the ArO excimer emission is only possible if both dissociation products are well separated from each other, for instance in different Ar shells, because recombination of the O atom pair is highly efficient in the Ar matrix. 54 cage can recombine, relax into the AЈ 3 ⌬ u , ͑ Ј=0͒ state, and eventually fluoresce into several vibrational levels Љ of the…”

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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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: A Coexpansion Experimentsmentioning

confidence: 74%

Section: Spectroscopic Characterization Of Photoreactionsmentioning

confidence: 99%

Section: A Coexpansion Experimentsmentioning

confidence: 99%

Section: A Coexpansion Experimentsmentioning

confidence: 99%

See 2 more Smart Citations

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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“…Previous studies on the mobility and diffusion of O atoms in different inert gas matrices [5][6][7][8][9] have reported several phenomena that can influence matrix isolation interpretation. According to Fournier et al, 5,6 O( 3 P) atoms have high mobility, e.g., 40-50 Å migration in solid argon at 10 K over the course of a few minutes.…”

Section: Introductionmentioning

confidence: 99%

Water-Related Matrix Isolation Phenomena during NO₂ Photolysis in Argon Matrix

et al. 2004

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Photolysis (350-450 nm) of NO(2) molecules trapped in argon matrices at 10 K has been studied using Fourier transform infrared (FTIR) spectroscopy to examine the mobility of the photolysis products, O((3)P) and NO, and their subsequent reactions. The formation of N(2)O(5) and N(2)O(3) from reactions of these mobile species with immobilized NO(2) and N(2)O(4) is confirmed. Water molecules from the background gases in the vacuum have been found to be isolated in the argon matrix during deposition of diluted NO(2) in Ar. The entrapped water molecules along with some of their NO(2) adducts have been characterized. Exposure of the matrix to photons to photolyze NO() resulted in not only internal matrix reactions, but also an enhanced deposition of ice over the surface of the argon matrix. This is caused by photodesorption of water molecules from the walls of the matrix isolation chamber and their subsequent condensation on the matrix surface. This ice overlayer has been found to give a very significant dangling OH band and a substantial librational band in the FT-IR spectra, indicating substantial surface area and internal porosity, respectively. The potential of using photodesorbed water to establish high surface area ice interfaces with dangling OH groups for heterogeneous photoreaction studies is discussed.

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Chemistry in Water Ices: From Fundamentals to Planetary Applications

Gudipati

Cooper

2012

The Science of Solar System Ices

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Concentration dependence of the spectroscopic and photochemical properties of atomic and molecular oxygen in argon matrices

Cited by 6 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

Water-Related Matrix Isolation Phenomena during NO₂ Photolysis in Argon Matrix

Chemistry in Water Ices: From Fundamentals to Planetary Applications

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Concentration dependence of the spectroscopic and photochemical properties of atomic and molecular oxygen in argon matrices

Cited by 6 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

Water-Related Matrix Isolation Phenomena during NO2 Photolysis in Argon Matrix

Chemistry in Water Ices: From Fundamentals to Planetary Applications

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Product

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Water-Related Matrix Isolation Phenomena during NO₂ Photolysis in Argon Matrix