Spectroscopy of the transition state: Elementary reactions of the hydroxyl radical studied by photoelectron spectroscopy of O−(H2O) and H3O−2

Arnold, Don W.; Xu, Cangshan; Neumark, Daniel M.

doi:10.1063/1.469343

Cited by 62 publications

(50 citation statements)

References 75 publications

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“…On prolonged irradiation, its absorptions and those of H 2 O 2 decrease, and the OH absorption continues to grow. The gas-phase photoelectron spectrum of H 2 O • • • O − obtained by Arnold and co-workers 33 showed a band separation of 3629 cm −1 , consistent with the argonmatrix assignment. Photosensitive absorptions which correspond to those reported for H 2 O • • • O were not detected in the present study.…”

Section: B Products Of the Discharge Experimentssupporting

confidence: 80%

The infrared spectrum of HOOH+ trapped in solid neon

Thompson

Lugez

Jacox

2012

The Journal of Chemical Physics

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When a Ne:H(2)O(2) mixture is codeposited at 4.3 K with a beam of neon atoms that have been excited in a microwave discharge, three new, photosensitive absorptions appear which can be assigned to the three infrared-active vibrational fundamentals of trans-HOOH(+). When the Ne:H(2)O(2) deposition system is pretreated with the vapors of D(2)O, the product absorptions include new peaks which can be attributed to vibrational fundamentals of trans-HOOD(+) and trans-DOOD(+). Density functional calculations of the vibrational fundamentals of the three hydrogen peroxide cation isotopologues support the proposed assignments. Broad, photosensitive product absorptions also appear near the positions of vibrational transitions of O(3)(-), and may be contributed by a weakly bound complex of that species with H(2)O.

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Section: B Products Of the Discharge Experimentssupporting

confidence: 80%

The infrared spectrum of HOOH+ trapped in solid neon

Thompson

Lugez

Jacox

2012

The Journal of Chemical Physics

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“…16 The presence of hydrogen peroxide and water in the PEUU offers several pathways by which radicals can transfer rapidly into the PEUU from the surface. It is known that the hydroxyl radical transfers by reaction with water 17,18 :…”

Section: In Vitro Treatmentsmentioning

confidence: 99%

Role of oxygen in biodegradation of poly(etherurethane urea) elastomers

Schubert

Wiggins

Anderson

et al. 1997

J. Biomed. Mater. Res.

106

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It is generally accepted that biodegradation of poly(etheruethane urea) (PEUU) involves oxidation of the polyether segments on the surface where leukocytes are adhered. The influence of dissolved oxygen, which is known to control oxidation of polymers in more traditional environments, was explored in this study. Specimens treated in vitro with hydrogen peroxide-cobalt chloride for 12 days exhibited a brittle, degraded surface layer about 10 microm thick. Attenuated total reflectance-Fourier transform infrared spectroscopy of the surface revealed that the ether absorbance at 1110 cm(-1) gradually decreased with in vitro treatment time to 30% of its initial value after 12 days. In contrast, 6 days in vitro followed by 6 days in air produced a decrease to 12% of the initial volume. Therefore, removing a specimen from the in vitro solution after 6 days and exposing it to air for the remainder of the 12 days actually resulted in more oxidation than leaving it in the in vitro solution for the entire 12 days. These results suggest that PEUU degrades by an autooxidation mechanism sustained by oxygen. By successfully modeling the depth of the surface degraded layer with a diffusion-reaction model, it was demonstrated that PEUU biodegradation is controlled by diffusion of oxygen into the polymer.

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“…As a consequence, the low-frequency vibrational modes are split due to tunnelling. The threshold for ground state H 3 O 1.18 eV 21 and neglecting possible bound states in the neutral OH-water complex. We have therefore measured the nearthreshold photodetachment cross sections at a fixed photon energy of 24410 ± 20 cm 1 for trap temperatures of 30, 85, 130, 180 and 205 K respectively, using the tomographic procedure outlined in the methods section.…”

Section: Near Threshold Photodetachment Of Hmentioning

confidence: 99%

Internal state thermometry of cold trapped molecular anions

Otto

Zastrow

Best

et al. 2013

Phys. Chem. Chem. Phys.

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− 2 anions has been performed in a cryogenic 22-pole radiofrequency multipole trap. Measurements of the detachment cross section as a function of laser frequency near threshold have been analysed. Using this bound-free spectroscopy approach we could demonstrate rotational and vibrational cooling of the trapped anions by the buffer gas in the multipole trap. Below 50 K the OH − rotational temperature shows deviations from the buffer gas temperature, and possible causes for this are discussed. For H 3 O − 2 vibrational cooling of the lowest vibrational quantum states into the vibrational ground state is observed. Its photodetachment cross section near threshold is modelled with a Franck-Condon model, with a detachment threshold that is lower, but still in agreement with the expected threshold for this system.

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Spectroscopy of the transition state: Elementary reactions of the hydroxyl radical studied by photoelectron spectroscopy of O−(H2O) and H3O−2

Cited by 62 publications

References 75 publications

The infrared spectrum of HOOH+ trapped in solid neon

The infrared spectrum of HOOH+ trapped in solid neon

Role of oxygen in biodegradation of poly(etherurethane urea) elastomers

Internal state thermometry of cold trapped molecular anions

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