One-Photon Ionization of Liquid Water upon 193 nm Laser Irradiation

Iwata, Akyhiro; Nakashima, Nobuaki; Izawa, Yasukazu; Yamanaka, Chiyoe

doi:10.1246/cl.1993.1939

Cited by 12 publications

(14 citation statements)

References 7 publications

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“…The present study provides more precision at the lower excitation energies because multiple shots could be averaged. The one-photon quantum yield at 193 nm 25 that the "quantum yield of ionization was a few percent". We are also in agreement with the original report of Boyle et al, 1 who estimated a quantum yield on the order of 0.005 near the absorption edge (but who suggested that the threshold for ionization was 6.5 eV).…”

Section: Resultsmentioning

confidence: 99%

“…At 25°C, equivalent conductivites for F -and HSO 3 -ions are 54.7 and 50 Siemen cm 2 /mole, respectively. 22 These numbers were corrected for temperature (recorded during each measurement) by dividing by the ratio of viscosities η(t)/η (25). A similar assumption (conductivity proportional to viscosity) was made to correct the specific conductivities of these ions for heavy water.…”

Section: Methodsmentioning

confidence: 99%

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Photoionization Yield vs Energy in H₂O and D₂O

2000

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A simple conductivity jump method was used to measure the escaped solvated electron yield following twophoton excitation of water with Raman-shifted light from an amplified mode-locked Nd:YAG laser. Between 7.8 and 9.3 eV, the quantum efficiency for the escape yields changes from 1.9% to 22%, with an almost exponential dependence on the excitation energy. Quantum efficiency in D 2 O is smaller and resembles the H 2 O behavior at 0.35 eV lower energy. The quantum yield measured for one-photon excitation near the water absorption edge at 6.4 eV is a surprisingly large 1.3%. We propose that the mechanism for low energy photoionizaton of water is best described as a dissociative proton-coupled electron transfer to a preexisting trap.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Photoionization Yield vs Energy in H₂O and D₂O

2000

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“…[8][9][10][23][24][25] This is surprising since the ionization potential of the gas-phase molecule is much higher ͑12.6 eV͒. 26,27 Correcting the gasphase ionization threshold for the electronic polarization energy of liquid water and the minimum energy of the ''quasifree'' electron leads to a Born-Oppenheimer ionization threshold higher than 8.5 eV.…”

Section: Introductionmentioning

confidence: 99%

Two-photon dissociation and ionization of liquid water studied by femtosecond transient absorption spectroscopy

Thomsen¹,

Madsen²,

Keiding³

et al. 1999

The Journal of Chemical Physics

185

198

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Articles you may be interested inIonization and dissociation dynamics of vinyl bromide probed by femtosecond extreme ultraviolet transient absorption spectroscopy J. Chem. Phys. 140, 064311 (2014); 10.1063/1.4865128 Photodissociation of thioglycolic acid studied by femtosecond time-resolved transient absorption spectroscopyOne-color two-photon mass-analyzed threshold ionization spectroscopy of ethyl bromide through a dissociative intermediate stateThe photodissociation and photoionization of liquid water following two-photon absorption at 266 nm is studied in the spectral range from 213 to 1108 nm with subpicosecond time resolution. Probing in the UV enables the first direct simultaneous observation of the photoproducts e aq Ϫ , H aq , and OH aq . This makes it possible to follow the geminate recombination kinetics between the photoproducts and to determine the relative yields of the dissociation and ionization channels. The concentration of hydrated electrons deduced from the visible and near-infrared transient absorption measurements decays by 40%Ϯ2% within the first 90 ps due to recombination with OH aq and H 3 O ϩ . Analyzing our measurements of the hydrated electron concentration using the independent reaction time approximation results in the relative yields of 82%Ϯ3% and 18%Ϯ3% for recombination with OH aq and with H 3 O ϩ , respectively. This is in excellent agreement with the relative yield of 82%Ϯ10% for recombination with OH aq determined directly from our ultraviolet transient absorption measurements. The contribution of hydrated electrons from direct ionization is insignificant when liquid water is excited below 9.32 eV and the ionization is likely to occur via dissociation and proton transfer. The transient ultraviolet absorption data shows that if ionization exclusively occurs via dissociation, 65% of the produced H͑hot͒ atoms react with the surrounding solvent molecules to produce hydrated electrons. If proton transfer, on the other hand, is the only process responsible for the ionization, our measurements show that the ratio between dissociation and ionization is 55%. Geminate recombination of OH aq and H aq fragments following the photodissociation at 9.32 eV is not observed indicating that the translation energy of at least one of the fragments is sufficient to penetrate the water solvent cage. Finally, we have measured the two-photon absorption spectrum of liquid water from 110 to 160 nm, and the spectrum is in good agreement with our ab initio gas-phase calculations of the two-photon absorption cross sections for the transitions involved.

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“…The plots were fitted by the straight lines with slopes of 1.4 ( 0.2 and 3.2 ( 0.5 for ArF and KrF lasers, respectively. The slopes in Figure 2 larger than 1 and 2, which are expected for formation of a hydrated electron with ArF and KrF lasers, 13 suggested that the carboxylic group is formed not only by photoionization of water but also by a secondary photoreaction. 17 A possible mechanism for the present surface photoreaction is depicted in eqs 1-8: photoionization of water (1); capture of a hydrated electron by the fluoropolymer (2); elimination of a fluoride ion from the fluoropolymer radical anion (3 and 4); attack of the • OH radical on the radical site on the polymer (5 and 6); elimination of HF from alcohols giving a carboxylic or ketone group (7 and 8).…”

mentioning

confidence: 82%

“…12 The present result is almost in good accordance with the reported value of 1-2 µs. 13 PTFE has no absorption at >180 nm, whereas water has an onset of absorption around 190-200 nm. 14 Essentially, this will be the same for other fluoropolymers and excitation of water can be expected for the irradiation at 185 and 193 nm.…”

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confidence: 99%

Excimer Laser-Induced Surface Reaction of Fluoropolymers with Liquid Water

Ichinose¹,

Kawanishi²

1996

Macromolecules

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One-Photon Ionization of Liquid Water upon 193 nm Laser Irradiation

Abstract: Water was photoionized through a one-photon process upon 193 nm laser irradiation. The quantum yield of photoionization was a few percent. Multiphoton ionization was not observed in this work, up to the laser fluence of 1.6 J/cm2.

Cited by 12 publications

References 7 publications

Photoionization Yield vs Energy in H₂O and D₂O

Photoionization Yield vs Energy in H₂O and D₂O

Two-photon dissociation and ionization of liquid water studied by femtosecond transient absorption spectroscopy

Excimer Laser-Induced Surface Reaction of Fluoropolymers with Liquid Water

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One-Photon Ionization of Liquid Water upon 193 nm Laser Irradiation

Abstract: Water was photoionized through a one-photon process upon 193 nm laser irradiation. The quantum yield of photoionization was a few percent. Multiphoton ionization was not observed in this work, up to the laser fluence of 1.6 J/cm2.

Cited by 12 publications

References 7 publications

Photoionization Yield vs Energy in H2O and D2O

Photoionization Yield vs Energy in H2O and D2O

Two-photon dissociation and ionization of liquid water studied by femtosecond transient absorption spectroscopy

Excimer Laser-Induced Surface Reaction of Fluoropolymers with Liquid Water

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Photoionization Yield vs Energy in H₂O and D₂O

Photoionization Yield vs Energy in H₂O and D₂O