On the Photoabsorption Spectroscopy of Water

Bursulaya, Badry; Jeon, Jonggu; Yang, Chia‐Ning; Kim, Hyung J.

doi:10.1021/jp992582g

Cited by 45 publications

(38 citation statements)

References 40 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…8,18 The relatively weak two-photon transition probability to the Ã state may originate from the atomic oxygen s ← p character of the excitation, even though the two-photon molecular transition is not strictly symmetry forbidden. 40 We are currently study- ing the ionization and dissociation yields in this region in an effort to clarify the nature of the excited state created by two-photon absorption at 8.3 eV.…”

Section: Discussionmentioning

confidence: 99%

“…First, the character of the excited molecular electronic state rapidly changes as higher Rydberg-type orbitals are increasingly likely to be excited. The higher Rydberg orbitals are more diffuse 18,39,40 and, at least in the gas phase, are not directly dissociative. 38 Moreover, with the transitions to higher Rydberg-type states once again involving promotion from the 1b 1 molecular orbital, nonadiabatic coupling of the excited state to the lowest ionization continuum ͓corresponding to the ͑1b 1 ͒ −1 cationic core͔ improves dramatically because of the decreasing need for nuclear reorganization as the excitation energy approaches the ionization continuum.…”

Section: B Nature Of the Ionization Mechanism As A Function Of Energymentioning

confidence: 99%

See 1 more Smart Citation

Excitation-energy dependence of the mechanism for two-photon ionization of liquid H2O and D2O from 8.3to12.4eV

Elles

Jailaubekov

Crowell

et al. 2006

The Journal of Chemical Physics

119

192

View full text Add to dashboard Cite

Transient absorption measurements monitor the geminate recombination kinetics of solvated electrons following two-photon ionization of liquid water at several excitation energies in the range from 8.3 to 12.4 eV. Modeling the kinetics of the electron reveals its average ejection length from the hydronium ion and hydroxyl radical counterparts and thus provides insight into the ionization mechanism. The electron ejection length increases monotonically from roughly 0.9 nm at 8.3 eV to nearly 4 nm at 12.4 eV, with the increase taking place most rapidly above 9.5 eV. We connect our results with recent advances in the understanding of the electronic structure of liquid water and discuss the nature of the ionization mechanism as a function of excitation energy. The isotope dependence of the electron ejection length provides additional information about the ionization mechanism. The electron ejection length has a similar energy dependence for two-photon ionization of liquid D 2 O, but is consistently shorter than in H 2 O by about 0.3 nm across the wide range of excitation energies studied.

show abstract

Section: Discussionmentioning

confidence: 99%

Section: B Nature Of the Ionization Mechanism As A Function Of Energymentioning

confidence: 99%

Excitation-energy dependence of the mechanism for two-photon ionization of liquid H2O and D2O from 8.3to12.4eV

Elles

Jailaubekov

Crowell

et al. 2006

The Journal of Chemical Physics

119

192

View full text Add to dashboard Cite

show abstract

“…Water molecules located near voidlike trap sites will be able to absorb photons of lower energies and, at the same time, provide a favorable environment for electron solvation [32,46].…”

Section: B Amentioning

confidence: 99%

Wavelength dependence of nanosecond infrared laser-induced breakdown in water: Evidence for multiphoton initiation via an intermediate state

et al. 2015

View full text Add to dashboard Cite

Investigation of the wavelength dependence (725 -1025 nm) of the threshold for nanosecond optical breakdown in water revealed steps consistent with breakdown initiation by multiphoton ionization, with an initiation energy of about 6.6 eV. This value is considerably smaller than the autoionization threshold of about 9.5 eV, which can be regarded as band gap relevant for avalanche ionization. Breakdown initiation is likely to occur via excitation of a valence band electron into a solvated state, followed by rapid excitation into the conduction band. Theoretical analysis based on these assumptions suggests that the seed electron density required for initiating avalanche ionization drops from 2.5×10 15 cm -3 at 725 nm to 1.1×10 12 cm -3 at 1025 nm. These results demand changes of future breakdown modeling for water including the use of a larger band gap than previously employed, the introduction of an intermediate energy level for initiation, and consideration of the wavelength dependence of seed electron density.

show abstract

“…[32][33][34][35][36] Unfortunately, a clear and consistent theoretical description of the electronically excited states of liquid water is not yet available because accurate electronic structure calculations are extremely difficult for such strongly interacting molecules. [34][35][36][37][38][39][40][41] 2PA spectroscopy provides a new window on the electronic transitions of liquid water because the symmetry selection rules are different than for linear spectroscopy. Absolute 2PA cross sections have been reported at a limited number of discrete energies.…”

Section: Introductionmentioning

confidence: 99%

Electronic structure of liquid water from polarization-dependent two-photon absorption spectroscopy

Elles¹,

Rivera²,

Zhang³

et al. 2009

The Journal of Chemical Physics

106

View full text Add to dashboard Cite

Two-photon absorption ͑2PA͒ spectroscopy in the range from 7 to 10 eV provides new insight on the electronic structure of liquid water. Continuous 2PA spectra are obtained via the pump-probe technique, using broadband probe pulses to record the absorption at many wavelengths simultaneously. A preresonance enhancement of the absolute 2PA cross section is observed when the pump-photon energy increases from 4.6 to 6.2 eV. The absorption cross section also depends on the relative polarization of the pump and probe photons. The variation of the polarization ratio across the spectrum reveals a detailed picture of the 2PA and indicates that at least four different transitions play a role below 10 eV. Theoretical polarization ratios for the isolated molecule illustrate the value of the experimental polarization measurement in deciphering the 2PA spectrum and provide the framework for a simple simulation of the liquid spectrum. A more comprehensive model goes beyond the isolated molecule picture and connects the 2PA spectrum with previous one-photon absorption, photoelectron, and x-ray absorption spectroscopy measurements of liquid water. Previously unresolved, overlapping transitions are assigned for the first time. Finally, the electronic character of the vertical excited states is related to the energy-dependent ionization mechanism of liquid water.

show abstract

On the Photoabsorption Spectroscopy of Water

Abstract: The first photoabsorption band of water around 8 eV is studied with the molecular dynamics computer simulation technique under ambient and supercritical conditions.

Cited by 45 publications

References 40 publications

Excitation-energy dependence of the mechanism for two-photon ionization of liquid H2O and D2O from 8.3to12.4eV

Excitation-energy dependence of the mechanism for two-photon ionization of liquid H2O and D2O from 8.3to12.4eV

Wavelength dependence of nanosecond infrared laser-induced breakdown in water: Evidence for multiphoton initiation via an intermediate state

Electronic structure of liquid water from polarization-dependent two-photon absorption spectroscopy

Contact Info

Product

Resources

About